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McGraw-Hill Series in Water Resources

and Environmental Engineering ENVIRONMENTAL

Rolf Eliassen, Paul H. King, and Ray K. Linsley
Consulting Editors
Bailey and Ollis: Biochemical Engineering Fundamentals
Bishop : Marine Pollution and Its Control
Biswas: Modelsfor Water Quality Managemeni
Bockrath : Environmental Law for Engineers. Scientisls, and Managers
Bouwer : Gro!{ndwater Hydrology
Canter: En vironmental Impact Assessment Howard S. Peavy
Chanlett: Environmental Protection
Professor of Civil Engineering
Gaudy and Gaudy: Micr obiologyfor Environmental Scientists and Engineers
Montana Scate University
Haimes: Hierarchical Analysis of Water Resources Systems: Modelling and
Optimization of L arge-Scale Systems
Hall and Dracup: Water Resources Systems Engineering
Donald R. Rowe
Linsley and Franzini: Water Resources Engineering Professor of Civil Engineering
Linsley, Kohler , and P aulhus : Hydrology for Engineers King Saud UniverSity
Metcalf & Eddy, Inc .: Wastewater Engineering.' Collec tion and Pumping of Wast ewater Saudi Arabia
Metcalf & Eddy, Inc.: Wastewater Engineering. Trealment, Disposal. Reuse
Peavy, Rowe, and Tchobanoglous : Environmental Engineering George Tchobanoglous
Rich : Low-Maintenance, Mechanically-Simple Wastewater Treatment Systems Professor of Civil Engineering
Sawyer and McCarty : Chemistry for Environmental Engineering Univers ity of California, Davis
Steel and McGhee : Water Supply and Sewerage
Tchobanoglous, Theisen, and Eliassen: Solid Wastes, Engineering Principles and
Management Issues

McGraw-Hill Book Company

New York St. Louis San Francisco Auckland Bogota H amburg
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Exclusive rights by McGraw-Hili Book Co., Singapore

for manufacture and export. This book cannot be re-exported
from the country to which it is consigned by McGraw- HilI.

40 39 38 37 36 35 34 33 32 31
15 14 13 12 11
Preface XI/ I

Copyright 1985 by McGraw-Hili, Inc.

All rights reserved. No part of this publication m ay be Intrnclu Cli on
reproduced or distributed in any form o r by any means ,
I- I T he Em'i ron lll c nt
or stored in a data base or a retrieval system, without
1-2 T he Im[lact 0 1' Il ulllam upo n th e Enviro nm e nt 2
th e prior written permissio n of the publisher.
1-3 Th e Im[lact o r th e En\ironm e nt upo n Hum an s 4
1-4 Impro \'c me nt of Envi ro nme nt al Qu a li ty 6
This book was set in Times Roman.
The editors were Kiran Ve rma and David A. Damstra. 1- 5 T he Ro lc of th e Environ ment a l Eng in ee r 7
The production supervi so r was Leroy A. Youn g. ReI-e rcnces ~

Part 1 Water
...Libra./},.()f.c;:()1"!9.ress .Ca~loging in Publication Data
2 Water Qu a lit y : Definiti ons, Charaderistics;
Peavy, Howard S. and Perspect ives II
Environmental engin ee ring .
2-1 T he Hyd raul ic Cycle a nd Water Qual ity 12
(MC Graw-Hili se ries in water resources and environ- PHY S IC A L W AT E R-QUA LITY PA RA M ETER S 14
mental engineering) 2-2 Suspend ed S,1 Iid , 15
Includes bibliographi ca l references and indexes.
2-3 T urbidit y 17
1. Environmental engineering . I. Rowe, Donald R.
2-4 Co lo r 18
II. Tchobanoglou s, George. III. Title. IV. Seri es.
2-5 Ta ste and Odo l 20
TD145.P43 1985 628 84-3854
2-6 Tempera ture 22
ISBN 0-07-0491 34-8
When ordering this title use ISBN 0-07 -1 00231-6 2- 7 Chemi stn of S" luti o ns ' 23
2-8 T o ta l Dissoh cd So lid , 28
2-9 Alkali nit\ 31
2 10 Hard ness
:2-1 1Fl uo ri de 3(,
2 12 Me tal s 37
2-1 ] Orga nH.:" 38
2- 14 Nutllc nh -1 4
Printed in Singapore

46 4-8 Filtration 165

' 4-9 Disinfecti o n ,. t
2-15 Pathogens 47
2-16 Pathogen Indicators
54 ~ 4-10 Dissolved Solids Removal 190
DiSCUSSIOn Topics and Problems ~ .
2-17 In-Stream Standards 54 '104 .
2-18 Potable Water Standards 55
2-19 Wastewater Effluent Standards 56 5 Engineered Systems for Wastewater Treatment
Discussion Topics and Problem s 57
and Disposal 207
References . 62
5-1 Wastewater Characteristics 208
3 Water Purification Processes in Natural Systems 63 211
5-2 Effluent Standards
64 5- 3 Terminology in Wastewater Treatment 212
3-1 Dilution 64 PRIMARY TREATMENT 2Pl
3-2 Sedimentation and Resuspension 65 5-4 Screening 217
3-3 Filtration 66 5-5 Comminuting 220
3-4 Gas Transfer 66 5-6 Grit Removal 221
3-5 Heat Transfer 71 5-7 Flow Measurement 224
73 5-8 Primary Sedimentation 224
3-6 Chemical Conversions
BIOCHEMICAL PROCESSES 74 5-9 Growth and Food Utilization 230
5-10 Suspended-Culture Systems 234
3-7 Metabolic Processes 75
511 Activated Sludge 234
3-8 Microorganisms in Natural Wat er Syst em s 79
5-12 Ponds and Lagoons 248
RESPONSE OF STREM...lS TO BIODEGRADABLE. 513 Attached-Culture Systems 255
ORGANIC WASTE 83 5-14 Secondary Clarification 268
. ~cl.~. P.i~iflf~c.t.iml.of Effiw:ots ...................................................... . 277
3-9 Dissolved-Oxygen Balance . . . . . . . .... ?;l. _ ...... . .. . . . ..... .
3-10 Dissolved-Oxygen Model
3-.11 Organic Discharge and Stream Ecology 94 279
5-16 Sludge Characteristics
ENGINEERED SYSTEMS 5-18 Sludge Digestion 285
5-19 Sludge Disposal 292
3-12 Physical Processes
3- i3 Chemical Processes
3-14 Biological Processes 5-20 Nutrient Removal 295:'
Di scu ss ion T o pics and Problem s 5-21 Solids Removal 301
Refere.nces 302
4 Engineered Systems for Water Purification 104 5-22 Wastewater Di sposal 303
5-23 Wastewater Reuse 306
4-1 Historical Overview of Water Treatment 105
Discussion Topics and Problems .314
4-2 Water-Treatment Processes 107
THEORY AND .APPLICATION 109 6 Environmental Engineering Hydraulics Design 324
110 324
11 3
4-4 So lid s Se paration \j) \ - \IJ) In 6- 1 Method s of Distributing Water 324
4-5 Settlin g Operatioll s 326
6-2 Di stribut io n Rese rvoirs
~ S'\ - \G1
4 -(, C llagulati o ll 1.1 1
~ 331
151 6-3 Di stribution Sys tem s
4-7 So ft enin g
333 7-9 Ox ides of N itrogen
6-4 Distribution System Components 461
335 7-10 Phot oc hemi cal Oxidant s
6-5 Capacity and Pressure Requirements 463
337 7-1 1 Ind oo r Air Po lluti o n
<6-6 Design of Distribution Systems 464
6~7 Hydraulic Analysis o f Di stribution Systems
346 Di sc uss io n T o pi cs a nd Pro blems 477
6-8 Cross-Connections in Di stribution System s 347 480
6-9 Constructi o n of W a ter Di stribution Systems Refe rences
6-10 Pumping R equired for Water Supply System s
WASTEWATER CO LLECTION Meteoro logy and Natural Purificati o n Processes 483
349 8
6-11 Types of Co llection Systems E L EME N T AL PR OPERT IES Of THE ATMOSP H ERE 483
-: 349
< 6-12 Types of Sewers 484
353 8- 1 Sca les of i\ lotill n
6-13 Collection System Appurten a nces 486
Basic Consideration s in the Design o f Sewers 354 go: Heat
6-14 491
360 i)-} Pressure
6-15 Design of Sanitary Sewers 493
Preparation of Contact Drawings and Specifica ti ons 369 8-4 Wlncl
6-16 495
371 8-5 MOisture
6-17 Construction of Sewe rs 495
37 1 8-6 Rcla tive H umidit y
6-18 Maintenan ce of Sewers
37 1
6-19 Design of Storm wa ter Sewers IN FLUE N CE OF i\ I LTEOROLOG IC AL PHENOMENA ON
372 495
372 496
6-20 Pumps 8-7 La pse Rat es and DI '> persio n
375 498
6-21 Pump Drive Unit s 8-8 Press ure Sys te ms and Di spe rsio n
378 498
6-22 Pump Application Terminology and Usage 8-9 Wind s and Di sper sio n
384 499
6-23 Pump Operating C haracte ristics and C urves 8-1 0 M OiS ture and Di spe rsio n
3')0 499
6-24 Analysis of Pump System s 8-11 Mod el ing
6-25 Pump Stations fo r Water and Wa stewater EFFECTS or A IR POLLUT IO N ON METEOROLOGICAL


8- 12 Change s o n the Mesoscale and Microscale
__ . __~ : 13__ ~~b 'Hlge.s _0.11_the_ M aC.fQseal e
6-26 Treatment Plant Desi gn ,--399, 510
6-27 Preparation of Hydraulic FFOfiks< <" <<" < <." " <" 0<" <--" , -- -. . -.. - - - - - - . . - Di sc uss io n T o pics a nd Proble ms
5 12
406 References
Discussion Topics and Problems
9 Engineered Sys tem s for Air Pollution Control 514
5 14
Part 2 . Air 9-1 Atm osphe ric Clea nsing Pr ocesses
9-2 Approa ches to C o ntaminant Cont ro l

-""""' '7 Air Quality : Definitions, Characteristics, and CON TR OL DEVICES rOR PARTICULATE CONTAM INA NTS 5 18
Perspectives 9-3 Gra vitati o nal Sel1! ing Ch a mbe rs 520
AIR POLLUTION -PAST , PRESENT , AND FUTURE 41 8 9-4 Ce ntrifu gal Co llec t () ,~S 523
9-5 528
418 Wc t Colkctnr,
7-1 Historical Overvie\>.' 53 3
420 '-)- (, Fa hr ic F ilt e r, ( Bag lHlllse Filt e rs)
'""""' 7-2 Global Impli ca ti o ns of A ir P o lluti on 536
424 9- 7 Elec tr os tat ic Prcc ipi Llt () fS (ESP) '
7-3 Units of Measurem ent
~. 7-4 Sources of poJlutan ts
429 540
431 9-9 ,\ OSor ptll)Jl
7-5 Particul a tes 557
44 2 ,-) 10 C o nli cns"tloll
7-6 H ydroca rbons 559
44 5 9- 11 ( 'omo u'>1lt)n
7-7 Carbon Monoxide 56J
449 l) _ I ~ , \utt.lllIl1 t l\r t:!l lh~H ) !l ( '~)flt r ol
7-8 Oxides o f Sulfur


11-10 Det ermination of Vehic le and Labor Requirements
607 ~'
Discuss io n Topics and Pro blems 565 615
II-II Collection Routes ~
Refe re nces 567
Part 3 Solid Waste
11-12 Transfer Station s
11-13 Location of Tra nsfe r Stations
11-14 Transfe r Means and Method s
622 ...t
10 Solid Waste: Definitions, Characteristics, and Mechan ical Volume Reducti o n 627

Perspectives 573 627
11 -16 Thermal Volume Reducti o n
TYPES OF SOLID WASTES 573 11.-17 Manual Co mpo nent Separa ti o n

10-1 Municipal Wastes 574
574 Landfi ll ing with Sol id Waste s 628
10-2 Indu strial Wastes 11-18
575 Design and Operation of La ndfill s 638
10-3 Hazard o us Wastes 11-19
Landfa rming 646
Deep-Well Injection 647
575 11-21
10-4 Sources o f Municipal Wa stes 648
Discuss ion Topics and Pro blems
10-5 Sources o f Hazardou s Was tes 576 652
10-6 Ph ys ical C omposition 576
10- 7 Chemical Co mpositi o n 582
10-8 Chan ges in Compositi o n 588 . 12 Engineered Systems for Resource and
Energy Recovery
10-9 Materials Flow in Societ y 588 653
10-10 Reduction in Raw Mat e ri a ls Usage 589
10-11 Reducti o n in Solid-Was te Qu a ntit ies 590 12- i Mechanical Size Alterati o n
Mechanical Component Separation
10-12 Reuse of So lid-Waste Mat e rial s 590 12-2 656-- ..
591 12-3 Ma gne tic and Electro mec ha nical Separa tio n
10-13 .. I'\TY .... 657
10-14 En e rgy Recovery 592 12-4 Drying and Dewatering
Day-to-Day Solid- Wa ste Managem ent 592 MA TERIALS-RECOVER Y SYSTEMS 657
Discuss io n Topics and Pro blems 592 657
12-5 Materials Specifications
Refere nce s 593 657
12-6 Processing and Recovery Sy"stems
)2-7 System Design a~d Layo ut
11 Engineered Systems for Solid-Waste Management 594 RECOVERY OF BIOLOGICAL CONVERSION PRODUCTS
II-I Functional Elements 594 12-8 Composting (Aerobic Conve rsion)
17.-9 Ana erobic Digestion
11-2 T ypi ca l G e neration Rates 595
11-3 Estimat io n o f Solid-Waste Qu a ntit ies 598 12-10 C o mbustion of Waste Mat erials
11-4 Fact o rs Tha t Affect G e nera ti o n Rat cs 598 12-11 Incin eration with Hea t Recove ry
12-12 Use of Refuse-Deri ved Fuel s (RDF)
12- 13 Ga sification
11 -5 On -S it e Handlin g 599 672
12- 14 Pyro lys is
11 -6 On-S it e Sto rage 599 672
11 -7 On -S it e Pr ocess in g of So lid Was tes 601 673
601 12- I 5 En ergy -Reco ve ry Systems
12- 16 Efficiency Fact or s 675
11 -8 Co ll ec ti o n Services 601
12- 17 Deterrninati on of t .ner g} Output and EtJi cicn cy
11 -9 T ypes o f Co llec ti o ll Sys tcm, 1i05


Discussion Topics and Problems 677
References 677

A Quantities and Units 679
B Conversion Factors 683
C Properties of Wat e r and Air 693
D Water Quality Standards 696

Indexes II
Name Index
Subject Index '

Eng inee rs and scientists from a n umber of re la ted di sci plin es ha ve been in vo lved
in the d evelopmc nt of an academic ba sis for th e und e rs tanding and management
of the envi ronment. Th e ' management of water qu a lit y has been dealt with in
mi crob io logy and s<Jn ita ry engi nee rin g courses; a ir po lluti o n pro blem s have been
---. covered in c hemica l and / o r mechanical eng in ee ring co urses; an d the management
of so lid waste, lo ng neglected by acad e m ic ian s. ha s bee n chiefly th e purvey of tho se
di rec tl y rcsponsible for hllu lin g and disposlli o pe rati o ns.
During th e la s t 10 to 13 ye ar s, sc h oo ls of e ng ine e ring ha ve made considerable
progress towa rd b rin gi ng the principles drawn from m any re lated acad emic
disciplines to ge th e r a nd unifyin g th em und e r the titl e en vironmen tal eng in ee rilll).
Not s urpri si ngly. texts .in .tbis re lative ly. new. subject. ar.ea. have d ev<!lo ped a long
cla ss ical , se paratist lines. Thus, there have been a number of texts featuring In-
depth treatment of one spec ific a rea (ie .. wate r , air , so lid waste) and few text s
attempting, to trea t the s ubjec t 01' e n vironme n ta l engineering as a whol e ,
The purpose of Elll'ironmental Enyineerinq is to brin g together and integrate
in a s in g le text the morc gC ntT ti suhJect matt e r of th e three principal areas of
.envirolJmental engince rin g -- water . ai r. a nd so lid-was te management. And, as
---. .Char. 1 indicat es, thi s int egra ti on goes he yo nd binding three text s in a sin g le cover.
Enl'irolltll('/I/(II Enqill('erilllj introduces a uniqu e approach to the ove ra ll
concep t o f e n viro nm e ntal enginee rin g, an ap proac h that e mpha sizes th e re la ti o n-
ship belll/een the princlr les observed in natural purification processes a n d those
employeed in eng in ecred p rocesses. First. th e ph ys ical , c he mi ca l, m a th e matical.
and biological principles of defining. quan tify in g, ane! measuring enviro nme n ta l
~'. quality a rc desCribed. Next. the processrs by which n a ture assimilates waste
material are discusscd and tlicnatul'al p ur ifica ti on rrocesses that form th e ba~cs
of engi neered systems a re deta iled Finally, th e e ng ineer ing principles and p ra ctices
involved In the design and operatil)n of conven ti ona l envi ronmen tal engineering
wor ks arc C()\'ercd at len)!t ll.

xiv PREFAn

The breadth and depth of th e matenal in thi s book precludes complete ENVIRONMENTAL ENGINEERING
coverage in a one-se m ster or o ne-qu a rte r course. H owever, the a rran gement of
the material lends itself to seve ral d iffe rent course format s.

I. For introdu c to r y e nginee ring courses at the sopho m ore or junior \i.:vel , C haps.
1.2,3 .7,8 . and 10 provide a n overv iew of the principles involved in e nviro n-
menta l en gi neerin g sys tem s. These chapters assume a basic knowledge of

c hem is try. biology, ph ys ics, and mathe matics . However , becau se m a n y
eng in eeri ng cu rri cu la co ntain few chemi st ry an d even fewer bi o logy or micro-
biology co urses . th e chapters review th ese subj ec ts in detail. The introd ucto r y
sec ti o ns of Chaps. 4. S. 9, II , and 12 may be utili zed to add relevance to th e
th eo ret ica l di sc uss ion s. A course following thi s format w ill satisfy ABET
requirements for e ngin ee ring scie nce.
2. If th e hrst a ppr oach is used fo r an introductory co urse. th e remainin g chapters
(4.5 ,6.9, II , and 12) ca n be used as a follow-up co urse in env ironmen tal
engineer in g design . Thi s co urse sho uld be res trict ed to e ng ineering s tud e nt s at
th e juni or or se ni o r leve l who ha ve co mpl eted ba s ic fluid m ec hani cs. Such a
co ur se would meet ABET' s e nginee rin g design criteria.
3. A m ore cla ss ical app roac h would be to use the first six c hapt ers as a text for
a o ne-se meste r or o ne -quart er co urse in water and wastewater engineering. A
second o ne-se mester/ qu a rt er course o n air-pollution control and so lid-was te
management would use Chaps. 7 thro ugh 12. D es igned fo r junio r- or se ni o r-
leve l e nginee rin g st ud e nt s that have co mpl e ted basic tluid mechanics, these
tw o ' co urses wi ll m ee t ABET criteria for e ngin eer in g design and scie nce, o r a n
approximate o ne to o ne ratio .
4. C hapte rs 1,2.3,7.8, and 10 can a lso bc lI sed for a companion course in en -
vironmental sc ience for nonen ginee rin g s tudent s , prov ided allowance is made
.. forthe iimited mar-hema ti ta lbackgrou n'd 6fthc' itlldenis: ' .

Whateve r the a pproac h used , th e text sho uld leave stud e nt s with a c lear
und erstanding o f th e prin c ipl es of all three o f th e maj o r areas o f envir omen tal
e n ginee rin g. U se r co mm e nt s a nd sugges ti ons conce rnin g the effec ti veness of this
approach would be g reatly appreciated .
The a uthors w is h to ac kn ow ledge til e fac t th at devel op ment and publication '.:
of Environmental El7,1jin eeriny wo uld not ha ve been possibl e wi th o ut th e he lp and
in spirati on o f o ur former pro fe sso rs, th e c ha lle nge and mot ivation o f our stud en ts ,
the assistance and e ncoura geme nt o f ou r co lleag ues, the patience a nd forebearance
of o ur edit o rs, and th e SUpP Grt and und e rstandin g of ou r familie s.

HOI1'ord S. Peon:
Donald R . R owe'
C eorql' T chohal/oglous


Environmental eng ineering ha s been defined as th e bran c h of eng ineering th a t is

co nce rn ed with protecting the en viron me nt fr o m th e p o tentiall y d e leterious
effec ts of human act ivit y, pro tecting human popu la tion s fr o m th e effects of a dverse
env iro nm ental factors, a nd improv in g e n viron m ent a l .q u a lit y for human health
a nd we ll -being. [1-2J
As th e above definiti o n im p lies, hum a ns interact w ith th ei r enviro nm e nt -
so metimes adve rsely imp acting the environmen t and some times bei ng adve rse ly
imp acted by p o llut ants in the env ironment. An unders tandin g o f the n a tu re o f
the enviro nm ent and of hum a n interaction w ith it is a neces ' ary prerequis ite to
unders tanding th e work o f the env iro nm enta l e ngi neer.


Simply stated, the e n vironmen t can be defined as one's surro undings. In terms of
the env iro nmental e ngineer's invo lvement , howeve r, a m ore sp ecific definition is
needed. To th e envi ronmental engineer. the word environment ma y ta k.e o n g loba l
ciimen s io ns. may refer to a very loca li zed area in which a sp ec ific problem must be
ad dr essed, o r may, in th e case of co nt ai ned en viron ments, refer to a sm a ll vo lume
o r liquid. gaseo ll s. or so lid materials w ithin a treatment plan t react o r.
The g loba l env ironment co nsist s of the atmosph ere, th e hydTosphere, and
the lithosph e re in w hi c h the life-s ustainin g resources of th e ea rth are co nt ained.
The atIJlOspi1l'rc.;t mixture of gases exte ndin g o utward fr om t~e s urface of th e ea rt h.
cvo lved from e lemeo ts o f th e ear th that were gas ified d urin g it s fo rmati o n a n d
metamorphos is . Th e hydrosphere consists o f th e oceans, th e lakes and strea ms.
a nd the s ha ll ow gro und wa ter bod ies that int erflo w wi th th e surface water. The
lithosphere is th e so il mant Ie th at wraps th e co re of th e ea rth .
The hiosphcre. a thin she ll that encaps ulates th e ea rth. is made lip o r the
;Itmosphc re a nd iltlwsphere adjacent to the surface o f the earth. toge th er \\it h th e

from a campfire. Eve n when use o f fire became common , the relatively small
hydrosphere. It is wi th in the b iosphere that the life form s of earth. includi ng
amoun ts o f sm oke genera ted we re easil y and rapidly dispersed and ass imilated
h umans. li ve. Li fe-sus taining ma teria ls In gaseo us, liquid , and so li d form s are
hy t he at m0sp here.
cycled t hr ough th e bi os p here, provid in g s us tenance to a ll living orga ni sms.
Early civi li za ti o ns o ft en drank from th e same rivers in which they bathed and
Li fe-s ustaining reso urces - air, food , and water - are withdrawn from the
dep osited th e ir wastes, yet the impact o f sLi c h u se was relatively s li g ht. as natural
biosphere. It is a lso into the biosphere that was te products in gaseous, liquid.
cleansing mec hanism s easily res tored water quality. These early humans used
and so li d form s are discharged. From the beginning of time, th e biosphere has
caves a nd other na tura l s helters or else fashioned their homes from wood, dirt,
received and assimilated the wastes generated by pla nt a nd animal life. Natural
o r a nim a l skin s. Often no madic, ea rl y popUlations left behind few items that were
sys tems have been ever active, dispersing s m oke from forest fires, dilutin g animal
not read il y bro ken down and absorbed b y the atmosphere, hydrosphere, or litho -
was tes washed int o st reams and rivers, and conve rtin g debris of pa st ge nerati o ns
sphere. And th ose items th a t were no t b ro ken down with time were so few in
of p lant and a nim al life int o soi l ric h enough to s upp or t future pop ul a tions.
number and so innocuo us as to present n o significant solid-waste problems.
F o r every na tur a l act of po ll ution, for eve ry und es irab le alteration in the
O nl y as ea rl y peoples bega n to ga ther toget her in larger, more o r less s table
ph ys ical. chem ica l, or bi o logica l charac ter is tics o f the enviro nm e nt , fo r everv
gro upin gs did their impact upon their loca l environments begin to be significant.
in ci dent that eroded the qua lit y of the immed ia te, or loca l, en viro nm ent , the r~
[n 6 1 A.D., cooki ng a nd heating fir es caused air- pollution problem s so severe th a t
were na tur a l acti o ns that res to red that qua lit y. Onl yi n rece nt years has it beco me
th e Ro man philosopher Seneca co mpl a ined o f " the stink o f the sm o k y chimneys."
apparent th a t th e sustaining and ass imil at ive capac it y of the bi os p here, th oug h
By the la te e igh teenth century, the waters o f the Rhin e and the Th a mes had
treme ndou s, is not, after a ll , infinite. Th o ug h the sys tem has o pe rat ed fo r millio ns
beco me too polluted to support game fi sh. Fro m the Middle. Ages the areas
of years, it has begu n to show sig ns o f stress, primar il y beca use o f the impact of
where food a nd human waste were dumped harbored rats, flies, and o th e r pes ts.
humans up o n th e environment.

Satisfying Acquired Needs

But these ea rl y evid ences of pollution ove rl oad were merely the prelude to greater
ove rl oads to come. With the d aw n o f the industrial revolution, humans were
[n a natural sta te, earth's life fo rm s li ve in eq uilibrium wi th the ir e n vironme nt.
bet ter able th a n ever to sa t isfy th eir age-old needs o f a ir. wa ter, food , and shelter.
T he numbers and ac ti v iti es o f each species a re gover ned by the reso urces ava ilable
In creasi n gly th ey turned th e ir a ttenti o n to o th er needs beyond th ose ass oc iated
to them. Spec ies in te raction is commo n, with th e was te prod uct of one speci es o ft en
With survival. By the la te nin eteen th a nd early twentieth ce nttlrje ~>.~.l!t 9.mobiles ........... .
fo rm in g the fo od s upply o f a n o th er. H umans alone ha ve the ab ilit y to ga t her
<lp pli a nces, a nd processed foods and beverages had become so p o pular as to seem .
.':Y9.n<;i'(heir. im mediate surro undin gs and p rocess th ose reso urces
necess ities, and meeting these acquired need s had become a maj or thruslof m o dern
in to diffe rent. m o re versa til e forms . These a bilities have made it poss ible for hum a n
indus tri a l societ y.
po pulati o n to thr ive and fl ourish beyo nd na t ura l co nst raints. But the natura l and
. U nlik e th e na tura l need; di sc ussed earlier, a cquired need s are usually met
m an ufac tured wastes ge nera ted a nd re leased into th e bi osphe re by these increased
by Items that must be processed 'or m a nuf<ic t'ure'd or refined, a nd the production,
numbers o f human be ings have up se t the natural equilibrium.
di s tributi o n, and use o f such items usually resu lts in more co mplex residuals,
Anthropogenic, or human-induced , po llut an ts ha ve ove rl oaded th e sys te m.
ma ny o f which are no t compatible wi th or readily assim ilat ed by the en viro nm ent.
The over loading ca m e rel a tive ly la te in the course o f hum a n int e ract io n wi th the
Take, for examp le, a familiar modern a ppliance-- the toas ter. The shell and
environment , perhaps because ea rly socie t ies we re primarily co nce rned wi th
the hea ting eleme nt s are lik e ly to be made of steel, the handle of th e lift le ve r of
m ee tin g natural needs , needs hu m ans sha re in C0m ll1 0n w it h mos t o f the hi g he r
plasti c. Copper w ires and synthetic insulation may be used in th e connectin g cord,
m a mm a ls. These peoples had no t ye t beg un to be concerned wi th meeting the
a nd rubber may be used o n the plug. In assess in g th e pollutants generated by the
acquired needs assoc iated w ith m ore advanced Civilizations.
manufacture and sa le of this simple app li ance, it would be necessary to include all
th e resources expe nd ed in th e milli ng o f th e met a ls, the ext racting and refining of
Satisfying Natural Needs th e pe tro leum, the sh ipping of th e vario us materials, then th e' m anufac turing,
shipping, a nd selling of the fini shed product. .The potential impac t o f a ll o f th ese
Earl y hum,!ns used nat ura l resoui-ces to sa tisfy th e ir need s for air, wa ter. fo o d, anc!
ac ti vities upon a ir an d wa ter quality is significan t. Furthermore, if the pollution
s he lt er. These natural. unpr ocessed reso urces we re readi lv a vai lab le in th e
poteilli a l in vo lving the manufacture and use of the heav y equipment needed for
bi osphe re, and th e re s iclues genera ted by t he use of such reso l;rces were genera ll y
t he ex trac ti o n and processing of th e raw materials used in the va ri o us to as ter
compa tible wit h, o r readil y ass imilat ed by, th e eIlI lron ment. Prllnitl ve humans
componen ts is considered , the list co uld go o n ad nauseum. And the so lid- waste
a te plant and a ni mal food s wi th o ut eve n di; tllrbing the atmosphere with the s moke

lik ely suffered from the il l effect s of air po lluti o n fo r centuries, but it is o nl y in this
disposal problems that arise when it is ti me to get rid of th e toaster become a
century that II1 creas ing ly heavy po ll ution has ca used hea lt h prob lems so dramat ic
further factor. as to be easil y a ttribut ed to air pollution . Several key incidents helped ca ll a tten ti o n
As a rule, meeting the acqu ired needs of modern societ ies genera tes more
to the poten tia lly dead ly effec t of air po ll ution. Severa l kille r smogs settled ove r
residuals thar: meeting natural need s, and these residuals a re lik elY to be less
London in the last quarter of the nineteenth century. but the tru e ex tent o f the
compatible with the environment and less li kely to be readil y assimila ted into the
air-po lluti on problem in th a t cit y did no t become apparen t until 4000 deaths and
biosphere. As societies ascend th e socioeconomic ladder, th e li st of acquired
countless illnesses were a ttributed to the Lond o n smog of 1952.
needs, or lu xuries, increases, as do the complex ity of th e production chain and the
Th o ugh the 20 dea ths ca used by a smog ove r Dono ra, Penn sy lva nia. in 1948
ma~s and complexity of the pollutants generated. Consequently, the impac t of
.raised so me alarm . It was not until th e New York i~ ve rs i o n of 1963 clcJlmed seve ra l
modern human popula tions upon the environment is of major concern to the
hundred li ves that thi s co untr y began to take the fi ght aga inst a ir polluti on ser io u sl\".
enviro nmental engineer: M onit o rin g o f th e sulfur diox ide, lead , and carbon mon ox ide leve ls in area s s u ~ h
as the smog-s hro ud ed Los An ge les bas in has revea led th at the hi gh leve ls of t hese
and other co nt aminan ts pose direc t and indirec t threa ts to human hea lth . Th ese
1-3 THE IMPACT OF THE ENVIRONMENT UPON HUMANS findings ha ve made air-po llut ion con tro l a top pri o rit y of the En viro nme nt a l
Protecti on Agenc y and a majo r conce rn of enviro nment al en gineers, who are
Tho ug h rivers become stagnant, skies smoke-shro uded , a nd dumping gro unds now ca lled upon to devi se man age men t programs designed to alter th e patt ern o f
od o riferous and unsightl y, populations generally manage to igno re their impact air po lluti on begun ce nturies ago a nd co ntinued until the prese nt tim e.
o n the environ men t unt il they begin to become awa re of the ill efrect s that a po llut ed O ther envi ronme nt all y relat ed hea lth pro blems also co nce rn th e en vIro n-
environment can have upo n thei r own hea lt h a nd we ll-being. Th o ugh stag nant menta l engi neer. Th e wid espread use of chemica ls in ag riculture an d in dus t ry
rivers , smoggy skies . a nd un sightl y dumps were aes th eticall y di spleasin g to the has introduced many new co mpo und s into th e environment. Some of these
citizens of ove rcrowded cit ies of earlier centuries, no att empt was made to re\erse co mpo und s ha ve been diffu sed in sma ll quantiti es th rougho ut the enviro nment.
the nega tive impact humans had o n thei r environm ent unlil it becamc ev iden t whi le others ha ve been conce nt ra ted at disposa l sites. Such che mi ca ls ma y be
th a t heavi ly polluted water, a ir, a nd so il cou ld exert a n eq ually negat ive impact spread through air. watc r, and so il , as we ll as thro ugh th e food chain. and thu s
on the health, the aes thet ic a nd cu ltu ra l pleasures, and th e econom ic op po rtunities pose a potential threa t to a ll human s.
of humans. The pesticide DDT was used extensively d uring the mid-centu ry decades and
has been instr umenta I. i.n the. eli.rpioalion .0J malari a in many p arts ofrhe i.\l ai rd. .. .
In addi ti on, thi s pesticide was used ex tens ive ly to control in sect pests on food and
Health Concerns fiber pla nt s. Its benefi cial use to humans was widely acclaimed , and its promoter.
Pa ul Mu ller. was awa rded a Nobel prize in 1958 for his contribu ti o n to publi c
Elemen ts of the air, the wa ter. and the land may host ha rmful biolog ical and
hea lth. Subsequ ent resea rc h. howeve r. has shown th a t DDT is a cumul a ti ve tox in
chem ica l agents that impac t the hea lth of hum ans. A wide range of comm un icab le
. tha t has adverse ly ;tfrccted many non target species. Traces of DDT can be found in
diseases can be spread th ro ugh elemen ts of the environment by hum a.n and
alm os t all li vin g o rg;lni sms thro ugho ut th e world - including human s. Alth o ug h
an imal waste product s. T his is most clea rl y evidenced. by th e plagues of th e M idclle
th e use of DDT is no\\' b:ln necl in the Un it ed States and seve ral other co untri es. the
Ages when disease spread t hroug h rats tha t fed on co ntamin ated so lid and human
chemical is st dl being manufa ctured. primari ly for use in seve ral develop in g
waste and disease carried by wa terbo rne para5ites a nd ba cteria ran rampa nt
co untries. par ticular ly in tro pi cal zo nes where its benefit s a re still cons id ered to
thro ugh the populatio n of Europe.
It has only been in th e las t century that the co rrelati on be tween wate rborne o ut weigh It s lia bilities.
A mo re rece nt example of chem ical tox ins th a t threaten health is the chemica l
b iological age nts and huma n diseases has been proved and effec tive preve nti ve
d ioxi n The format illil of this chemical. the scientific name o f wh ich is 2,3.7,R-
measures have been taken. Thro ugh immuniza ti on a nd env ironm ental contro l
tetrach loro-dibenzo paradioxin. is an unint entional by- product of a manufac turlll g
programs, the majo r diseases transm itt ed via the environment ha\'e all but bee n
process used with so me herhi cides anc! wood-preserving co mpounds. It is also
eliminated in deve lo ped count ries. No country, however, is totall y immun e fr om
fo rmed in t he prod uct io n of some d isinfectan ts ancl ind ustri a I clean in g co m pou nd s.
o utbreaks of env ironmen tall y tra nsmitted disease. The tran smiss io n uf viru ses
Di ox in is an ex treme ly toxi c substance. and it s presence in excess of I ppb (part
and proiozoa has proved particu la rl y difficu lt to co ntrol, .and lapses in go()d
per billi o n) in the en\' ilo nmen t;d ele ment s becomes cause fo r concern . (On e pa rt
sanitary practice have res ulted in min o r epidemics of o ther wa terborne diseases.
per bill io n co rrespo nds to o ne drop of wa ter in a sw imming poolme:l slIring IS i"t
P o ll ution of th e atm osphere has also posed severe health pro blems Ih at are
of great concern to environment al engi neers. Peop le in crowded citics have wiele, .\ 0 ft lo ng. and 11 ft dee p.)

C hem icals contai ni ng diox in residua ls have been used on a widespread basis devising environmental st ra teg ies. Neve rthe less, the en viro n me nt a l eng inee r
during the las t few decades. and the level of th is chemica l in th e general environ- sho ul d be an imp o rtan t member of a ma nageme nt team th a t incl ud es perso n s
ment is no t currently known. The discovery o f di o xin res idu a ls in waste-dis posa l drawn from a wide va riety of disc iplines. The input o f the en viro nment a l eng ineer,
s ites a nd in so il<; that were con tam ina ted t h roug h app lication of the paren t materia l especia ll y in assessing the li ke ly respo nse of the en viro nment to vari o us levels o f
has ca used g reat co ncern and ha s resu lt ed in ex pensive c lea n in g effor ts. Th e co nt amin a nt load ing a nd in we ig hin g th e va ri o us tec hnica l soluti o ns that m a y be
c rea tion of a "s uperfund" in the Environme n ta l Pro tection Agency. ini ti a ll y proposed, is a necessa r y co mpo nent o f a ny en viro nmenia l stra tegy.
fund .e d at seve ra l bil lio n d o llars. is bu t a s ta rt in the effo rt s to mi t iga te th e ha za rd s En viro n me nt a l engineers are usua lly m o re d irectl y associa ted w ith the imple.- .
of c hem ica ls in the enviro nm en t. menta ti o n of the ellvironmenra/caclics tha t a re th e m ea ns fo r ach ievin g the g o a ls
se t forth in a s pecific portion o f a given en vi ro n ment a l stra tegy. T he engineer 's
par t in thi s imp leme nt a ti o n co ns is ts pr ima rily o f th e d esign, co ns tru cti o n , and
Oth e r C onc ern s
o pe ra ti o n o f treat m e n t fac ilit ies fo r water, a ir, a nd so lid was te. F o r example, the
C lean ai r and wa terare an aesthe ti c de li g ht , yet ci ty dw e llers ha ve a ll bu t forgo tt e n env iro nme nt a l en g ineer wo ul d be involved d irec tly in the a d d itio n o f te r ti a r y
the s mell o f clea n a ir. a nd clear. sparkling lakes. rivers. :lI1d st reams are becoming processes to remove p hosp horus fro m t he effl uent o f a was tew a te r-trea tment
increasing ly rare. Litt ered streets and highw ays ' o tTe nd . rather than deli g ht. and facility emptying into Lake E t ie. th e insta ll a tion o f a hydroca rbo n rem oval system
unfe nced junk ya rds and u nco n tro lled d umps give fu rt her evidence o f th e aest het ic- at a gaso line refine ry ~ys t em in Los Ange les. o r th e d esign o f a so lid -w aste pro-
al ly d ispleasing e ffec t o f improper so lid-waste di s posa l techniques. cess ing pla nt In Phi lade lp h ia .
O u r c ult ura l as we ll a s our aes th etic heritage is a lso being los t to poJlut io n.
The Parthen o n in Athens. t he Sta tue of L rberty in N ew Yo rk ha rbor. the s ta tues
a nd fr escoes in Ve nice have withstood the o ns laug ht of the cleme nt s for centuries, 1-5 THE ROL E OF THE ENVIRONMENTAL ENGINEER
ye t are in increas ing danger of being dest royed by t he constituen ts o f a p o llu ted
atmosphere. ;\S po lluta nts en ter a ir, wa te r, o r so il, na tural p rocesses such as diluti o n, biolo gica l
And poll ution poses econom ic threats to hu man popu lations Lake E fl e o nce co n vers io ns, a nd c hemica l reac tio ns convert was te m a teri a l to m o re acceptable
su p po rt ed a thrivi ng fis h ing ind ustry a nd a ll th e a tt endant process ing a nd s hi pping fo rms a nd d isperse t he m thro ugh a large r vo lume. Yet th ose na tura l processes
fac il ities assoc iat ed with th a t indu str y. ye t th e eco no mic po tenti a l o f the lak e was ca n no 1'.1 nger perfo rm the c leanup alo ne. T he trea tme nt fac ilities d es ig ned by the
nearl y lost befo re se ri o us cle anup effo rts were begun . Th e s ilting in o f r ive rs. e n viro nmenta l engineer are ba sed o n the princip les of se lf-cleansing obser ved in
harbors. and rese rv oirs du e to unco ntro lled eros io n. often exacerbated by hum a n . nattl re.'.~ lIt. t he enKi.n( pr 9<;:.e$$e~ a tnplify a nd op tim ize the o per a ti o ns o bser ved
ac til'ities, threaten s to strengt he n so m e ind ustries'a nlle' expeiisebfolhe"r"s. in na ture to hand le large r vo lu mes o f po lluta nts a nd to trea t th em m o re ra pidly.
Erll'ironmenta l e ng ineers are com mitt ed to pro tec tin g huma ns fr om th e t hrea ts Engineers adapt the prin c ip les o f na tural mecha nis ms to eng in ee red sys tems fo r
a po lluted environment pose to human health. aesthetic :lnd cultural e njoy m ent, po ll u ti o n co nt ro l w hen th ey constru ct ta ll stack s to di sperse a nd di lute air
;Ind eco no mi c we ll-bei ng. po llutan ts, des ign biologica l treatmen t fac il ities for th e remova l of o rgani cs
from was tewa te r. use che mica ls to ox id ize a nd precipita te ou t the iro n a nd
manga nese in drinki ng-wa te r s u pplies, or bur y so lid wastes in co ntr o lled la ndfill
Occasio na ll y, th e e n viro n men ta l enginee r m ust d esig n to reve rse o r co untera ct
Vitall y co ncern ed with the improve ment o f environmental qua lit y, the el1\'iro n- na tura l processes. For examp le, the containers used fo r d isposa l o f haza rdo us
m e nt:." engineer p la ys a n impo rta nt" ro le in environmen tal mana ge m ent progra ms. was tes such as to xic chemica ls and radioac ti ve m ate ri a ls mus t iso la te th ose
Such programs might be sa id to inl'olve tllO distinct aspec ts -en vi ronme ntal m a terials from the en vi ro n men t in o rder to p reven t th e onse t of the n a tura l, b ut
s trat eg ies and e Jlvir o nm enta l ta c ti cs. [I-IJ LlIlim lllll e/1(o/ sr rl/r cqics are co mp l'e- hi g hly u ndesirab le. processes of d ilut io n a nd d ispers io n.
hensil'e pl ans tha t usua ll y address a va ri ety o f prob le ms that co nfront a sing le a rea . As will be de m o nstr a ted thr o ugho ut this' tex t, a n und e rs ta nd ing o f na tural
T y pica l'elll'iro nm e nl a l strate g ies might be a prugram to IInpn l\e the qualit y of an q engineered. purifica ti o n processes. requ ires an understand ing of th e bio logical
Lak e Erie. to im p rove the ai r quality of the Los Ang e les basin. or to collect a nd and chemica l react io ns invo lved in these processes. T hus, in addi tion to bem g
p ro pe rly iJispose of tlie so li d W;lste fr o m th e c it y of Philad elphia, know ledgeab le in the ma th em a tica l, physica l, a nd en gi nee rin g sCiences, . the
Enl'ironmental strategies are lI sua lly worked O UI in public and political envi ro nmenta l e nginee r mus t a lso be we ll grounded in th e subject areas o f c hemist r y
~ l r e n" s, Cl) nsid era ti o ll s mu s t inc lu d e economic. s(lcia l. and demograph ic fa c to rs. a nd microbio logy. s ubject a reas no t usua ll y emp hasized in eng inee rl1l g c urncul a .
II ist<,ric;I1h. elll'ironJllental CIli!lnee rs ha\'e Iwt l'I:lycd ;1 highh visible ru le In Indeed . an und erstanding of bio logica l and c hem ica l pri nciples is as esse ntt a l to

the environmental engineer as the understanding of statics and strength of materials PART
is to the structural engineer.
The environmental engineer's unique role is to build a bridge between biology
and technology by applying all the techniques made available by modern engineer-
ing technology to the job of cleaning up the debris left in the wake of an indis-
criminate use of that technoiogy. The delicare balance of our biosphere has
been disturbed. and the state in which we now find ourselves is a direct consequence
of our having ignored the limits of the earth's ability to overcome heavy pollution
loads, and of our having been ignorant of the. constraints imposed by the limits of WATER
the self-cleansing mechanisms of our biosphere.
A keen awareness of these natural constraints plays an important role in the
work of environmental engineers. For example, the laws of conservation of mass
and energy prevent the destruction of pollutants. and the engineer is bound by
these limits. The principles of waste treatment must therefore be to convert
the objectionable material to other, less objectionable forms: to disperse the pol-
lutants so that their concentrations are minimal: or to concentrate them for
isolation from the environment.
In all instances, the end products of the treatment of polluted water or air
or of the disposal of solid wastes must be compatible with the existing ~ nviron resources and must not overtax the assimilative powers of hydrosphere.
atmosphere, or lithosphere. In structural engineering. the engineer can simply
specify a larger or stronger beam to carry a heavier load. The environmental
engineer, on the other hand, must accept the carrying capacity of a stream, an
airshed, or a landmass because these can seldom be changed.
It is the purpose of this text to demonstrate how the environmental engineer,
working within these constraints, uses all available technological tools to design
.-... efficient control and treatment devices that are molleled after the natural processes
...... '(hili hit'ye' so 'fbrig' p'r'eservec! olii b{cisphe~e. 'Fo;'o~iy' 'by' b'r'i~gi~it'~~il~~l~gy';~t~ ' .'.
harmony with the natural environment can the engineer hope to achieve t he goals
of the profession-the; protection of the environment from the potentially del-
eterious effects of human activity, the protection of human populations from the
elTects of adverse environmental factors. and the improvement of environmental
quality for human health and well-being.


11 Bella , D. A., and W. S. OvenoJl' "Environmental Planning and Ecological Possibilities," pre
sented at the annual national environmental engineering meetlf1g of ASCE, St. Louis. M o .
October 18- 22. 1971.
1-2 "Guidelines for Environmental Engineering Visitors on ECPD Accreditation Tean'!s," Engineers
Council for Proli::ssional.oevelopment. United Enginee ring Cellt er, 34-5 East 47111 St.'-New York .
October 1977.


The availability" of a water supply adequate in terms of both quantity and quality
is essential to human existence. Early people recognized the importance of water
from a q uanti ty viewpoint. Civ il ization developed around water bodies that could
support agriculture and transportation as well as provide drinking water. Recog-
nition of the importance of water qua lity developed more slowly. Early humans
cou ld judge water qua lity only through the physical senses of sight, taste, and smell.
Not until the biological, chemical, and medical sciences developed were methods
available to measure water quality and to determine its effects on human health
and well-being. . ~
It was not until the mid-nineteentrrcentUTy-rhatthe relationship between'hmmrn ..... . .... ~ .
waste, drinking water. and disease was documented. Several more years intervened
before the facts concerning this relationship became widely accepted and remedial
action was taken. In .1854,* Dr. John Snow, a public-health worker in 'London,
noted a high correlation between cholera cases and consumption of water from a
well on Broad Street. Noi only was cholera running the nelgh~orhood
around the well, but outbreaks of the disease in other parts of the city could be
traced to indiv idua ls who had had occasion to drink from the Broad Street well.::
Although the proof was conclusive by modern epidemiology standards, the evidence
was not accepted by Snow's contemporaries. It is alleged that he physically
removed the pump handle to prevent LIse of the contaminated water. thus abating
the epidemic. [2'-2IJ
Advances in the germ theory of disease were made by Pasteur and others in
the lafe nineteenth century, and by 190.0 the concept of waterborne disease was
well accepted. The development of the science of water chemistry roughly paralleled
that of ivater microhiology Many of the chemic~1s used in industrial processes

*- Th i~. da le i... li sted as 18"",9 ill $u m~ publi c ati o ll ~

Atm os ph e re
and agriculture ha ve been identified in wat e r. H owever, th e effor t to id entify
.(her chemical' compounds which may already be fo und in trace qu a ntities in
many wa ter supplies and (6 delermirietheir effect b ti huma n hea lth was onl y
~ cently begun . It is likely tha t new analytica l techniques will b e de ve lo p ed th a t
~ill identify compounds not yet known to exist in water, and it is co ncei va ble th a t Condensation

-lese materials will also be linked to human health . Thus, the science o f wa ter '
quality will rem a in a ch a llenge for engineers a nd scientists fo r yea rs to co me.
Lik e all sciences, the science o f wa ter qu a lit y h as develo p ed it s ow n t ermin o logy
and the means of quantifying these terms. The purpose of this cha pt er is to intro -
d.uce the read er to the modern co n cepts o f water qu a lity. The mea ns b y w hi c h th e
. ature and extent of contaminants in wate r a re me as ured a nd ex pressed a re'
Qresented alon g with th e so urces of vari o us co nt a min a nt s that find th e ir way int o
Earth 's
.: aler. An understanding of the m a terial in thi s cha pter will b e essenti a l in su b- surface
~equent chapters dealing with water-quality cha nges in b o th n a tur a l and eng inee red
.}s tems.


-Water is o ne o f the m ost a bund a nt co mp o und s fo un d in na ture, cove rin g a pprox i-

-- ;

,n a tely three-fourths o f the surface o f the ea rth . In spite o f thi s a pparent ab un d an ce, Aquifer< o
...s;evera l fac tors serve t o limit th e a m o unt of wa ter a va ila ble fo r human use. As
~ J1own in T a ble 2-1 , over 97 pe rcent o f the to ta l wa te r suppl y is co nt a ined in th e ~
100/, 011
..Qcea ns and other saline b o di es of wa ter a nd is n o t readil y usa ble fo r m os t purp oses.
)f the rem a ining 3 p e. cent, a little o ver 2 percent is ti ed up in ice ca ps a nd g lac ie rs Fi gll rl' 2- 1 H ;.dro log1 c cycle
~nd , alon g with atrp o spheric and soil moisture, is inaccess ible. [ 2- 17J Thu s. fo r
:, e ir ge neral li velih ood a nd the suppo rt o f th e ir va ried technical a nd ag ri c ultur a l
activities, hum an s must depend up o n the rema ining 0.62 percent fo und in fr es h- Wate r is ina COllst an t sta te of mot io n. as depic ted in t he h yd ro logic cyc le s h ow n
-"ater lak es, ri ve rs, and g ro undwa ter supplies. in Fig. 2- 1. Atmosph e ric \Ia ter condenses and fall s to th e ea rt h a s ra in. snow. o r
so me othe r form of rrec ipita tio n. On ce o n t he ear th 's surface. wate r flOW S into
-:-T able 2-1 World wate r distribution strea ms, lakes. and eV'e ntu a lI y th e oceans. or rer co lates th ro u gh t he so il and into
VoJume. 10 ' 2 m '
aLJu ifer s t ha t eventua ll y disc harge int o s u rface wa te rs. T h ro ug h evaporat ion
Locati o n
fr o m surfa ce waters or by evapotran sriration from p lants. wate r mo lecu les return
La nd areas to the a t mosrh e re tll repea l the cyc le . Although th e move me nt t hr o ug h so me p a rts
Fresh wa ter ta kes 125 0.009 of the cyc le may be re la ti ve ly rar id . comr lete recyc ling o f g rou ndwa ter mu st o fte n
Sa line lakes a nd i nland seas '104 0.008
be measu red in gco logic ti me.
Ri vers (ave rage insta nt aneo us vo lume) 125 0.000 1
67 0.005 Wat e r in n ature is most nedriy pure in its ev aporation stat e. Beca use the ve r y
act of co nd e nsa tion usua ll y requires a surface. o r nucle i. wate r ma y aCLJuir~
So il moist ure
G roundwater (above dept h o r 4000 m ) 8,350 0.6 t
Ice ca ps a nd glac iers 29,200 2. 14 imp uri ti es ~I t the VC I'Y mo ment of co nde nsa li o n. Ad dit io n a l im pu rit ies are'added
37,800 2.8 as th e liqu id w; lt e r t ravels t hrou g h Ihe rema ind e r of t he hvdrolof!.ic cvcle and comes
int o co n tac t w it h m ate ri a ls 'in the ~ti r a nd on o r henea til th e s~lrra~e of the ea rr 'h
Total land a rea (rounded)
~!\ tm os ph ere (wa ter VO pM) 13 0.00 1
H uman ac ti vi til:s contr ib ute furthcr Impurittes In the fo rm of indu st rial a nd d o-
Ocea ns 1. 320,000 97.3
mes ti c w; lstes. ag l'icu ltu ra l chemica ls. a nd <l t her. less obv ious co n ta mi nan ts.
-To ta l all iL'ca tlon s trc'unded) 1.360.000 100 Ultimately. these ImJlure wa ters will Co tllr lete the hyd ro logic cycle and re t ur n to
the ,lltll os phc rc ;,s re lalll'ely rure water 1l1()i<:cu ies. H owever. it IS w,ltcr q ual itv
So urce : Ad a rt ed fr,)]l1 T lxld . 12- t 7J


Di sso lved Collo ida l Suspend ed or non fiil e r"ble
Size of particl e. 11m As noted ea rli er, so lid s can be dispersed in water in both suspended and dissolved ..
10 - 2 10 - 1 10 100
forms. Althou gh some dissolved so lids may be perceived by the physical senses,
I I ! I they fall more appropriately under the ca tegory of chemica l parameters and will
iO - 8 10 - 1 be di scussed more fully in a later section.
Size of p"rtici e, mm
Figure 2-2 Size cl.ssification of solids in wa ler. (Fr oln ;V/e !calj & Eddy , In c. [l-R].) So lid s suspended in water may consist of inorganic o r organic particles or of
im misc ible liquids. In organic so lids such as clay, silt, and o ther soil constituents are
in th e int ermed iate s tage which is of grea test co ncern becau se it is tIle qu a lit y at co mm on in surface water. Organic material such as plant fibers and biological
this stage th at will affec t human use of the water. so lid s (a lga l ce lls, bac teria, etc.) are also common constituents of surface waters.
The impurities acc umulated by wa ter throughout the hydro log ic cycle and as a These materials are often nat ural contaminants resulting from the erosive action
result of human ac ti vities may be in both suspended and disso lved fe rm. Suspend ed of wa ter fl ow in g over surfaces. Because offne filtering capacity of the soil, suspended
mat erial co nsists of particles larger than molecular size th at are suppor ted by material is seld o m a co nstituent of groundwater.
bu oya nl and visco us fo rces within the water. Disso lved material consists of Other suspe nd ed material ma y result from hum an lise of the water. Domes tic
mo lecu les o r io ns (see Sec. 2-7) that are he ld by the molecular stru cture of wa ter. wastewa ter usua lly contai ns large quantities of suspended so lids th at are mostly
Co ll oid s are vei- y sma ll particles that tec hnica ll y are suspend ed but oft en ex hibit organic in nature. Industrial use of water may result in a wide variety of suspended
man y of the cha rac ter isti cs of disso lved substa nces. Size ran ges of di sso lved, impurities of either orga nic or inorganic nature. Imm'iscible liquids such as oils
co llo idaL a nd suspended substances are shown in Fig. 2-2. and greases are often constituents of wastewater.
Wal eI' pulluriol1 ma y be defined as the presence in wa ter of impurities in
such quantity and of such nature as to impair the use of the wa ter for a stat ed Impa cts
purpose. Thu s the definition of water qua lit y is predicted on the int ended use of
Suspended materi al may be objectionab le in water fo r severa l reasons. It is
the water , and a gross det erminati o n o r the qu antit y of suspended and d isso lved
impuriti es. whi le useful III some cases, is no t sufficient to co mpletely define water aesthet ica ll y di spleasing and provides adsorpt ion sites for chemical and biological
agent s. Suspended organic so li ds ma y be degraded biologica lly, resulting in
qua lit v. Man v pa rameters have evo lved that qualitativelv reflect the impact
tha t v~ri6usi;n pti i-i ii'es .have onseIectec! ',y',iter .Ll ses.- An ~I I Y tic,i i -p~oc~(i ~;~~~' h~ ;~" -
. " .. .... ". objecii() nable by-products. Bio logically active (live) sllspended solids may include
di sease-ca usin g orga ni sms as well as orga ni sms such as tox,in-producing strain s of
been deve loped th at quantitatively measure these para meters. Standard ;'v1 elhods
a lgae.
/01' Ih e Examinaliol1 of WaleI' and Wa sl ew(J( er. [2- I SJ has been the auth orita ti ve
stand ard for test procedures fo r many yea rs. For detailed cove rage of the subject
. the interested reader is referred to thi s' publica tion and to an Enviro nmental iVI easurement
. Protectio n Age ncy publica ti on that offers sim ila r informatio n. [2-9J Th ere are seve ral tests avai lable for measuring so lid s. Most are gravimetric 'tests
A kn owledge of the pa rameters most commo nl y associated wi th wa ter- and in vo lving the ma ss of resid ues. The total solids t esc quantifies all the solids in the
wast ewa ter-treatment processes is esse nti a l to th e en vironmental engineer. water. suspend ed and disso lved, orga nic and inorgan ic. Thi s parameter is measured
The remai nd er of this chapter will be devoted to a disc ll ss ion of param eters used by eva porating a samp le to dryness and weighing the residue. The 'total quantity
to assess th e ph ys ical. chemica l. and bio log ica l charac teristics of wa ter. T estin g of residue is exp ressed as milligrams per liter (mgj L) o n a dry-mass-of-solid s
procedures described for each parameter are based on those desc ribed in Stal/dard basis. A drying temperature sligh tl y above boiling (I04 c C) is sufficient to drive off
,V /di wris [2- 15J t he liquid and the water ad so rbed to the sllrface of the particles, wh ile a temperature
- of about 180C is necessa ry to evaporate the occl uded wa ter.
Physical Water-Quality Parameters . Mos t suspended so lids can be remo ved from water by filtration . Thus, the
suspended fraction of the so lid s in a water samp le can be app rox im ated by filt er-
Ph ys ica I para meterS define t hDse cha racterist ics of \\'ater t ha t respond to t he senses ill [! th e wa ler, drying the residue and filler to a constant wei ght at 104C ( l C).
of sig ht. t(luc ll. ta ste. or sme ll. Suspend ed so lids. lurbiclity. co lol-. taste an d odor. ~ llId Lieterminillg the ma ss of th e residue retained on the filter. The result s of this
O/l SIJ,,"i/ei/ soliris II:'SC are also expressed as dry mass per vo lume (mil ligramsper
;Ind temperatu re fall int o thi s ca tego ry.

liter). The amount of dissolved solids passing through the filters, also expressed as Use
milligrams per liter, is the difference between the total-solids and suspended-
Suspended solids, where such material is likely to be organic and/or biological
solids content of a water sample.
in nature, are an important parameter of wastewater. The suspended-solids
It should be emphasized that filtration of a water sample does not exactly
parameter is used to measure the quality of the wastewater influent, to monitor
divide the solids into suspended and dissolved fractions according to the definitions
several treatment processes, and to measure the quality of the effluent. EPA has
p~esented ~arlier. Some colloids may pass through the filter and be measured along
set a maximum suspended-solids standard of 30 mg/L for most treated waste-
With the dIssolved fraction while some of the dissolved solids adsorb to the filter
water discharges.
material. The extent to which this occurs depends on the size and nature of the
solids and on the pore size and surface characteristics of the filter material. For
this reason, the termsfilterable residiles and Iloll{ilrerable residues are often used.
Filterable residues pass through the filter along with the water and relate more
closely to dissolved solids, while nonfilterable residues are retained on the filter
A direct measurement of suspended solids is not usually performed on samples
and relate more closely to suspended solids. "Filterable residues ,. and" non-
from natural bodies of water or on potable (drinkable) water supplies. The nature
filterable residues" are terms more frequently used in laboratory analysis while
of the solids in these waters and the secondary effects they produce are more
the" dissolved solids" and "suspended solids" are terms more frequently used in
important than the actual quantity. For such waters a test for turbidity is com-
water-quality-management practice. For most practical applications, the distinc-
monly used.
tion between the two is not necessary.
Turbidity is a measure of the extent to which light is either absorbed or scattered
Once samples have been dried and measured, the organic content of bot h total
by suspended material in water. Because absorption and scattering are influenced
and suspended solids can be determined by firing the residues at 600C for J h.
by both size and surface characteristics of the suspended material, turbidity is
The organic fraction of the residues will be converted to carbon dioxide, water
not a direct quantitative measurement of suspended solids. For example, one
vapor, and other gases and will escape. The remaining material will represent the
small pebble in a glass of water would produce virtually no turbidity. If this
JJ1orgamc, or fixed. residue. When organic suspended solids are being measured ,
pebble were crushed into thousands of particles of colloidal size, a measurable
a filter made of glass fiber or some other material that will not decompose at the
turbidity would result, even thoughthe mass of solids had not changed.
elevated temperature must be used. The following example illustrates the calcula-
tions involved in suspended solids analysis.
.. ~ .... " ..... ~?,.a~p!~ .2: I .:. pt;!l)!I,l!ng. ~~~. ~.Qn~.enlmtiQ/1 . .o( sllSpended . solids :. A resid ue
Most turbioity in surface waters results from the erosion of colloidal material
analysis is run on a sample or water as rollows. Prior to filtering, the crucible and filter
such as clay, silt, rock fragments. and metal oxides from the soil. Vegetable fibers
pad are kept overnight in Ihe drying oven. cooled. and the dry mass (tare mass) or the
pair determ1l1ed to be 54.352 g. Two hundred and fifty milliliters or the sample is drawII and microorganisms may also contribute to turbidity. Household and industrial
through a hlter pad contained in the porous-bottom crucible. The crucible and filter pad wastewaters ma y contain a wide variet y of turbidity-producing material. Soaps,
are then placed 111 a drY1l1g oven at 104(, and dried untit a conSlant mass of 54.389 g is cietergents. and emulsifying agents produce stable colloids that result in turbidity.
reached. Determ1l1e the suspended solids concentration of Ihe sample. Although turbidity llle<ISttrCme nts are not .commonly run on wastewater. diS-
SOLUTION charges of wastewaters may. ilicrease the turbidity of natural bodies of water. .
I. Determine the mass of solids removed.
Tare mass + solids = 5-1.3S9 g Impacts
- Tare mass = 54.352 g
When turbid water in a small. transparent container, such as a drinking glass.
Mass of solids = 0.037 g is helel up to the light. an aestheticallydispleasing opaqueness or "milky" colora-
.= 37 mg tion is J.pp:lrent. The col1oiLialm<lterial a ssocia ted with turbidit y provides adsorp-
2. Determine the concentration of the solids. tion sites for chemicals that Illay be harmful or cause undesirable tastes and odors
ano for biological organisms that mav be harmfuL Disinfection of turbid wa ters
is diffi c ult because o f the adsorptive cll~iracterislics of some colloids and because
mg solids x 1000 mL!L
-~--.---- .-.- = conc in mg L
I11L of sample . th e solids Illay partiall y shield organisms fr o m the disinfectant.
37 x 1000 In natural water bodies. turbidity may impart a brown or other color to wetter.
...- - - - . - = 148 l11 o :L
250 depending o n the light-absurhing prope rti es of the so lids. and may interfere with

li g ht pe netra ti o n and photosy nthetic reacti o ns in strea ms a nd la kes. Accumula- Sources

tion o f turbidity-cau sing particles in po ro us streambeds res ult s in sediment de-
pos its th at ca n ad ve rsel y affect the fl o ra and faun a of the s tream. After contact with orga ni c debris such as leaves, conifer needles, we~ds, or wood,
water pick s up tannins. humic acid, and humatesand takes on yellowish-brown
hues. Iron oxides cause reddish water, and manganese oxides cause brown or
blackish water. Industrial wastes from textile and dyeing operations, pulp and
Turbidit y is measured pho to metrica ll y by determining th e percentage of light of a paper production, food processing, chemical production, and mining, refining,
given intens it y that is either absorbed o r scattered . The o rig inal meas urin g and slaughterho use operations may add su bstantial coloration to water in re-
a ppara tus, ca lled a J ackson ltIrbidim eler. was based on light abso rpti on and ceiving streams.
employed a long tube and standardi zed candle. The candle was placed beneath
the g lass tube that was th en housed in a b lack metal s hea th so that th e light fr o m
the candle cou ld only be see n from above the apparatus. The wa ter sa mple was Impacts
th en p ou red s low ly into the tube until the lig ht ed candl e was no longe r vis ible,
i.e., complete absorp ti on had occurred. Theg la ss tube was calibrated with readings Colo red water is not aes thetica lly acceptable to the general public. In fact, given a
fo r turbidity produced by s uspen s ions o f silica dioxid e (Si O l ), with o ne Jackson c hoice consumers tend to choose clear. nonco lo red water of otherwise poorer
turbidity unit (JTU) being eq ual to th e turbidit y produ ced by I mg Si0 2 in I L o r qu a lit; -o~et trea ted potable water supp'lies with an objectionable color. Highly
dis tilled water. co lored water is unsuitable for laundering, dyeing, papermaking, beverage
In recent years this awkward ap pa ratus has been re placed by a turbidit y manufacturi ng, dairy prodlJcti o n and other food processing, and textile and
meter in which a standardized electric bulb produces a light that is th en direc ted plas li e pro duction. Thus, the color of water affects its marketability fo r both do-
through a sma ll sample via l. In the absorption m ode, a photometer meas ures th e mesti c and indu strial use.
li gh t intens it y o n the s ide of the vial opposite from the lig ht so urce, w hile in the While true co lor is not usually considered unsanitary or unsafe, the organic
sca tterin g mode, a photometer measures th e li g ht inten s it y a t a 90 c an g le fro m th e co mpounds cau sing true color may exert a chlorine demand and thereby seriously
lig ht source. Alth o ugh most turbidity me te rs in use today wo rk o n th e sca tt e rin g red uce the e ffe c tiveness of chlorine as a disinfectant. Perhaps more important are
principl e, turbidit y cau sed by dark s ubsta nces th ilt absorb ra th e r than rerlect the produc ts fo rmed by the combination of chlorine with so me color-producing
li gh t s ho uld be meas ured by the absorption technique, h)rmazin. a c hemical o rganics. Pheno lic compounds, common constituents of vegetative decay products, .
compound , provides m o re re produc ible' sta nd ards th a n S iO 2 a nd has rep laced it prod uce ve ry o bjecliql)<ible. taste and.od.of, ~.ornP'ou.nds. \vit~. chlor.i l1 e: .A.~~)t\~)["!<;i,IJy." .. . , .. .. . ... .
as a refe rence. Turbidity meter readin gs a re now expressed as /ormm ill lIIrhidit y so me compo;ind's of naturally occurring organic acids and chlorine are either
lIliits. or FTU s. Th e te rm nephelometry IUrbiditr Llllits (NTU) is o ft e n used to kn ow n to be. o r a re suspected of being. carcinogens (cancer-causing agents).
indicate th a t the test was ru 'n accordi ng to Ih e sc alte rin g pr inci ple ,

. Measurement
Turbidit y meas ur ement s are norma ll y mad e' o n "c lea n " waters as op posed to Although severa l method s of COIOf measurement are available, methods involvin~
wastewaters. Na tur a l wa ters ma y ha ve tUI'bid ili es ran ging fro m a few FT Us to co mparison with standardi zed co lored materials are most o ften used. Color:
seve ral hundred . EPA drinking-waleI' s tand a rd s specify " m~p;i!llulll o f I FTU . comparison lubes containing a se ries of sta ndards may be used for direct com-
while th e American W a ter W o rk s Assoc iati o n has SCi 0.1 FT L! as it s goal for pariso n or water samples that have been filtered to remove appa rent color. Results
drink ing water. [ 2- 1] are expressed in true color units (TCUs) where one unit is equivalent to the color
produced by I mgj L of platinum in the form of chlorplatinate ions. For colors
o ther Ihan ye ll ow is h-brow n hues. especially for colored waters originating from
2-4 COLOR indu strial was te effi uents, special spec trophotom~ trjc tech niques are usually
. emp loyed.
Pure wa te r is co lo rl ess. but water in nature is often eoki red by foreig n s ubsta nces. In fieldwork . instruments employing colorcd glass disks that are calibrated
Water w hose co lo r is part ly du e to s uspe nd ed maltcr is sa id 10 have lI{J{'(/rcnt color to t he color slandards are o ften used . Because biological and physical changes
Co lo r co ntributed by disso lved so lid s th ai rema lll aha 1"C lllll\';li o f suspended uccllrri ng during storage may affec t color. samp les s hould be tested within 72 h
mailer is kn ow n as lrue color. of co ll ec t ion.

Use ' Measurement

Color is not a parameter usually included in wastewater analysis. In potable Direct measurement of materials that produce tastes and odors can be made if the
water analysis; the common practice is to measure only the true color produced cau sative agents are known. Several types of analysis are available for measuring
by organic acid resulting from decaying vegetation in the water. The resulting taste-producing inorganics. Measurement of taste- and odor-causing organics
value can be taken as an indirect measurement of humic substances in the water. can be made using gas or liquid chromatography. Because chromatographic
analysis is time-consuming and requires expensive equipment, it is not routinely
perfo rmed on wat er samples. but sho uld be done if problem organics are suspected.
H o we ver. becau se o f the synergism noted earlier, quantifying the sources does not
necessarily quantify the nature o r Intensity of taste and odor.
Quantitative tests that employ the human senses of taste and smell can be
The terms taste and odor are themselves ,definitive of this parameter. Because the used for this purpose. An example is the test for the threshold odor number (TON).
sensations of taste and smell are closely related and often confused, a wide variety Varying amounts of odorous water are poured into containers and diluted with
of tastes and odors may be attributed to water by consumers. Substances that enough odor-free distilled water to make a 200-mL mixture. An assembled panel
produce an odor in water will almost invariably imparLa..taste as well. The con- of fi ve to ten " noses" is used to determine the mixture in which the odor is just
verse is not true, as there are many mineral substances that produce taste but no barely detectable to t he sense of smell. The TON of that sample is then calculated,
odor. using the formula
A + B
Sources TON (2-1 )
Many substances with which water comes into contact in nature or during human wh ere A is the volume of odorou s water (mL) and B is the volume of odor-free
use may impart perceptible taste and odor. These include minerals, metals, and water required to produce a 200-m L mixture. Threshold odor numbers correspond-
salts from the soil, end products from biological reactions, and constituents of in g to variolls sample volumes are shown in Table 2-2. A similar test can be used to
wastewater. Inorganic substances are more likely to produce tastes unaccompanied quantify taste, or the panel can simply rate the water qualitatively on an "accept-
by odor. Alkaline material imparts a bitter taste to water. while metallic salts abilit y " scale .
may give a salty or bitter taste.
Organic material, on the other hand, is likely to produce both taste.and.odor,. .... .. .. ..... ..... .
A multitude of organic ch-emicals may cause taste and odor problems in water, Table 2-2 Threshold odor
with .petroleum-based products being prime offenders. Biological decomposition numbers corresponding 10
of organics may also result in taste- and odor-producing liquids and gases in water. sample "olume dilul~d to
Principal among these are the reduced products of sulfLlr that impart a " ro tten .200 mL
egg" taste and odor. Also. certain species ~f algae secr~te 'an oily substance that
Sa mpfe vo lume (A),
may result in both taste and odor. The comb,ination.of two or more substances, mL TON
neither of which would produce taste or odor by itself, may sometimes result in
taste and odor problems. This synergistic effect was noted earlier in t he case of 200 1.0
organics and chlorine. 175 I I
150 U
125 1.6
100 2. 0
Impacts 75 2.7
67 3.0
Consumers find taste and odor aesthetically displeasing for obvious reasons,
50 4 .D
Because water is tliought of as tasteless and odorless, the consumer associates ,, 0 5.0
taste and odor with cont"amination and may prefer to' use a tasteless. odorless 25 8.0
water that might actually pose more of a health threat. And odors produced by 10 20.0
organic substances may pose more than a problem of simple aesthetics. since some 2 100
of those substances may be carcinogenic. 200
---+--- - ---_..

Use reacti o ns in vo lving dissolution of so lids are accelerated by increased temperatures.

Alth o ugh odo rs can be a problem with wastewater. the taste and odor parameter The so lubilit y of gases. o n the other hand , decreases at elevated temperatures.
Because bio log ica l ox idatio n o f o rganics in streams and impoundments ' is de~ "
is on ly associated with potable water. EPA does not have a maximum standard
pendent o n an adequate supply of dissolved oxygen, decrease in oxygen solubility
for TON . A m ax imum TON of 3 has been recommend ed by the Public H ea lth
Service a nd se rvesas a gu id e lin e rather th an a lega l standa rd. [2- lgJ is und esi rable. T he relationship between temperature a nd dissolved oxygen
levels is s hown in Table C-3 of the appendix.
Temperature also affect s other physical properties of water. The viscosity of
water increases with decreasing temperature. The maximum density of water
occ urs at 4C, and den sity decreases on either side of that temperature, a unique
phenomenon among liquids. Both temperature and density have a subtle effect
Te mpe rature is not used to e va lu a te direc tl y either potable wa te r or was tewa te r.
on plankto nic microorga nisms in natural water systems. The relationship of
It is_ however, o ne of the mos t importa nt p arame te rs in na tura l surface-wa ter
temperature a nd density to st ratification of impoundments is discussed in Chap. 3.
systems. The temperature o f surface wate rs governs to a large extent the biological
s pecies present a nd their ra tes of activ it y. T empe rature has a n effec t on most
chemical reactions th a t occur in natural wa ter systems. Temperature a lso has a
Chemical Water-Quality Parameters
pronounced effect on the so lubilities of gases in wa ter.
Water has been called the universal so lvent , and chemical parameters are related
Sources to the so lvent capabilities of water. Total dissolved solids, alkalinity, hardness,
fluorides, metals, organics. and nutrients are chemical p a rameters of concern in
The temperature o f natural wa ter sys tems responds to many fac to rs. th e ambie nt water-quality management. The following review of some basic chemistry related
temperature (temperature o f the surro unding atmosphere) being th e m os t un i- to solutions s ho uld be helpful in understanding subsequent discussions of chemical
ve rsa l. Generally, shallow bodies of wa ter are more affected by ambie nt temp era- par ameters.
tures than a re deeper bodies. The use of water fo r di ssipa ti on of was te heat in
indu stry and the subsequ e nt discharge of th e heated water may result in dramatic.
th oug h perhaps loca lized. temperature change~ m receiving streams. Removal of 2-7 CHEMISTRY OF SOLUTIONS
forest ca no pi es and irri gat io n return flows can also res ult in increased stream
.. . .. . ..... .. ... te mp'enitllte: ......... . - ..... .... . . . . .
An atom is the sm a llest un it of each of the elements. Atoms are building blocks
from w hi ch molecules of elements and compounds are constructed. For instance,
I rnpacts tw o hydr oge n atoms combine to form a molecule of hydrogen gas:

Coo ler wate rs lisu,tll y have a wide r d i\'ersity ofh io lllglc; iI s pecies. At lower tempera- H+ H --> H2
tures. th e rate of biological ac ti vity. i.e .. utiliza t io n of fo od s upp li es. growth. Adding one a tom of oxyge n to the hydroge n molecule results in one molecule
reproduction. etc.. is s lower. If the temperature is inneased. biolog ica l act ivit y of the compound wa ter:
increases. An increase of loce is usuallv s ufficient to doub le the biological acti v it y,
ifesse ntial nutrients are present. At elcv:lted tempcratllres anti increa sed metabolic 1-1 2 + 0 --> H 20
rates. urga nisms that are more eflicicnt at rood IItilizatl n n and reproduction A relative mass has been assigned to a single atom of eac h element based on a
rlouflsh. while llthe r species decli'ne and ,Ire pC,rhaps e limin ,lteci a lt ogether. mass of 12 for carbo n. The s um o f the atomic m ass of all th e atoms in a molecule
Accelera ted growth of a lgae often occurs in \\arm \\a;tcr ;llld can becoille a problem IS the lIlu /cclila/' mass of that m o lec ule. The atomic mass of hydrogen is I arid the
when ce l" cluster into algae Illat s. Natural secretl(lIl o f pils by ,i1 gJe 111 the mat s . atomic mass of oxyge n is 16. Thus, the molecula r mass o f the hydrogen molecule is
and the decay pr oducts o f dcad a lgae ce ll s Cdll n:sllit ill la sle and odor pl'oblem s, 2 a nd the mo lec u lar mass o f water is 18. A mole of an e lement or compound is its
Higher-order species: s uch as fi sh. arc ,dkclCd dram;llica ll y by Icmper,i ture a nd molecular mass expressed in common mass units. usually grams. A mole of
by dissolved oxygen le ve ls. which a rc ;( , rll l~ ctl(ln o r tcmperatmc. Game fi s h hydrogen is 2 g, while a mole of wa ter is 1g g. One mole o f a substance dissolved
ge nera ll y requ ire co o ler temperatures ;Incl 11I1,!hcr dl sso l\e Ll -\lxygell le vels. in suffi cien t wa ter to m a ke o ne liter of soluti o n is called a one molar solution .
T e mpera ture c hanges a lTec t the rc,lctioll rates ami so lubilit y le ve ls of chemicals. Bonding of element s int o compounds is so metimes acco mplished by electrical
a s ubj eci more fu ll y exp lored ill later s e c tlnn ~ (l r I hi ~, L'ilaptel. Mus t c hemical forces resultin g from tran sferred electrons. When these compounds dissociate

In water, th ey prod uce species with oppos ite c harges. An exa mple is sodium Eq ui va lents a re very impo rt a nt in wa ter c hemistr y. In additi on to being useful
chloride : in calc ul a tin g c he mi ca l qu a ntities for des ired reac ti o ns in wate r and was tewater
treatment, equ iva lents a lso prov id e a means o f express in g var iou s co ns titu ents o f
di sso lved so li d s in a co mm o n term. An eq ui va lent o f o ne substance is c hemi ca ll y
The charged species a re ca lJed ions. Positively charged io ns a re ca lled cal ions, equa l to a n equi va lent of a ny o th e r substance. Therefore, th e co nce ntra ti o n o f
and negatively charged ions a re called anions. The number o f p osi tive charges sub sta nce A ca n be expressed a s a n equiva lent co nce nt ra ti o n o f s ubstra te B by th e
must equal the number of negative c harges to prese rve electrica l neutra lit y in a fo llow ing meth od .
chemical compound. The number o f charges o n an io n is referred to as the va lence
of th a t ion. Thus, the va lence o f sodium (Na +) is 1, w hile the va lence of calcium (g, L)A
- - - -- x (g/eq ui v) B = (gj L)A ex pressed as B (2-2)
(Ca 2 +) is 2. So me compounds, ca lled radicals , als o p ossesscha rges. An exa mple o f (gjeq ui v)A
a cationic radica l is a mm o nium (NH 4 +), wh ile carbo na te (CO) 2 - ) is a n a nioni c
Hi sto ric a ll y, co nstitu e nts o f d issol ved so lid s have been reported in te rms o f
radic a l.
equ iva leJll ca lc ium carbo na te co nce ntrations. The fo llowi ng exam ple illustrates
Wh en io ns or radic a ls react w ith eac h o th er to fo rm new compo und s, t he
thi s tec hniqu e.
reactions m ay not a lways proceed o n a o ne-t o -one bas is as was th e case fo r sodiu m
ch loride . The y do, however, proceed o n a n equi va lence basi s that can be 'related
Exa mpl e 2-3: Determinin g e'luiv a lenl co ncen lr a li ons What is the equi va le nl ca lcium
to electroneutrality. Technically, th e equivalence o f an element o r radi ca l is defi ned
car bo nale con ce ntratio n 0 1'( 0) I 17 mg/ L o fN aC I a nd (b) 2 x 10 - 3 m o l o fNa CJ ?
as th e number o f h ydrogen atoms th at e lem ent or radic a l ca n hold in combinati o n
or can replace in a reacti o n. In most cases, th e equivalen ce o f a n io n is the sa me as SOLUT ION
the abso lute va lue o f it s va lence. An eqllivalenl of a n e le ment o r rad ica l is it s g ram
(iI ) I , One equiva le nt o r ca lCi um ca rbona te is
molecula r mass di vided by it s equiva lence. A m illieq ui valent is th e mo lec ular
mass expressed in m illigrams d ivid ed b y the equ iva le nce a nd is o ften m o re 40 1- 12 + 3( I 0) "
useful in water c hemistry beca u se co nce ntr a ti o ns o f disso lved su bsta nces are mo re -- '---
2- ' = 50 g/eq uiv = 50.000 mg/ equl v = 50 mg/ mequlv
o ften in the milligrams per lit er range. Comp o und s are fo rmed by th e co mbin a ti on
of e lemen ts o r ra dic a ls o n a o ne-t o-o ne eq ui va lent basis. The ca lcul a ti o n o f equi va- 2. On e .equivalen t o f S(l(\ IlIl11 chloride is
lents is illustrated in Exa mple 2-2. 23 + 35.5
= 58,5 g/equlv = 5 .5 mg/ mequi v
Example 2-2 : Calculating equivalents H ow many grams o f calci um will be required to
. . . . . .... ... c o mbi'lie' w,ih'90'g'of carb<Jriiite'io fo rm'cid c ium' ca rbo na le?
3, By Eq , (2-2)
11 7 mg!L .
l. Ca rbo na te (CO / - ) is a radica l composed o f carbon and oxygen. In thi s particula r - _- - - ' -,- x 50 mg/ mcqui v = 100 mg/ L o f NaCi as.CaCO ,
58,) mg/ mequlv
com bin a li o n. carbon has an a lomic m ass of 12 and a va lence of + 4. wh il e oxygen ha s
a n atomic m ass of 16 a nd a va lence o f - 2. Therefo re. th e radica l has a to tal valen ce of (il) I , One mo le o f a su bsl:ln cc di\ided by ils ;'a lence is o ne equ ivalent.
- 2 a nd an equivalence o f 2. One eq uiva len l o f carbo na-I e is
2 x 10 - .1 mo l/ L
12 + 3( 16) ..____ ..- - - - = 2 x 10 3 equi v/ L
- - - - = 30 g/ eq ui v I m o l/ equiv
2. The calcium Io n ha s an a to mic mass of 40 a nd a va lence o f + 2 , Ihe refore. o ne equ iva len t 2, Th us, 2 x 10 - .1 equi\ L x 50.GOO mg iequi v = 100 mg.' L
o f calcium is
40. Man y so lid su bs ta nces. particular ly th ose with crysta ll ine stru ctu re, io niz e
- = 20 g/ equi v
2 re adi ly in wat er. Wa ter m ayor ma y no t be a chel1) ical reac ta n t in th e process.
3. The number of eq lli valent s o r ~a lcium mu st eq ual the number of eq ui va lent s o f ca rbo n- I n Eq, (2-3), wa ter is a reactant. w hil e in Eq. (2- 4) it is not.
ale. th'ercfllre .
Ca O + H20 (2-3)
90 g .
..- ----- = 3 equ lv or carbo n ate
30 g; equiv NaC I + 11 /') (2- 4)
Thererore. 3 equi v x 20 g/ equiv = 60 g o f calc ium. a nd th a t amoun l w ill be required to
reac t wio h 90 g o f c'lr nl> na te. Wh en wat er is no t a reac t:lnl. it is c ust0m ar y to o mi t it fr om th e eq uati o n ,

If x is the I1ll1nhe r of moles of Mg2 + resulting from the disi;ociation . then OH - is

The double arrows in Eq. (2-4) indicate a reversible conditi o n. That is, the
equal to 2x . Therefore.
solid form (NaCl) may be dissociating into its io nic co mponents (dissolution), or
the ionic component s may be recombinin g int o the so lid fo rm (precipitatioll). [X][2XJ2 = 9 x 10 - 12
When the solid material is first contacted with water, the net reaction will be toward 4x J = 9 X 10.- 12
the ionic form. If a sufficient mass of solid is present. a condition of dynami c X = 1.3 x 10- 4 Illol/ L = Mg
equilibrium will be reached in which the rate of disso luti o n and the rate of pre- 2x = 2.6 x 10 - m o ljL = OH
cipitation will be exactly equal. At thi s pOint, the water is saturated with the
1.3 x 10 - 4 m o l/ L
dissolved species. 3. - - ----- - .- x 50..0.0.0.. mg!equiv = 13.0. mg,'L of Mg as CaCO J
Conditions of equilibrium can be expressed by the /"1I(/SS action equation. For ' 0..5 mol/equiv
the ge neralized reactio n 2.6 x 10 - 4 mol/ L
4. - - -- - -.- - x 50..0.0.0. mg/ equiv = 13.0. mg /L ofOH as CaC0 3
I mol/equlv '
A,Bv .\:A + vB
So lid compound lonie component s In addition to solid substances, many gases also dissolve in water. Elements
fr o m some of these gases may combine with water or with substances in the water
the mass action equation is to produce compounds or radicals that can be recovered in a solid form, thus
becoming a part of the dissolved-solids load. An example is carbon dioxide.
[AYEB}' (2-5)
- - -- K CO 2 + HzO H ZC0 3 I-J ' + HC0 3 - (2-7)
a nd
Tlie brackets around' t he io nic and so lid species ind icate molar co ncentrat ions. Th e (2-8)
K value is an equilibrium constant for a given substance in pure water at a given
Both the bicarbonate (HC0 3 - ) and carbonate (CO/-) are recoverable in solid
At equilibrium, the solid phase does not change concentrati o ns because fo rm.
dissolution and precipitation are equal. Thu s
Table 2-3 Solubility products of selected ion pairs
and [AY[B}' = KK , = Ksp (2-6)
K ,p al Significance in
. EqllilibTinm equatiun . . .. . . .. ... '25(" ...... . 'envrronmental errgineering' .... .. . ..... ........ .
The quantity K ,p is known as the solubility product for the io n pair. If the co ncentra-
tion of either or both o f the ions is increased, the prod uct o f th e ioni c concentration MgCO , ~ Mg' + + C O,' - 4 x 10 ' , Hardness remo va l, scaling.
will exceed the K sp and precipitation will occur to maJJ1t ain eq uilibrium co nditions. MgtOH), ~ Mg " + 20W 9 :x 10 - 12 Hardness rem oval. scaling
CaCO J ~ Ca" + CO J
.. , 5 x 10 - 9 Hardness remo va l, scaling
The solubility products for several substances common to natural water systems
C'utO H), ~ Ca" + 20H- 8 x 10 - b Hardness removal
are given in Table 2-3. Use of the solubilit y product to calculate ionic concentra-
CaSO., ~ Ca" + SO.
,. 2 x 10 - , Flue gas liesulfurization
tions is illustrated in the following example. Cu(O H), ~ Cu " + 20H 2 x 10 - 19 Heavy me tal removal
Zn(OH ), ~ Zn' " + 2 0H 3 x 10 - 17 Heavy metal removal
Example 2-4: Determining equilibrium concentrations The sol u bili lY prodllct for the NI(OH), ~ Ni ]+ + 20W 2 x 10 - I b H eavy metal removal
dissociation of Mg(OH), is shown in T a b.Ie 2-3 as 9 x I () - 12 De term ine Ih" co ncentra ("r(O I'/) , ;:"" C'r" I- lO H (, x 10 - 3J H eavy metal removal
AI( OI'l) J ~ AI' . + lO l r I x 10 - 32 Coagulation
t io n o f M g" a nd OH - a t eq uilibrium. ex pressed as milligra:ns pe r liler or (":1('0 3 ,
Fc(O H ), ~ Fe" + ,OW (, x 10 - j(, Coagulation, iron re m ova l. corrosion
Fc(O H) , ~ Fe" + 201-1 5 x 10 - " Coagulation, If all rem()\;!I, corrosion
SO l. UT IO N 1'v11l(O H ), ~ Mn" + ,OW I x 10 - Jb Manganese re mo val
MII(Ol-!) , ~ Mn " + 20W ~ X 10 " 1-> Mangane se removal
I. W rite the equa ti on for the reacti on C : , (PO.) , ~ 3Ca " + 2 P0 4
,- I x 10 " 27 Ph os phalc rem oval
CaHPO. ~ Ca" + HPO/ x 10 - 7 Phosphate rem ova l
Mg(OH) , == M g" + l O ll ' C a F , :.= Ca " I- 2 r -
.,. cr
.,x 10 - I I Flu o rid a li o n
I\ ~ ( 'I ~ Ag 3 x 10 - 10 Chloride anal ys is
2, The so lubil ity producl equa t ion becomes l~ aSU ., :.= Bal ' + SO.,' I x 10 - 10 Sulrale analysis

S o"r,l' : Adarleli from Sawyer and M cCa rt y. [212].


2-8 TOTAL DISSOLVED SOLIDS specific cOl/dl/cra l1ce, is a fun c ti o n o f its ionic str ength. Specific conductance is
meas ured by a co nductivit y me ter employing the Wheatstone bridge prjnciple.
The material remaining in the water after filtration for the suspended-so lid s The stand a rd procedure is to measure the conductivity in a cubic-centimeter
~~~I)'sisis considered to be dissolved. This material is left as a solid residue upon field at 25 C a nd express the res ul ts in millisiemens per meter (mS/ m).
evaporation of the water and constitutes a p a rt of total so lids discussed in Sec . U nfort un a tely, specific cond uc ta nce and concentration of TDS are not
2-2. re la led o n a o ne- Io-o ne bas is. Only io nized substances con tribute to spec ific
conductance. Organic mo lcc ules and co mpo unds that dissolve witho ut ioniz ing
are not measured. Additionally. t he magnitude of the specific conductance is
influenced by th e va lence of Ihe ions in so lution , their mobility, and relative
Dissolved material results from the solvent action of wa ter on so lid s. liquid s, a nd numbers. Th e te mperature a lso has an import a nt effect, with specific conductance
gases. Like suspended material. dissolved substances may be organic or inorganic increasi ng as I he water temp era l ur e increases. Conversion of units to milligrams
in nature. Inorganic substances which may be dissolved in water include minerals, per lit er o r milliequi valent s per lite r mus t be made by use of an appropriate
metals. and gases. Water may come in contact with these substances in the a tmo- constant. A multiplier ranging fr o m 0.055 to 0.09 is used to convert millisiemens
sphere, on surfaces, and within the soil. Materials from the decay product s of to milligrams per liter. [ 2-1 5J T o use spec ific co nductance as a quantitati ve test,
vegetation. from organic chemicals, and from the organic gases are common s ufficie nt anal ys is for filte ra ble residue must be run to determine the convers ion
organic dissolved constituents of water. The solvent capabi lit y of water makes it factor. For thi s reaso n. spec ific co ndu ctan ce is m os t often used in a qualitative
an ideal means by which waste products can be carried away from industrial se nse to mo nitor changes in TDS occ urring in natural streams or treatment
sites and homes. processes.

Impacts Use
Beca use no distinct io n amung the co nstituents is made. the TDS parameter is
Many dissolved substances are undesirable in water. Di ssolved minerals, gases.
and organic constituents may produce aesthetically displ eas ing co lor, tastes. and in clud ed in the a nal ysis o f wa te r and wastewater only as a gross measurement of
odors. Some chemicals may be toxic. and some of the dissolved organic con- th e disso lved material. Whil e this is o ft en sufficient fo r was tewaters, it is frequently
stituents have been shown to be carcinogenic. Quite often , two or more dissolved des irable to know more about th e co mp os ition of the solids in water that is in-
tended for use in p otabl e suppli es. agric ultur e. and some industrial processes.
substances-especially organic substances and members o f the halogen group -
will combine to form a conlpound whose characteristics a're' mO ore" obje<iioriaofe -.. , .. ' .. ,.. .. -' .. . When th is isthecase: tests forseverat 'Oflhc'j'onic CO"m;(rtuents of TDS are made.
than those of either of the original materials.
Not all dissolved substances are undesirable in water. For example. essentiall y Ion Balance
pure. distilled water has a flat taste. Additionally, water has an equ ilibrium state The ions us ually acc o unting fo r th e vas t maj o rity of TDS in natural waters arc
with respect to dissolved constituents. An undersaturated water will be" aggres- listed in Tab le 2-4. Those Ii.<;ted uncler maj o r constituents a re often sufficient to
sive" and will 'more readily dissolve materials with which it comes in contact.
Readily dissolvable material is sometimes added to a relativeJy pure water to
Table 2-4 Common ions in natural waters
reduce its tendency to dissolve pipes and plumbing.
Major con stituen ts, Secondary co nstituents.
1.0- 1000 mg! L O.O t I O.n rng . L '
Sodium fron
A direct measurement of total dissolved solids can be m ade by evaporat ing to
Catcium StrollliUn1
dryness a sample of watet which has been filtered to remove the suspended solids. M agnesium Potassiulll
The remaining residue is weighed and represent s th e IOwl dissolved solids (T DS) Bien rbona Ie Car bonale
in the \vater. The TDS is expressed as milligrams per liter o n a dry-ma ss basis. Sutfal c Nltrale

~ ..... The organic and inorga;1ic fractions can be determined by firing the residue at Chloride Flu or1(k
BL)r On
600 ~ C as discussed in Sec. 2-2.
S, i1 Cl
An approximate analysis for TDSis often made by determining the electrical
conductivity of the water . The ability of a water to conduct electricity. kno\\'n ;I S th e

characterize the dissolved-solids content of wa ter. These are called common ion s It is important to arrange the cations and anions in the order shown for convenience
and are often measured individually and summ ed on an eq ui valent basis to in determining types of hardness and the quantities of chemicals needed for
represent the approximate TDS. As a check , th e sum of th e anions should equal so ftenin g, a subject m o re fully developed in a later chapter of this text.
th e sum of the cations beca use electroneutralit y must be preserved. A significan t Several of the constituents of dissolved solids have properties that necessitate
imbalance suggests that additional cons tituents are present o r that a n erro r has specia l .attenti on. These constituents include alkalinity, hardness, fluoride, metals,
been made in th e ana lys is of o ne or more of th e iOIlS . The fo ll owin g exam ple organics, and nutrients.
illu stra tes the io n balance p roced ure.
Example 2-5: Testing for ion balance Tes ts for common ions are run o n a sam ple of
wa ter and the results are show n be low. If a 10 perce nt e rror in the bala nce is acce pt ab le, 2-9 ALKALINITY
should the analysis be co nside red complet e?
Constituent s Alkalinity is defined as the quantity of ions in water that will react to neutralize
Ca' > = 55 mg/ L HCO , - = 250 mgl L hyd rogen io ns. Alkalinity is thus a measure of the ability of water to neutralize
Mg2+ = 18 mg/ L SO.' - 60 mg/ L acid s.
Na + = n
mg/ L C I = 89 m gi L

l. Conve rt the co ncen tra ti o ns of cations a nd anions fr o m milli grams per lit er to milli-
equ iva lents per liter and slim them . Constituents of alkalinity in natural water systems include C0 32 - , HC0 3 - ,
- - - - . - - - - - - - - --- - - - - _. _ - - - - - - -- - - - - OH - , HSi0 3 - , H 2 B0 3 - , HPO/ -, H 2 P0 4 -, HS -, and NH30 [2-3] These
Ca ti ons Anion s compound s result from the dissolution of mineral substances in the soil and
a tm osphere_ Phosphates may also originate from detergents in wastewater
[on Cone , Equiv , Eq uiv co ne, Ion Cone , E4Uiv , Equiv cone, discharges and from fertilizers and insecticides from ag ricultural land. Hydrogen
mg/ L mg/ mequiv meq / L mgi L mg/ m ~ quiv m ~q ui v/ L sulfide and ammonia m ay be products of microbial decomposition of organic
Ca 2 , material.
55 40/ 2 2.75 HCO , - 250 6 1/1 4.10
M g2+ 18 243/ 2 1.48 SO.
60 96/ 2 1.2 5
By far th e most co mmon constituents of alkalinity are bicarbonate (HC0 3 -),
Na+ 98 23/ I 4.26 cr 89 ... 355 / I . . .. . 2.5 1 ca rb onate (CO/ - ), and hydr oxide (OH - ). In addition to their mineral origin,
- these su bstances can originate from carbon dioxide, a constituent of the atmosphere
T o tal io ns 8.49 786
and a product of microbial decomposition of organic material. These reactions
a re as fo llows:
2. Calcu la te percent of er ror.
8.49 - 7.86 CO 2 + H2O H 2 C0 3 * (dissolved CO 2 and
- - - - 100 = 8~" (2-9)
7.86 carbonic acid)

H2C0 3 * H+ + HC0 3 - (bicarbonate) (2-10) .

Therefo re, accept ana lysis.

A co mm o n iOIl balance can be displayed conve ni en tl y in th e form of a bar

HC0 3 -: H+ + C0 3 2 - (carbonate) (2-11 )
diagram. A bar diagram for th e water in Example 2-5 ca n be drawn as shown be low. +
CO/ - + H 2O H C0 3 - OH - (hydroxide) (2-12)

rn c(juiv / L 0 2.75 4 . )':\ The reaction represented by Eq. (2-12) is a weak reaction chemically. Howev:er,
ut ilization o f th e bicarbonate ion as a carbon so urce by algae can drive the reaction
to th e ri ght and resu lt in su bstanti a l accum ulati o n of OH - .. W ater with heavy
a lga l g rowths often has pH va lues as high as 9 to 10.
!-l eo ) (T Because the reac ti ons represented by the above equations invo lve hydrogen or
hyd roxide ions, the rela ti ve qu a ntities of the alkalinity s pecies are pH dependent.
m e'll/iv, L 0 4.10 5.3:' ! .Xh These relatio nships a re show n graphically in Fig. 2-3.

r-- ~ 14

1\\ 12

HC0:i 10
....l 70
O~ 60 \ / r\ 1:
olr +, CO/~

,l -
U .50 \ \/ \ 6

~ CO/~ HCO:;
,S 40 / 'L 4

I I +
30 \ / \ / oL----------------------------------------------------
\ C0 3 ! \/ Milliliters of titrant
20 Figure 2-4 Alkalinity titration curye

10 \ "- B 2 C0 3 '
V J\ If acid is added slowly to water and the pH is recorded for each add it ion, a
[7 OW V \
~ V titration curve similar to that shown in Fig, 2-4 is obtained, Of particular significance
are the inflection points in the curve that occur at approximately pH 8,3 and pH 4.S,
6,5 7 7.5 8 8.S 9 9.5 10 10.5 II
The conversion of carbonate to bicarbonate [Eq. (2~14)J is essentially complete
at pH 8.3. However, because bicarbonate is also an alkalinity species, an equal
Figure 2-3 Alkalinityspecies vs. pH. Values are calculated for water at 25C containing a total alkalinity amount of acid must be added to complete the neutralization. Thus, the neut r aliza~
of 100 mg/L as CaC03. (From Sawyer and McCorry [2-12].) tion of carbonate is only one~half complete at pH 8.3. Because the conversion of
hydroxide to water is virtually complete at pH 8.3 (see Fig. 2~3)..all ()ft.h.e )ly~r9xide.
and one~half of t.he carbonate have been measured at. pH 8.3. At pH 4.S all of the
Impacts bicarbonate has been converted to carbonic acid [Eq. (2~ I S)], including t.he
In large quantit.ies, alkalinity imparls a bitter taste to water. The principal ob~ bicarbonat.e resulling from t.he reaction of t.he acid and carbonate [Eq. (2~14)].
jection to alkaline water, however, is the reactions that can occur between alkalinitv Thus, t.he amount of acid required to titrate a sample to pH 4.S is equivalent to the
and certain cations in the water. The resultant precipitate can foul pipes and othe-r total alkalinity of the water. This 'point is i1iustra'ted in t.he following example.
water-systems appurtenances.
Example 2-6: Determining total alk'alinity A 200~mL sample of water has an initial pH.
of 10. Thirty milliliters of 0,02 N H 2 S0 4 is required to titrate the sample to pH 4.5.
Measurement What is the total alkalinity of Ihe waler in milligrams per liter as CaCO,')

Alkalinity measurements are made by titrating the water with an acid and de- SOI.ti nON
termining the hydr9gen equivalent. Alkalinity is then expressed as milligrams per Because each rnilligr;llll of ().02 ;V H 2 SO'4 will neutralize I Illg of alkalinity. t h ere IS
Ii.ter ofCaCO J . If 0.02 N H 2 S04 i~ used in the titration, then 1 mL of the acid will 30 rng of alkalinity in the 200-nlL sample. Therefore. the concentration of alkalinity
neutralize 1 mg of alkalinity as CaC0 3 . Hydrogen ions from the acid react with expressed as milligrams per lite'r will he
the'alkalinity according to ihe following equations:
30 mg 1000 rn L
H+ + OH- x 150 mgj L
H 20 (2-13) 200 Illl L
C0 3 2 - + H+ HC0 3 - (2-14) If the volume of acid needed to reach the 8,3 endpoint is known. the spec ies of
HC0 3 - + H+ H1CO, (2-15) alkalinity can also be determined. Because all of the hydroxide and o n e~half

of the carbonate have been neutralized at pH 8.3, the acid required to lower the Use
pH from 8.3 to 4.5 must measure the other one-half of the carbonate, plus all of the Alkalinity measurements are often included in the analysis of natural waters to
original bicarbonate. If Pis the amount of acid requ ired to reach pH 8.3 and M determine their buffering capac ity. It is also used frequent ly as a process control
is the total qLiantity of acid required to reach 4.5, the following genera lizations variahle in walt;r and wastewater treatment. Maximum levels of alkalinity have
concerning the forms of alkalinity can be made: not been set by EPA for drinking water or for wastewater discharges.
if P = i'vI, all alkalinity is OH -
P = M / 2, all alkalinity is CO/-
P = 0 (i.e .. initial pH is below 8.3), all alkalinity is HC0 3 - 2-10 HARDNESS
P < M ; 2, predominant species are CO/ - and HC0 3 -
P > M / 2, predominant species are OH - and CO/ - Hardness is defined as the concentration of multivalent metallic cations in solution.
At supersaturated conditions. the hardness cations will react with anions in the
In observing the pH dependency of the species in Fig. 2-3, it is noted that the water to form a so lid prec ipitate. Hardness is classified as carbonate hardness and
quantity of OH - becomes significant at pH less than about 9.0. Without intro- l1oncarbonate hardness, depending upon the anion with which it associates. The
ducing significant error, it can be assumed that the OH - of samp les with pH hardness that IS equivalent to the alka linity is termed carbonate hardness, with
less than 9.0 is insignificant. The CO/- would then be measured by 2P and the any rema ining hardness being called noncarbonate hardness.
HC0 3 - would be measured by the rema inder (M - 2P) One method of calculat- Carbonate hardness is sensitive to heat and precipitates readiiy at high
ing the quantities of ea~h species is illustrated in the following example. temperatures.

Example 2-7: Determining alkalinity species Determine the species , al~lI Ihe quantity of Ca(HCOJ)z ~ CaC0 3 + CO 2 + HzO (2-16)
each specie, of alkalinity in Example 2-6 if the 8.3 equivalence point is reached at II mL
of acid.
Mg(HCO J )2 ~ Mg(OH)z + 2CO z (2-17)

Becallse the initial pH is 10, the initial pOH of the water is4. A Jeterl1linatio ll of the OH . The multivalent metallic ions most abundant in natural waters are calcium and
concentration can be made as follows. magnes ium. O t hers may include iron and manganese in their reduced states
(Fez +, M n 2+), stront ium (Sr2+), and aluminum (AI3+). The latter are usually
10 - 4 mol OH- I equi\ 50,000 mg CaCO, . fo'uiioinriiuch .smaI1er' 'cjllaiiiiii'es' 'thaii' cafCiu'iri--ilno--mag'nesiurrCarld' ro"i--:ilJ ....
[OW] = --'---L -- x ;;;;1 OH- X -I cqulv-- -
practica l purposes. hardness may be represented by the sum of the calcium and
= 5 mg/ L as CaCO,
magnesium 19ns.
2. Five milli!Jters o f acid would be required to measure the OH - in a I-L sample. H ow-
ever. this sample is only 200 mL so the necessary volume of acid is:
Impacts .
5 --- = 1.0 mL . Soap consumption by hard waters represents an economic loss to the water usee
Sodium soaps react with multivalent metallic cations to form a precipitate, thereby
3. If I mL of acid measures the OH -. then 10 mL of acill measures one-half of the carboll- losing t heir surfactant propert ies. A typical divalent cation reaction is:
ate and 10 more will be required to measure the remaining one-half of the CO /-,
leaving') mL to measure the HCO) - . (See Fig. 2-4.) Thus. the quantity of each species 2NaCO/_~ 1 7 H33 + cation 2+ ---> cationz+(COzCI,H33)z + 2Na+
is as follows. Soap Precipitate (2-.18)
OH - (calculated from pH) '= 5 mg i L Lathcring does not occur until all of the hardness ioils are ~recipitated, at which
20 mg 1000 mL
point the water has been" softened" by the soap. The precipitate formed \;ly har~
CO , = x 11l(J mg , L ness and soap adheres to surfaces of tubs, sinks, and dishwashers and may stam
. 200-mL L
clothing, dishes, and other items. Residues of the hardness-soap precipitate may
I) mg 1000 IIlL remain in the pores. so that skin may feel rough and uncomfortable. In recent
HCO J - .. _. x .15 mg i L
200 mL L years these problems have been largely alleviated by the development of soaps
Total albllnity 150 Il1g ' L Glnd detergents that clo not I'cact with hardness.

Boiler scale, the res ult of the carbonate ha rdness precipitate ma y ca use o ther anima ls in large quantities, wh ile small concentra tion s can be beneficial.
considerable economic loss throu gh fouling of water heaters and hot-wa ter pipes. Concen trati o ns of approx imat ely 1.0 mg/ L in drinking wa ter help to prevent
Changes in pH in the wa ter distribution systems ma y also result in deposits of dental cavi t ies in ch ildren. During fo rm ation of permanent teeth , flu o ride co mbines
precipitates. Eicarbonates begin to convert to the less so lu ble carbonates at pH chem ica lly with too th e namel. resulting in ha rd er. stro nger teeth that are more
val ues above 9.0. res istant to decay. Flu o rid e is often added to drink ing water suppl ies if sufficient
Magnesium hardness, particularly assoc ia ted with the sulfa te ion. has a quan titi es fo r good dental format ion are not natura lly present.
laxative effect o n perso ns un acc ustomed to it. Magnesium concentrati ons of less Ex cess ive JJ1tak es of flu o rid e ca n res ult in discolo ra ti o n of teeth. Noticeable
than 50 mgj L are desirable in pot a ble wa ters, alth o ugh ma ny public wa ter supplies disco lora ti o n, ca ll ed mOl/lillY. is relat ive ly common when fluoride concentrations
exceed thi s amount. Ca lcium hardness p rese nts no public health .prob lem. In in drinking wa ter exceed 2.0 mg/ L but is rare whe n co ncentrat io ns are less th a n
fac t: ha rd water is appa rentl y beneficial to the human ca rdiovascul ar system. [2-4J 1.5 mgj L Adult t ~e th are no t affect ed by flu oride. a lth ough both the ben efit s and
li abili ties of fluorid e during too t h-for mati o n years ca rr yove r in to ad ulth ood .
Excess ive dosages of flu o rid e can a lso result in bone flu o ros is and other skeleta l
abno rma liti es. Co ncentration s of less than 5 mgj L in drinkin g wa te r are no t lik ely
H ardness ca n be measured by using spect rop ho tome tric techniqu es or chemica l to ca use bon e flu oros is o r related pro blems, and so me wa ter supplies-a re known
titration to determine th e quantity of calcium a nd magnesium io ns in a give n to ha ve so mew hat hi gher flu oride co ncentrat ion s with no disce rni ble pr051 em
sample. Hard ness can be measu red directl y by titrati o n with eth ylenediam ine other than severe mottl;n g of leelh . On the assum pti o n tha t peop le drink mo re
tetraace t ic acid (EDT A) using eri oc hrome bl ack T (EBT) as a!' ; ~ .. . .. , .. _ LD J wate r in warmer clim a tes, EPA drinkin g-wale l' sta nd a rd s base upper li mi ts fo r
reacts wi th th e divalent met a llic cat io ns. forming a comp lex th at is red in co lo r. fl uor id e o n ambien t temperatures. Th ese standard s a re d isc ussed mo re fu ll y in
The EDT A replaces the EBT in the co mpl ex, and when the replacement is complete, Sec. 2- 18.
th e so luti on changes from red to blue. If O.O J M EDTA is used, 1.0 mL of the
titra nt measures J.O mg of ha rdness as CaC0 3 .
All meta ls are so lu ble to some exten t in wa ter. While excess ive a m o unts of a ny
Analysis for hardness is co mm o nly made on na tura l waters and o n wa ters in-
meta l may present hea lth haza rds. o nl y th ose metal s tha t a re harmfu l in relati ve ly
tended fo r potable suppl ies and fo r certain indu stri al uses. Hardness ma y range
.... small ly.labeled .t ox ic : oth er meta ls fa ll int o th e no ntox ic
fro m practically zero to severa-j. hundred; 'or 'even ' several ' thou sand; 'IYaYts per '
grou p. So urces of meta ls in natura l waters inc lude disso luti o n from na tural
million . Although accep ta bility leve ls vary acco rding to a co nsumer's acclim at io n
deposits a nd discharges of d omes tic. indu stria l. or ag r icultura l wastewaters.
to hardness, a generally accepted class ifica ti on is as follows:
Meas urement of me ta ls in wat er is usua lly mad e by atom ic abso rpti o n spectro-
ph otometry.
So I'l . < 50 mgi L as C"CO,
Mod e ral e ly hard . 50-- 150 mg i L as CaCO,
Hard. 150-300 mg/ L a s CaCO,
Very pard > 300 mg; L as CaCO,
Nontoxic Metals

In add iti o n to the hard ness ions. calc iulll and magn esi um. o th er no ntox ic meta ls
The Public Health Service 'standards recommend a maximum of 500 mg/ L co mm o nl y found in wa ter include sodium. iron. manga nese. a lu minum, copper.
of hardness in drinking water. [2-18J A ma xi mum limit is not set by the EPA and zinc. Sodium. by rar the mos t cOlllmon no nt ox ic Illetal fo und in natural waters,
standa rd s. IS ~Ib un e!ant in the ea rth 's crust ~I nd is highl y reac ti ve wi th oth er elements. Th e
sa lt s o f sodium are ve ry so lub le in water. Excessive co ncentrat io ns ca use a bi tt er
taste ."l wa ter a nd are" health halard to'cardJ< lc and kidne y pati ent s. Sodium is
2-11 FLUORIDE also co rros ive to Ill etal surfaces and . III large co nce ntrati o ns. is tox ic to p lant s.
Ir on ;lJld ma nga nese quit e fr equentl y occur toge ther a ne! present no health
Generally associated in na ture with a few types of sedim entary or igneou s rocks. h ~l Z~ \r(i s a t co ncentratiollS normilily f'nli lld ill natur;l l wa ters. As no ted in Sec. 2-4.
fln or ide is seldom found in appreciable qu a ntities in surface wa ters and a ppears in iron an e! man ga nesc in vc ry small quantities Illay cau se co lo r pro blems. Iron
gro undwate r in on ly a felY geograph ical regio ns. F lu or id e is toxic l\) humans and C (ln C<: l1tr ~ ltl()n S of 0.3 Ill g/ L. and ma nganese cnnce ntr atioJls as low as 0.0 5 mg/ L

can ca use co lor problem s. Additionall y, so me bacteria li se iron and man ga nese dissolved form. these materials usually consist of starches, fa ts, proteins, alcohols,
co mpounds for a n energy sou rce, and the resulting sli me grow th may prod uce acids. a lde hydes. a nd esters. They may be the end product of the initial microbial
taste a nd odo r problems. decomposition of pla nt oranimaHissue, or they may result fr o m domestic or
Wh en significant quant ities of iron are enco untered in natura l wa ter sys tems. industrial wastewater discharges. Although some of these materialS can cause
it is usuall y assoc ia ted with chloride (FeCI2). bicarbo nate [Fe( HC0 3)2]' o r co lo r, tas te, a nd odor pro blems. the principal problem associated with bio-
s ulfate [Fe(S04)] anions a nd exists In a reduced state. In the presence of oxygen, degradable organics is a secondary effect resulting fr o m the acti on of micro-
the ferrous (Fe 2 ' ) io n is ox idized to the ferric (Fe J +) io n a nd forms an insoluble o rganisms o n these substances.
co mpound wi th hydroxide [ Fe(O Hhl Thu s. signifi can t quantiti es of iron wi ll Mi cro bial utilization of dissolved organics can be accompanied by ox'idation
usua ll y be found o nl y in systems devoid of oxygen such as gro und wa ters or per- (addition of oxygen to, or the deletion of hydro gen from, elements of the orga'nic
haps th e bo tt om layers of stra tified lakes. Simi la rl y. manganese ions (MnH and molecule) or by redu ct ion (addition of hydrogen to, or deletion of oxygen from,
Mn..) ' ) associa ted wi th chlo ride, nitrates . a nd su lfat es are so luble, wh ile ox idized elements of the o rganic molecule). Although it is possible for the two processes
compou nd s (M n J , and M n 5 +) a re virtually insolu ble. It is poss ible. however, for to occur simultaneously, the ox id ation process is by far more efficient and is pre-
o rganic acids de ri ved fr om decomposing vege tation to c he lat e iro n and ma nga nese dominant when oxygen is available. In aerobic (oxygen-present) environments,
and prevent their ox idat ion a nd subseq ueht p rec ipit a ti on in natu ra l wa ters. the end products of microbia l decompositio n of organics a re stable and acceptable
"The other no nt ox ic metal s are ge nerally found in ve ry sm all quantities in co mpou nds. Anaerobic (oxygen-absent) decomposition results in unstable and
natura l wate r sys tem s. and most wou ld ca use ta ste probl ems lo ng befo re toxi c objectionab le end products. Should oxygen later become ava ilable, anaero bic
len.: ls were reached. Howeve r. copper a nd zin c are sy nergetic and when both a re end product s wi ll be ox idized to aerobic end products. The oxygen-demanding
present. even in small quant iti es. may be tox ic to Illany bio logica l spec ies. nature of biodegradable orga nics is of utm ost importance in na tural water systems.
Wh en oxygen utilizat io n occurs more rapidly than oxygen can be replenished by
Toxic M etals transfer from the a tm osp here, anaerobic conditions that seve rely affect the ecology
of the system will resull. This situation is cove red in more detail in the next chapter.
As noted earlier. toxic meta ls are harmful to huma ns and other urgan isms in The a mo unt of oxygen co nsumed during microbial utilization of o rganics
sm:t11 quant ities. TOX IC meta ls that may be disso lved in wa ter IIl clud e arsenic. is called the biochemica l oxygen demand (BOD). The BOD is measured by de-
barium. ca dmluill. chro mium , lead, mercury. and sil ver. C umulative toxin s such as termining the oxygen co'nsumed from a sample placed in an air-tight container
arsenic. cadmluill. lead. a nd merc ur y a re particu la rly hazardous. Th ese metals are and kept in a con tro lled environment for a prese lected period of time. In the
concentrated by the food cha in . thereby posing th e g rea tes t dan ge l' to orga ni sms sta ndard test: a 300-mL BOD bottle is used and the sample is incubated at 20C
. ' ric',ii" t he lOt>' (~ t' The' th,i j ii. for 5 days. Light must be excluded from the incuba to r to prevent a lga l growth that
Fort una tely. toxic meta ls are present in o nl y minute quant it ies in most na tural may prod uce oxyge n in .the bo ttle. Because the saturati on concentration for
water sys tems. Alth o ug h natural sources of all th e tO XIC me ta ls exist, signifi ca nt oxygen in water at 20C is approx imately 9 mg/ L. dilution of the sa mple with BOD-
c()nu.:nt ration In "ate r can usuall y be traGed to mini ng. industrial. or agricultural free, o xygen-sa turated water is necessary to measure BOD va lues greater than just
Sllurces. a fe w milligrams per .liter. . '.. .
Th e BOD of ad iluted sam ple is calculated by
2-13 ORGANICS BOD = 001 - DO F (2-19)
Many organic materia ls are so lu ble in water. Organics in na tur'al water systems
mCl)' come from natural sou rces or ma y resu lt fr om human activities. Mo st na tura l where 001 a nd DO F are the initial and final di ssolved-ox ygen concentrations
o rganics consis t of th e decay products of organi c s.o lid s, wh ile synth etic o rga ni cs (mg/ L) and P is the decimal fracti o n of the sa mple in the 300-mL bottle . .
are usual ly the resu lt of was tewa t.e r discharges or agricultura l practices Di sso lved Ran ges of BOD covered by various dilution s are shown in Table 2-5. These
o rg,l nics in \va ter are usuall y divided int o two broad categor ies': biodegrada ble val ues ass ume an initial dissolved-oxygen concentration of9 mg/ L in the mixture.
and n()no io(/cg radable {refractory). ' with a minimum of 2 and a max imum of 7 mg/ L of O 2 being consumed . Calcula-
ti o ns of BOD s from this testing procedure a re mustrated in the foll ow ing example.
Biodegradable Organics Example 2-8: Determinin g BOD ) The BOD of a wastewa ter is suspected to range from
HICldegr'adahlc ll1ateri~ t1 consists of o rganics t hat call he utilized for food by 50 to 200 mgjL. Three dilutions are prepared to cover thIS range. The procedure is the
l1~ltLII;lIh llcclirring mlul)() rganisms \\'ithin a reasonahle lengrh (If time. In same in cach casc. First the sample is placed in the standa rd BOD bo ttle and is then

Table 2-5 Ranges of BOD values covered by utilized is propo rtional to the amo ttnt available. Mathematically, this can be
various dilutions expressed as follows:
By direct pipetting into elL,
By using percent mixtures 300-mL bottles - kL, (2-20)
J~ mixture Range of BOD .mL Range of BOD
where L, isthe oxygen equivalent of the organics at time 1, and k is a reaction Con-
0.01 20,000-70,000 0.02 30,000-105,000 sta nt. The units of L, are milligrams per liter, and the units of k are d- 1.
0.02 10,000-35,000 0.05 12,000-42,000 Equation (2~20) can be rear ranged and integrated as follows:
0.05 4,000- 14,000 0.10 6.000-21,000
0.1 2,000-7 ,000 0.20 3,0007 10,500 elL,
0.2 1,000-3,500 0.50 1,200-4,200 - = - k ell
"' 0.5 400-1 ,400 1.0 600-2,100
1.0 200-700 2.0 lOO-I,050
2.0 100-350 5.0 120- 420
5.0 40- 140 10.0 60- 210 Lo L,
10.0 20-70 20.0 30- 105
20.0 10-35 50.0 12- 42 L,
4- 14 1000 6- 21 In - - = - kl
50.0 Lo
100.0 0-- 7 300.0 0- 7
L, = L OI.'.-k' (2-21 )
Source: From Sawyer and McCarty, [2-12J
The term Lo in this equation represe nts the total oxygen equivalenl of the organics
at time 0, while L, represents th e amount remaining at time r, and decays ex-
diluted to 300 mL with organic-free, oxygen-saturated water. The initial dissolved ponentially with time, as shown in Fie. 2-5.
oxygen is determined and the bottles tightly stoppered and placed in the incubator at The oxygen equivalent remaining is not the parameter of primary importance.
20C for 5 days, after which the dissolved oxygen is again determined. .
However, the amount of oxygen llsed in the consumption of the organics, the BOD"
can be found from the L, value. If Lo is the oxyge n equivalent of the total mass of
... Wastewater , DOl , DO" O 2 used, BOD ,.
mL mg/ L mg/ L mg!L p mg/L

5 9.2 6.9 2.3 0.0167 138

10 9.1 4.4 4.7 0.033 142
20 8.9 1.5 7.4 0.067 110
If the third value is disregarded (the final DO being less than 2.0 mg/ L), th e average
BOD of the wastewater is 140 mg! L.

Most natural water and municipal wastewaters will have a population of

microorganisms that will consume the organics. In sterile waters, microorganisms
must be added qnd the BOD of the material containing the organisms must be
\' determined and subtracted from the total BOD of the mixture, The presence of
toxic materials in the water will invalidate the BOD results.
The BODs only represents the oxygen consumed in 5 days. The total BOD . .
or BOD for any other time period. can be determined provided additional informa-
Tim e days
tion is known or obtained. The rate at which organics are utilized by micro-
organisms is assumed to be a first-order reaction: that is. the rate at which organics Fi:!lIrr 2-~ non and oxygcn-t;: qul\a lc!l1 rdaliO n shir~ .

orga nics. then the difference between th e va lue Lo a nd L, is iht: l)xygen equivalent Table 2-6 Typical values of k and Yu for various
cons um ed. o r th e BOD exe rted . Mathematicall y waters

)" ~ L o - L, k. d - I
WJlc r Iype base t' mgL .
)" Lo - L ot'
Tap water <0. 1 0- 1.
.\' , Lo(l - e - kl) (2 -22) Surface waters 0. 1- 0.23 1-30
Wea k municipal wastewater 0.35 150
wh ere )" represents th e BOD, of th e waler . Th e va lu e of v, approaches Lo
Strong municipal wil ~ te\Valer 0.40 250
asymptotica lly. indica ting that ' the total. or ultim ate, BOD (v..) is eqUid 10 th e Trea led efll lleni 0. 12.. 0.23 10-30
initial oxygen equ iva lent o f th e water Lo. Th ese relationships are shown in Fig.
Equati o n (2-22) represen ts the BOD exe rted by the carbo n compo nent of The use of Eqs. (2- 22) and (2-23) is illustrated in the foll ow ing example.
th e o rgani c co mpo unds. Other co mpo nents of orga n ics, such as nitroge n and sulfu r,
ma y also be ox idi zed by microorganisms. resulting in a n oxygen demand . Equatio ns xamPJe 2-9: BOD conversions The BOD 5 of a wa stewa ter is determined to be J 50 mg/ L
sim ilar to Eq. (2-22) ca n be derived for these reactio ns. at 20C. The k va lue is k fl o wn tll be 0.23 per da y. What wou ld the BODs be if the test
The va lu e of J.:. de termin es the speed of the BOD reaction wi thout in flu encing were rUIl at I S" C'.'
th e m,lgnitude of th e uftim ate BOD. This iss howll grap hi ca ll y ill Fig. 2-6. Numerica l (
values ~f J.:. ran ge fr o m abo ut 0.1 to 0.5 d - '1 depending o n the nature'of the orga ni c OLl'T ION

mo lec ul es. Simple compounds such as sugars and starches are easi ly utilized by the
microorganisms a nd ha ve a high J.:. ra te, while co ~nplex mo lecu le's such as phenol s I. Determine the ultimate BOD.
a re difficult to ass im il a te an d have low k n du es. S(,lme typica l va lu es of k are show n r
in Tab le 2-6. r =I --
U_ e-- 1a
The \'a lu e of k for any given o rgani c compound is temperature-depend ent.
Beca use microo rganisms a re mo re ac ti ve at highe r temperatures. th e va lu e of k 150
I__ -e--~s
increases wi th increasin g temperatures. The c han ge in k can he approxima ted by
the \ an't H o fl~Arrhe niu s model: .. =. 220 .mgj L. .. . ..... ... ....... ........ .

(2-23) 2. Correct the k va lue for 15C.

i\ va lu e of 1.047 for 0 is o ft en ~I se d a lth o ugh (I is known t'o \'ar: sll lllC\\l!at with
te mperature ra nges. [2-8J
k " = 0 23( 1.04r 5)
= 0. 18

J. Calcu la te)'8
,l ', = .1',.( I _ e- k ')

.1'" = 220 (I _ (' - 0 . 1 8 8 )

168 mg !L

Nonhi odegradabl c Organics

So me organ ic materials are resis tant to bio log ical degradation. Ta nnic and lignic
acid s. ce llulose. and phen ols are o ft en fo und in natural wa ter systems. These
co nstituen ts of woody plant s biodegrade so slow ly that they are usually con-
sid ered refractor y. Mo lecules with excep tio nall y stro ng bonds (some of the poly-
J-'i g ll l"(' 2-6 Ij O I) l"\L' / (1\'11 ;1 ') a lunction of reaction \..'11I1 S (;\nl /.: sacc harides) and ringed struc tu res (benzene) are essen ti a lly non bi odegradable.

An example is the d etergen t compound a lkyl benzene su lfo na te (ABS) w hich, discharges o r tlame inc in era ti o n) to fo rm nitrogen ox ides. A lth o ugh a few bio-
with its benzene ring, does no t biod eg rade. Being a surfactant, A BS ca uses frothin g logical spec ies are a ble to ox idize nitrogen gas. nitr oge n in th e aql:atic environ-
and foaming in wastewater tre a tment pla nts and increases turbidit y b y stab iliz ing ment is derived prim a rily from so urces o th er than atmospheric nitrogen.
colloidal suspensions, Thi s problem was largely alleviated when detergent manu - Nitrogen is a consti tLi en t of proteins, ch lorophy ll, and many o th er biologica l
facturers switched to a linear a lk yl sulfonate (LAS) compound, whi ch is bio- co mp o und s. Upon the dea th of plants or anima ls, complex orga nic ma tter is
degradable. Many of the organics assoc iated with petro leum a nd with it s refining broken d ow n to simple fo rm s by bacteria l decomposition. Pro teins, for ins tan ce,
a nd processing also contain benzene a nd are essentially non bi o d eg rada ble. are conver ted to am in o ae id s and further red uced to ammo ni a (NH3)' If oxygen is
Some organics are n o nbi odegrad a ble because they are toxic to organisms. prese nt, the ammon ia is oxid ized to nitrite (N0 2 - ) a nd th en to nitrate (N0 3 - ).
These include the organic pesticides, so me industrial chemicals, and hydrocarbon Th e llItrate ca n then be reco ns titut ed in to li ving organic matter by photosynthetic
co mpounds that have co mbined with chlorine. plants.
Pesticides, including insecticides a nd herbicides, have found wide-spread Other sources o f nitrogen in aquatic systems include anima l was tes, chem ical
use in modern society in both urba n a nd agricultural settin gs. P oo r application (part icu lar ly c hemica l fer tili ze rs), and wastewater discharges. Nitrogen from
prac tices and subsequent washoff by rainfall and run o ff m ay result in co ntamina- th ese sou rces may be disc ha rged di rect ly into strea m s or ~ay enter waterways
ti o n.of-s.~rface streams. Orga nic insec ti cid es are usuall y chlorinated hydroca rb o ns through surface run off o r groundwa ter discharge. N itrogen com pounds ca n be
(i .e., a ldrin, dieldrin. endrin, a nd lindane), while herbicid es are usua ll y c hl oro- oxid ized to nitrat e by so il bac te ri a a nd ma y be carried int o th e gro und wa te r by
phenoxys (e.g., 2A-dichlorophenoxyaceti c acid and 2.4,5-trichlorophenoxy- perco latlllg wa ter. Once in th e aq ui fe r. nitrates move fr ee ly with th e g round wate r
propionic acid). Many of the pesticides are cumulative tox ins and cause severe Aow. Grou~dwater co nt a min at ion by nitroge n from animal, feed lo ts and sep ti c -
problems at the higher'end o f th e food c hain . An example is th e nea r-extinction o f tank d rain field s ha s heen record ed in numer o us in sta nces. [ 2- 10,2- 11, 2- 13J
the brown pelican that fe ed s o n fi sh and o ther macr oaq uatic spec ies by the in- I n adchtlon to the overennchme nt p roblems a llu ded to earlier, nitrogen can
sec tic ide DDT, the 'u se o f which is now banned in the United States. h3ve o the r se riou s consequences. Ammon ia is a gas at tempera tures a nd pressures
Measurement of no nbi odeg rad able orga nics is usuall y by the chemical oxygen normally found In natural wa ter sys tems. The gas (N H )) exis ts in equilibriulTl
d emand (COD) test. Non bi o deg rad ab le o rga nics m ay a lso be estimated fr o m a With the aqueous ion ic fo rm called ammo nium (N H .. +).
to ta l organic carbo n (TOC) analys is. Both COD and TOC meas ure the bi o-
(2-24 )
-. degradable fraction o f the o rga ni cs, so the BOD" must be subtracted fr o m the
COD or TOC to quantify the non biodegradable o rganics. Specific o rga ni c com- The hydroxyl io n co nc entrati o n of the water. and thu s the pH. co ntro ls th e relati ve
po und s can be identified a nd quantified thr o ugh analysis by gas c hro matog ra ph y ..... . .... .... . . .... ab unc.I<l nc.eo f e'1c~ s p ec ies Ox id a ti on of N H 3 and N H4 + to nit ra te an d o n to
. .. ... . . . . ... . . . . . . . . . . .. .... .... ... .... .... .. ... ,.- . .................... ... .
nitrate by aquatic microbes res ult s in an additiona l bioc he mi ca l oxygen demand
as discussed in th e preceding sec tion.
2-14 NUTRIENTS Nitra te po iso nin g in infant an im a ls, Incluciing humans. can ca use se ri o us
rroblems a lld even de'lth. /\p pal"cil tl y. the lower acidity ill an II1fant 's in test in a l
. Nutti!!nt s are eleme nts essential to the growtli aod repr od ucti on o f plaI}ts and tr3ct permit s growth o f nitrat e- red ucing bacteria th at convert the nitr a te to nitrite
animals, and aquatic species depend o n th e surro undin g water to provide their which is th e n ahsorbed int o the bloodstream. Ni tr ite has a greater affinity fo;'
. nutrients. Although a wide va riet y of minerals and trace e leme nts can be classified hell1oglobll1 th a n cioes oxyge n and thu s rep laces oxygen in t he blood comp lex .
as nutrients, tho;e requ ired in ~ost abundance by a qu a tic species a re carbon. The body IS d eni ed essen tia l oxygen and. in ext reme cases. the vic tim suffocates .
nitrogen. and p'hosph o ru s. Carbon is readily available from man y so urces. Carbon Beca use oxyge n star va ti o n results in a blu ish di sco lora ti on of the bodv, nitrat e
dioxide from the a tmosphere, a lk a linit y. a nd decay pro du c ts o f orga nic m a tt er all poisoning has been referred to as the " blue baby" sy ndrome. a lt houg h the corr~c t
suppl y carbon to the aquatic sys tem. In most cases, nitroge n an d phosphoru s term is Illel/l cllloq/oiJincl1Iia. Once the Aora of th e intestinnl tract has full v de-
are the nutrients that are the limiting fac to rs in aquatic plant grow th . A discussion \clopecl. usually ~i ft er th e age of 6 mon th s, nitrat e convers ion to nitrite and's u b-
of the consequences o f ove renri c hment with nitrogen a nd phosphorus is prese nted 'sequent m ethemog lohi nemia 'fro'm drinking water is seldom a problem. For-
in Chapter 3. tun :lle ly. the natmal ox idarion of nitrite to nitra te occ ur s quick ly so th at sign ificant
()llantilies nfnitritcs are no t found in natural \\atcr.
Tests for nitr oge n form s in water commonly include ana lys is for ammonia
Nitrogen (11ll"ludlng bo th ammonia and ammonium). nitrnte. and orga nic nitrogen Th e
Nitrogen gas (N 2 ) is the prim ary co mponent of the ea rth 's a tm osphere and is results u fth e analyses are usua ll y expressecl as milligram s per ,iter of the p~rticular
extremely stabl e. It wi ll react w ith oxygen under high-energy cond itio ns (elec tri ca l s pec lcs as n itrogen. Tests fo r ammonium and org~ l nic nitrogen nre more comll1on

o n was tewa ter and other polluted waters, wh ile the test fo r nitr:lte is th e most ete rs, because their presence or absence may indicate in general terms the character-
common o n c lea n-wat er sa mpl es and tre a ted was tewa ters. IstiCS of a given body o f water. As an example, the general quality of water in a
trout stream would be .ex.pected lo exceed that o f a stream in which the pre-
d o mmant species o f fish IS carp. SlInIia rl y, abundant algal populations a re associ-
Phosphorus ated With a water ri c h in nutrients. '.
Ph os ph or us appears ex clus ive ly a s phos phat e (P0 4 ) - ) in aquatic en vi ro nm ents. Biologists often use a species-diversity index (re lated to th e number of species
There are seve ral form s of phosphate, however. inc ludin g o rth op hos phate, and the relative abundance oforga.nisms in each species) as a qualitative parameter
conde nsed phosphates (pyro-, meta-, and po ly ph ospha tes). and orga nica ll y bou ll d fo r streams and lakes. A body of water hostin g large numbers of species with well-
ph osp hates. Th ese ma y be in so luble or particulate fo rm or ma y be cons titu ents of balanced numbers of individuals is considered to be a health y system. Based on
plant or a llJlnal ti ss ue. Like nitrogen. ph os phates pass through the cycles of their kn own tolerance fo r a given pollutant, certain organisms can be used as
decompos iti() n and phot osy nthesis. mdl
. ca .tors
C of the prese nce o f pollutants. A more det a iled coverage of this t OplC
. IS
Ph os phate is a const itue nt o f soi ls and is used ex tens ive ly in fertili zer to rep lace give n m hap. 3.
and /o r s uppl e ment natu ra l quantities o n ag ri c ultural la nd s. Ph ospha te is a lso a
constituent o f anima l was te and may beco me incor po rated into th e so il in grazing
and fe edin g areas. Run o tT from ag ri cu ltu ra l areas is a m ajor co ntribut o r to ph os-
phate in s urfa ce waters. The tenden cy for phosphate to :ld so rb to so il particles
limit s it s mO\'eme nt in so il mois tur e and gro und wa ter, but res ult s ill it s trans po rt Fro m the perspectIve of human use and consump ti on~ the most impor ta nt bio-
Int o surfa ce wa te rs by ero sion. logical organis ms III water are pathogens, those organisms capable of infecting,
Muni cipa l wastewater is ano th er major so urce of phosphate in s urface water. or o f transmlttmg dIseases to, humans. These orga nisms are not na tive to aquatic
Condensed ph os phat es are used extens ive ly as builders in detergents , and o rga nic sys tems and usually require an anim a l host for growth and reproduction. They can,
ph osph at es ar e co ns tituent s o f body was te and food res idue. Other so urces inc lud e however, be tra nspo rted by natural water systems, thu s becoming a temporary
indu st rial waste in which ph os phate compounds are used fo r suc h purposes as me mber of the aqua tI c community. Many species of pathogens are ab le to survive
III water and maintain their infectious capabilities fo r sign ifican t periods of time,
boiler-wZi te r co ndit ioni ng.
While p hos phates are n o t toxi c and do no t re prese nt a direct hea lth threat These. waterbo rne pathogens include species o f bacteria, viruses, protozoa, and
to human o r o ther o rgani sm s, the y d o rep rese nt a se riou s indirect threat to wa ter hetm1l1ths (parasitic worms). The characteristics o f the p~im ary waterborne
path oge ns are listed in Table 2-7.
qualit y. As no ted earlier. phos pha te is o ft e n th e limitin g nut rie nt in s urface wa ters.
-Wf1 e ilth e"iv~1ibb l e sLlppli ls ini.:re::i se d, rapid grow th o f aquatic plant s usually
results. w ith seve re co nsequences. Ph os phat e can a lso interfere with wa te r- Bacteria
t reatl11ent processes. Co ncen tr a tion s as low as 0.2 mg/ L interfere with th e c he mical '
coag ulati u n o f turbidit v. [2-20J The word bact eria co mes fr o m th e Greek word meaning " rod " or "staff," a
Ph os phat es are mea s ured co lor imet ri call y. Orth o ph osphates can be meas ured s hape characteristic o f mos t bacteria. Bacter"ia a re sin'gle-ceU microorganisms,
dir ect ly. whi le co nd e nseu form s mu st be converted to o rth ophosphate by ac id usually co lorless, and are the lowes t fo rm of life capable of synthesizing proto-
h vdl"U lyza tiun and o rg anic phosphates must be con verted to orthophosphates by pla sm fr o m the surrounding environment. In addition io the rod s hape (bacilli)
<lcl d dig es ti o n . Resu lts l)f the analys is are reported a s milligr:lms per lit er o f phos- mentioned above, bacteria may also be sphe rical (cocci) or spiral-shaped (spirilla).
ph a te ;IS phosphoru s. Care ful handlin g o f sa mples pri o r to a nal ys is is c ru c ial. F o r Gas tr 0 1l1test1l1 al disorders a re common symptoms o f most diseases trqnsmitted
eX;IIl1 pie. ac id-\\~I s h c d g lass bo ttles sho ul d be used for sa mpling, as bottles washed by wate rbo rne pat hogenic bacteria.
in pl; us phate d etergen t ma y co ntaminat e sa mp les. C holera, the di sease that ravaged Europe during the eighteenth and nine-
tee nth centuries, is tran smitted by Vibrio comma. Among the most violent of the
waterborne bacteri a l diseases, cholera causes vomiting and diarrhea that, without
Biological Water-Quality Parameters treatme nt. resu lt in dehydration and death. Symptoms of typhoid. a disease
tran smitted by th e wa terbo rne pathoge n, Salmoll ella typhos{l, include gas tro-
Water ilia: ser\'e as a m ed ium in \\ hich lit era ll y th ousa nd s o f biological sr ecies IIltestllla l di so rders, high fever. ulceration o f the intestines, and possible nerve
spend pa rt. ir not ;dL ,)1' their lire cvc les. Aquatic organisl11s 1'<1nge in s ize <Ind damage. Although immuniza tion o f indi viduals a nd disinfection of water supplies
C(ll11 pl cxit:- from th e sma ll es t singl e-ce ll microorganisl11 to th e larges t fi s h. All ha ve el l mlnated cholera and typhoid in m os t parts o f the world, a reas of deve lop-
Il1 cl11hCl"S o r th e hil)lo~lca l cnm l11l1l1it y a rc, to so m c ex te nt. wa te r-qu ;d itv p~lram- Ing cu untrIes where overc rowding and poo r sa nit a ry cond iti on s preva il still

Table 2-7 Common waterborne pathogens Immunization of individuals has reduced the incidence of polio to a few
isolated cases each year in developed nations. Outbreaks of hepatitis are more
Organism Disease
common, with around 60,000 cases reported in the United States each year.
Bacteria Most of the hepatitis cases result from persons eating shellfish contaminated by
Francisella lUlarensis , Tularemia (deer fly fever) viruses from polluted waters, [2-2J although an occasional outbreak will occur at
Leptospirae Leptos pirosis campgrounds or other facilities where crowds gather and where water-supply
(Wei!'s disease, swineherd's disease, protection and sanitary facilities are poor.
hemorrhagic jaundice)
Salmoneila paratyphi (A,R,C) Para typhoid (enteric fever) Although standard disinfection practices are known to kill viruses, con-
Salmonella typhi Typhoid fever, enteric fever firmationof effective viral disinfection is difficult, owing to the small size of the
Shigella (S.jfexneri, S. sonnei, S .. dysenteriae, Shigellosis (bacillary dysentery) organism and the lack of quick and conclusive tests for viable virus organisms.
S. boydi!) The uI.1certainty of viral disinfection is a major obstacle to direct recycling of
Vibrio comma (Vibri~ cholerae) Cholera (Asiatic, Indian, El Tor)
wastewater and is a cause of concern regarding the increasing practice of land
Viruses application of wastewater.
Enteric cytopathogenic human orphan (ECHO) Aseptic meningitis, epidemic exanthem,
(ECHO) {nfantile diarrhea
Poliomyelitis (3 types) Acute anterior poliomyelitis, infantile Protozoa
The lowest form of animal life, protozoa are unicellular organisms more complex
Unknown viruses Infectious hepatitis
in their functional activity than. bacteria or viruses. They are complete, self-contained
organisms that can be free-li ving or parasitic, pathogenic or nonpathogenic,
Entamoeba histolytira Amebiasis (amebic dysentery, amebic
enteritis, amebic colitis) microscopic or macroscopic. Highly adaptable, protozoa are widely distributed
Giardia lamblia Giardiasis (Giardia enteritis, lambliasis) in natural waters, although only a few aquatic protozoa are pathogenic.
Helminths (parasitic worms) Protozoal infections are usually characterized by gastrointestinal disorders
Dracunculus medinensis Dracontiasis (dracunculiasis ; dracunculosis, of a milder order than those associated with the bacterial infections discussed
medina; serpent, dragon , or guinea-worm earlier. Protozoal infections can be serious nonetheless, as illustrated by an epi-
. infection) demic in Chicago in 1933 in which over 1400 people were affected and 98 deaths
Echinococcus Echinococcosis (hydatidosis; granulosus; dog
resulted when drinking water was contaminated bY ,sewage containing Entamoeba
Schistosoma (S. mansoni, S.japonicum, Schistosomiasis (bilharziasis or .. Bill Harris " histolytica. [2-14]. Many .of .giardiasis,. D[backpaekers 'disease,' have' 'been .
S. haematobium) or .. blood fluke " disease) reported in recent years among persons that drank untreated water from surface
streams. This infection is caused by Giardia lamblia, a protozoan that may be
carried by wild animals living in o r near natural water systems.
Under' adverse environmental circumstance, aquatic protozoa form cysts
experience occasional outbreaks of these two diseases. Temporary lapses in good that are difficult to deactivate by disinfection. Usually complete treatment, in-
sanitary practices sometimes result in outbrea~s of gastroenteriti? caused by some cluding filtration , is necessary to remove protozoal cysts. .
of the other bacterial pathogens listed in Table ?-7.
Viruses The life cycles of helmil1ths. or parasitic worms, often involve two or more animal
hosts, one of which can be human , ' and water contamination may result from
Viruses are the smallest biological structures known to contain all the genetic human or animal waste that contains helminths. Contamination may also be via
information necessary for their own reproduction. So small that they can only be aquatic species of other hosts, such as snails or insects. While aquatic systems can
"seen" with the aid of an electron microscope, viruses are obligate parasites that be the ve hi cle fo r transm itting helminthal pathogens, modern water-treatment
require a host in which to live. Symptoms associated with waterborne viral met hod s are very effective in destro ying these orga nisms. Th'us, helminths pose
infections usually involve disorders of the nervous system rather than of 'the ha za rds primarily to th ose persons who come into direct con tact with untreated
gastrointestinal tract. Waterborne viral pathogens are known to cause polio- water. Sewage plant opera tors. swimmers in recreational lakes polluted by sewage
myelitis and infectious hepatitis, and several other viruses are known to be, or o r stormwater runoff from ca ttl e feedlots. a nd farm laborers employed IJ1 agn-
suspected of being, waterborne. Cultural irriga ti on operat ions are at particular risk. [2-5J

b._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ____
A. Presump tive tes t
50 WA T ER
r Inoc ula Ie laur yl tryp lose b ro lh ferme nta lion lubes and incubale 24 2 h a l 35 C O.SoC


( I) (2)
Cas p roduced No gas, o r gas produ c tion doubt ful
Posit ive Incub a le additi ona l 24 h
An a lys is of wa ter fo r a ll the kn ow n pa th oge ns wo uld be a very time-consumin g
presumptive ( lo lal 4 8 3 h)
a nd ex pensive pro positio n. Tests for specific path ogens a re usua ll y made o nl y [esl
whe n there is a reaso n to suspect t ha t th ose particula r o rga ni sms a re prese nt . (a ) (b)
At other ti mes. th e pu rity of wa ter is checked using ind icato r o rganisms . Cas pro du ced . N o gas produced
. Positi ve Nega live test
An indicator organ ism is one whose presence p res umes that co ntami nat ion has tes t Colifor m group absent
occur red a nd sugges ts the natu re and exte nt of t he co ntam ina nt(s). T he idea l
B. Confirmed le st
path ogen indica to r wo uld ( J) be ap plica ble to a ll types of wa ter. (2) al ways be
present 'w il en pa t hogens are present . (3) a lways be a bsent when pa thogens a re l Inoculate la ury! tryplose broth fe rme ntation tu bes and incubat e 24 2.h at 35 C O.SoC

a bsent. (4) lend itse lf to ro utine qu a ntit a ti ve tes ting procedu res wit ho ut in te r-
ference fr om o r co nfu sio n of res ults beca use of ex tra neo us o rgan isms. a nd (5) for ( I) (2 )
Cas p roduced No gas, Or gas prod uc tion doubt fu l
the sa fety of la bora to ry perso nn el. no t be a pa thoge n it se lf. [2-6J Transfer to In cubate addi tional 24 h'
Most of the wat erbo rn e pathogens are lilt rod ucecJ t hroug h fecal con tamina tio n confirma tory brilliant ( to tal 4 8 3 h)
green lactose bi le bro th
of wa ter. Thu s. any o rga ni sm na ti ve to t he in tes tinal trac t o f hu malls and meet in g Incub"le 48 ! 3 It al
(a) (b)
the above criteri a wou ld be a good indica tor organism. The (lI"ganisms mos t 35 C ! O.SoC
Cas produced No .gas p rod uced
nea rl y mee ting these req ui re ments be lo ng to t he fecal co lifor m glo up. Composed o r d oub l ful Negative tes t
. of severa l st rain s o f'bacteri a, p ri ncip a l of whic h is Escherichia coli. these orga ni sms (a) ( b) Confir m as in B(l) Colifo rm gro up absent
Cas p roduced No gas produced
are fou nd exc lu sive ly in t he int est ina l tract of warm -blooded anllll~ " s a nd arc Coliform group Nega tive lest
exc reted in la rge n umbers wit h feces . Feca l co lifo rm o rgan isms arc nonpa t hogenic confirmed Colifo rm group absent
a nd a re belie ved to have a lo nger surv iva l time o utsid e th e a nim a l body tha n d l) C. Com pie led test
mos t path ogens. Beca use the d ie-o rT rate of feca l co liform , is loga rithm iC. the
number of sur viv ing organisms may be an ind icat io n of th e time la pse sin ce
l Inoc ulate la ury l tryp lose broth fe rmentation tubes and incuba te 24 2 h at 35 C O.SoC

conta min a tion . ( I) (2)

Th ere are o ther co liform gro ups whi ch fl o urish o utside the intestina l tract of Gas produce d. Transfer [Q confirmatory brill ia nt No gas, or gas p ro du c tion do u btful
gree n lac tose bile Incubale 48 3 h al In cubal e addit io nal 24 h (I ot al 4 8 3 h)
a nll11 al s. Th ese orga nisms a re nati ve to th e soi l anc! decayi ng vegeta tin n a nd are
.. .... 35.C..D.tC .. . .... . . .. .. .. . ... . . .
oft en fo un d in wa ter tha t was in rece rr t' co nt ac t' wi th' th ese m,lwr"i !d"s". Bc'c,i lI SC'
the life cycles of so me pa thogens (pa rti c ul arly helminth s) may inc lu de periods (a) (b) (a) (b)
Gas prod uced No gas pro duce d Gas produ ced o r No gas prod u ced
in the soil, this gro up of co lifo rm o rga ni sms a lso se rves as a n Indica to r of patho-
Transfer 10 End o o r EMB plales Negative test do ub t ful Negat ive te st
ge ns. Incub",e 24 2 h at oS C D.5C Coliform gro up absent Conti n ue as in C( I) Coli fo rm group
It is the usua l prac tice in .th e United Sta tes to use the to ta l co li form gro up (th ose abse nt
of bot h feca l a nd no nfeca l o ri gin ) as indica tors nf the sa nitar y q ua lity of d rinking ( I I) (1.2)
wa ter. whi le the indi ca to r of cho ice for wastewa ter emucn ts is the feca l co lifo rm Typical OR alypical coliform colonies Negati ve colonies
gro up. Rela ti ve ly simp le tests have been dev ised to deter mi ne the p resence of Transfe r to agar slant and laury l try ptose bro th fermentat ion tube Coli fo rm group
Incubale aga r slanl 181024 hand lauryl tryplose brolh abse nl
co lifo rm bacter ia In wa ter a nd to enumera te the qu a nt ity. T he tes ts 1'0 1' to ta l 24 2 h 1048 3 h at 35 C O.5C
co liform orga nisms employ sli ghtl y differen t cultu re medi a and lowe r Illcubat ion
te mperat ures t ha n th ose used to iden tify feca l co li form organisms. ( a) (b 'j
T he membra ne-fi lter tec hnique. a tec hniq ue po pu lar with cnVlrl.lllmenta l Gas produced No gas produced
engin ee rs. g ives a direc t co un t of co lifo rm bac teri a. In thi s tes t. a por tion of the Gram-st ain portion Nega tive tes t
of ::lgar sian I grow th Colfform group absen l

sa mple is fi ltered thro ugh a memb ra ne. the po res of whi ch d o lI ut exceed 0.45 li m .
Bacteria are re tamed on the hlter tha t is t hen placed on selecti ve rn ed ia to prul1lu te
(II I ) ( 1.1 2)
growth of co ii form bacteria wh ile in h ibiti ng growt h of o th er spec ies. The memb rane

Cram-nega tive rods present, 11 0 spores prese nt Spores or grampositive rods and sp ores presen t
and medi a are incuba ted a t the ap propfl ate tem perat ure' fDr 24 h. a ll owing co li - Completed tesl: coliform group presen t Com ple led lest: coliform group abse n t
Gram posit ive and negative rods hoth presen[
fo r m bacteria to grow intn vis ible co lonies th at are t hen cll un ted . The resul ts arc Repeat pro(cdu re beginning at 1.1

re pc)I"ted In n umbe l' o f o rga nisms per 100 m L of wat er
Fig ure 2-7 P roceuure J','r r u nnin g lotal coliform analysis by th e m uli iple.[ube fe r mentat ion met h od.
(From SlanJaul Melhods [2.15].)

An a ltern a ti ve met hod often preferred by micr o bi o logists is th e mu lti p le- (M P N) o f colifo rm ba c te ri a in J 00 m L o f the wa ter sa mp le. Th is meth od is ill us-
tube ferment a tio n test. Colifo rm o rgan ism s are kno w n to ferment lac tose, w it h tra ted in th e fo ll ow ing exam ple.
o n e o f the end prod u cts bei n g a g as. A brot h containing lactose a nd othe r sub-
sta nces whic h inhi b it n o nco lifo rm org a n ism s is p laced in a series of test t u bes wh ich
Exam pl e 2- 10 : Determin ing th e most probable num ber of co lifo rms A stand a rd m u ltiple -
a re then inocul a ted wit h a d ecimal fract ion of I mL (100. 10,1.0, 0. 1. 0.0 1, etc.).
tube fe rm e nt a ti on test .is ru n o n a sa m p le o f wa te r fro m a surfa ce strea m. The resu lts of
These tubes are inc u bated a t the appropria te tempe ra ture a nd inspec ted for
the an a ly sis fo r t he c'o n fi rmed tes t a re shown be lo w .
d ev~l opment of gas. This fi rst stage of the procedure is ca lled the pres umpt ive l est.
a nd tu bes wi th gas deve lopmen t are pres umed to have colifo rm s present. A sim ilar
tes t. called th e confirmed leSI, is t he n set up to c o nfirm the prese nce o f co li fo rm
Size o f sa m ple. N o. posiJl ve No . nega li ve
o rgan ism s. A schema t ic o f"th is process is sho wn in Fi g. 2-7. A sta tistica l me thod is mL
used in co nju nc tio n wi th Table 2-8 to de termine th e m os t pro ba ble n u m ber -----
10 4
Table 2-8 MPN index and 95 % confidence limits for va ri ous combina ti ons of
0. 1 .4
positive results when fiv e tubes a re used per dilution (10 mL, 1.0 mL, 0.1 mL) 0. 01 I 4
95 ~-:; co nfid e nce 95\ co nfi d e nce O.DOI 0 5
l im its limit s
C ombin a tion MP N index C o mbi n a t io n MP N in dex
o f p osit ives /1 00 mL Lowe r U ppe r of p os it i\"c~ . 100 mL Lowe r Upper D ete rm ine th e m os t p roba bl e numbe r o f co lifo rm orga n ism s.

0-0-0 <0 4-2-0 22 67

. 0-0-1 2 < 0 .5 4 -2- 1 26 9 78
0-1 -0 2 < 0 .5 4 -3 -0 27 9 80
4 < 0 .5 II 4 -3- 1 33 II 93 Se lec t a series whe re th ree tubes ea ch have pos iti ve res u lts (n o t necessary, b u t reco m -
4-4-0 34 12 93 me nd ed): use samp le size s 10. I . and O. I
o En te r T ahl e 2-8 w ilh th e number o f pos iti ve tubes Ollt o f fi ve (4. 2, I) : T he cor res pond-
1-0-0 2 < 0 .5 5-0-0 23 70
31 II 89 ing M P N is 26 wit h ;, ra n ge o f 9- 78 o rgani sm s pe r 100 m L p oss ible a l a 95 pe rce nt
1-0- 1 4 < 0 .5 II 5-0- 1
4 < 0 .5 II 5-0- 2 43 15 110 co nfid e nce le vel.
1- 1-0
1-1 - 1 6 < 0 .5 15 5- 1-0 . . .3~. II .. ...93 . .- .. ... ... ... . .
.. ' " T-2-0 .. .. .. ..... o.. . .. . '<'0)" " '1 5 " 5- 1- 1 46 16 120
5- 1 2 63 21 150 ALTER NA TE S OL UT IO N

2-0-0 < 0. 5 I, 5-2 -0 49 17 130

70 23 170 I Selec i samp le sizes 1.0 , O. f , an d U.O f.
2-0- I I 17 5- 2-1
2- 1-0 7 17 5-2 2 94 28 220 2. h o m Ta ble 2-X, Ihe co rre s po ndin g M PN is 9 a nd Ih e 9 5 pe rce nl co nfi d e nce range is
2- 1- 1 9 2 21 5-3 0 79 25 190 2 thr o ugh 2 1.
2-2-0 9 2 21 5-3- I 11 0 31 25 0 3. Bec <l use Ill e se ri es 01' sam pl es used is o ne- Ie nlh o f Ihe 10, I, an ci O. I samp le sizes used
2-3-0 12 3 28 5-3 -2 140 37 340 in l hc lab le. muil ipl y Ihe val ues by 10. T he re fo re . Ihe M PN o r l hc sam pl e is 90 o rga n-
3-0-0 8 19 5-3 -3 I KO 44 51)0 ism s pe r 100 m L a nd th e 9 5 pe rce nt co nfide nce ran ge is 20 to 2 10 .
3-0- I II 25 5 4-0 130 35 300
3-1-0 It 25 5- 4- 1 1711 43 490
~2 0 70n Samp lin g lec h n iqu es and s uh se qu ent ha nd li ng o f the sa mpl es a re extrem ely
3- 1- I
4 34
5- 4-2
5-4 -3
I. ()O()
'I m[1 o rt :lIlt beca use sa mp les ca n ea sil y be co nt a min a tecl . D e ta iled p rocedures fo r
samp li ng. sa'm p'le prepa rat io n, a nd ste rili za tio n o f labo ra to ry equ ipme nt fo r bo th
--- 4-0-0
4-0 -t
5- 5-0
5-5 I
350 12(1
7~ 1J
th e me mbr an e fili er tec hni q ue a nd t he muli ip le- tu be tec hniqu e are p rese nt ed in
SWI/r!ord At !'1hoi/.I. [2- 15J
4 - 1-0 17 46 5-5-2 <;40 180 1.400
It sh uu ld be em[1ha sized aga in th a t pa thoge ns arc no t Id en tifi ed by the co li-
4- 1-1 2I 63 I 5-5 -3 no }OO 3.200
fo rm l e~ t. Th e p re se nce of co lifo rm orga ni sm s in wa te r d oes. ho we ve r. indica te
4- 1-2 26 ') 7K 1. 600 (41) 5,gOO
2' - ) - ) 2 2,40(1 tha i so m e por ti() n uf th e wa ler ha s recen tl y co n tac ted so il o r d eca ying veg eta ti o n
t) r h:t, hlT ll l ilro lig h the Int es tinal tra c t ora w:lrm -hl oocl ed an im a l. T he a ss umpt ion
SOl/ r cf: Fro m Sm ilh . r2 14] Illlh l tilt'n ht: 11 l: I(k tha t pa th oge ns Illa ), have acco m pa n ied th e co lifo rm bac teria.


Water-Quality Requirements 2-18 POTABLE-WATER STANDARDS

W ater-qua lit y requirements va ry acco rding to the pro posed use o f the water. Sta nd a rd s for drinkin g wa ter have evo lved over the years as knowledge of the nature
Detailed desc ripti o ns of the qualit y criteria for agricultural use, fish and wild life and elfec ts o f various contaminants has grown. Current ly, it is considered desirable
propagat ion. s pecific indu stri a l a nd recrea ti o nal uses, and powe r ge nera ti o n are tha t dr inking wat er be free o f suspended so lids and turbidity, that it be tasteless
prese nt ed elsew here, [2- 7, 2-6, 2- 17]. and s uch desc ription s are beyond th e sco pe a nd odorless. th a t di sso lved in organ ic so lids be in moderate quantities, and that
o f this text. Water unsuitable for o ne use m ay be quite sa tis fac to ry fo r another. o rga nics. toxic substances, a nd pathogens be absent. As more is learned about the
and wa ter may be deemed acceptable for a pa rti c ular use if water o f be tt er qu a lity co nstituents of water. additional requirements will probably be added to thi s list.
is no t ava ilable. . making drinkin g-w a ter requirements even m o re stringent.
W a ter-q uality req uire m e nt s s hould no t be co nfused w ith wa te r-qualit y The World H eal th Organizat io n has established minimum criteria for drinking
sta nd ard s. Set by the po tenti ,il use r. wa ter-qualit y req uirem ents re present a known wate r th a t a ll na ti o ns a re urged to meet. These standards are listed in T a ble 2-9.
or ass um ed need and a re based o n th e pri o r ex perience o f the water use r. Waler- Co untries with m o re advanced technol ogy generally have sta nd a rd s that exce~d
qualil.'r' standards a re set b y a gove rnmental agency and represent a sta tut o ry t hi s qua lit y.
req uire ment. For exa mpl e. a farm e r ma y hlOW fr o m prior ex perie nce Ihat highly
sa lin e wale r will damage th e crops. bUI th ere a re n o o ffi c ial wa ter- qualit y s ta nd ard s
that sa y s uch wa te r ca nn o t be used fo r irri ga ti o n purp oses. Table 2-9 Drinking-water standards of the World Health Organization
In th e U n ited Sta tes. s tand ard s have bee n pro mul ga ted fo r strea ms a nd lak es.
for public wate r s upplies. and for was tewa ter disc harges: Stand a rd s fOI surface Concentrations in milli g ram s per liter

wa ters. potabl e wa ter. a nd was tewa ters a re di sc ussed in th e fo llowi n g scc ti on: W H O Internali o nal (1958) WHO Euro pean (1961)

Per mi ssib le Excessive Maximum Reco mmended T o le ran ce

Chem ica l constit uen t iimit limit lim it limit limit
2-17 IN-STREAM STANDARDS ,\lI1monia (N H,) 0.5
A r st.:nic 0.2 0.2
Ca clnllulll . .. . . . . . . . . . . 0.05
F o r reaso ns o f aes t he t ics as we ll a s hea lth . it is ge ne rall y co ns id e red de s irable to
Calci um 75 200
--'m ;;;rii il;ii ' water sys te ms at as hi g h a quality leve l as poss ible . /\11 SO o f th e Ch lo ride ~OIJ 600 350
s t:l! es ha ve set minimum qual it y s tand ards for a ll s urfa ce wate rs lVilh in th eir C hr omi um (hexava lent) 0.0 5 0.05
boundar ies. These standard s o ft e n re Aec t th e be ne fi c ia l use lilad e o f til e stream. Cn prcr 1.0 1.5 3. 0'
That is. mo re stringent sta nda rd s are app li ed to a strea m used as a so urce o f water Cyanide 0.01 0.0 1
Fluo r id e 1.5
for muni ci pal rurr oses th a n to streams lI sed fo r o th er purp oses.
I ron 0 . .1 1.0 0. 1
Man y fa c to rs affec t stream qualit y. W as tewa ter di scharges and o th e r human Lea d 0.1 0. 1
ac ti vities o ft e n ha ve s ign ifi ca nt impac t o n in-stream wa ter qualil Y Th ese ac ti vities Magnesi um 50 150 125t
m ay lend th e mse lves to con tr o l by legis la ti o n and gove rnm en t reg ulati o ns. F o r Magnesium + sod iu m sulfate s 500 1000
examp le. co nsis tent with w ha t it be lieved to be publi c o rini o n. th e U nit ed States Manganese 0. 1 0.5 0. 1
Ni trat e (as NO,) 50
C o ngress passed the Water P o lluti o n Co ntr o l Ac t o f 1972 ( Publi c L~t w 92-500)
Oxygen. di sso lwd (milllmulll) 5.0
a nd , w ith min o r modi fi ca ti o ns. renewed it in 1977. A sta ted goa l o f thi s legis la ti on Ph e nolic c<) mpo und s (a s phen o ls) 0.001 . 0.002 0.001
is that a ll s urface wa ters in th e United Sta tes be maintained a t " fi sha ble, sw im- Se le nium 0.05 0.05
mab le " qualit y. Attaimnen t o f thi s goa l s ho uld re sult in a qualit y s uffi c ie nt fo r Sul fat e 200 400 250
m os t wa ter uses and simpl ify trea tm ent processes for wate rs int end ed fo r po tabl e T ot ,iI so lid s ' SOU 1'00
Zinc 5.U 15 5.0
and indu stria l use.
While leg is lati o n such as Public La w 92-500 ca n con tr o l so me as pects o f wa ter After 16 h co nta ct \\1 th "ell pipes. hilt "'ato r entering a disl r iblltion system s ho uld have less than
pol iutillil. th~ geo illgy o f a wmershcd. coupled with Ol her natura l ph cno m ena . is D.I)) mg/ L o f co pper.
o ft en th e co n trolling factor in wate r CJua lit y. Thi s fact mu st be co ns id ered if in - t If there is 250 rn g; L o f sulf:lIc prlsoIH. Illa)!"csillrn sho uld not exceed 30 mg! L.
s trea m water-qu al it y s tand a rd s ar~ 10 be reali sti c. S()/I/'n': Ad"p ted fr o nt Todd . [2- 17J

The Safe Drinking Water Act of 1974 (Public Law 93-523) mandated the U,S, levels imposed by the potable-water standard s, Treatment of surface water for
Environmental Protection Agency to establish drinking-water standards for all potab le use will a lwa ys bc rcquired, the nature and level of treatmen t dependll1g
public water systems serving 25 or more people orhavingJ5 or more connections, o n the in -st ream qu a lit y o r th e water so urce.
Pursuant to this mandate, EPA has established maximum contaminant levels for
drinking water delivered through public water supply distribution systems,
These standards were published in 1975 under Title 40, Subchapter D, Part 141 DISCUSSION TOPICS AND PROBLEMS
of the Code of Federal Regulations, [2-19J The maximum contaminant level (MCL)
of inorganics, organic chemicals, turbidity, and microbiological contaminants 2-1 Name th e phys ical wat er-qualit y parameters of concern to environmental engineers.
are shown in Tables D-l through D-5 of the appendix, EPA has also issued 2-2 Discuss th e so urces a nd impacts of suspended so lid s.
proposed ~egulations to serve as guidelines to the states with regard to the 50- 2-3 How are suspended so lid s mea surerP
called secondary drinking-water standards, [2-16J These appear in Table D-6
2-4 An analvsi s for suspe nded so lid s is run as follow s: ( I) A fibergla ss filter is dried to a
of the appendix, constan t ma;s of 0.137 g; (2) 100 mL o f a sa mple is drawn through the fi lt er ; a nd (3) the filt er
and res idue are placed. in a dr ying over at 104C until a co nstant ma ss of 0. 183 g IS reached.
Determine the suspended-so lid s concen tra ti on in milli grams per lit er.
2-19 WASTEWATER EFFLUENT STANDARDS 2-5 One hundred milliliters of th e frltrate from a suspended-so lids ana lysis is placed in an
ev aporation di sh whose tare Illass has been determined to be 327.48 5 g. The co ntents of th e
The water Pollution Control Act of 1972 (Public Law 92-500) mandated the di sh are evaporated to dryness. and th e lotal mass of the dish and so lid s is fou nd to he 327.5 17 g
Environmental Protection Agency to establish standards for wastewater dis- Determine the quantit y of filterable residue (in milli grams per lit er).
charges. Current standards require that as a minimum all municipal wastewater 2-0 Th e cr ucib le. tilter pad . ;lIld so lid s of Example 2- J arc rlaced in" muftle furnace at 600"C
be treated to "secondary" standards shown in Table D-7 of the appendix. More for I h. Afte~ cooling. the mass is delermlned to be 54.367 g. Dete rmin e the coneent ration o f th e
stringent standards may be imposed where necessary, and in some cases less vo latile (orga nic suspend ed so lids)
stringent standards may ' be permitted for small flows. Industrial disc hargers are 2-7 The evaroration di s h and resid ue from Prob. 2-5 is placed In a Illuflle furn ace at 600C
required to treat their wastewater to the level obtainable by the "best available for I h. Aftercooling.lts ma s, IS found to be 317.498 g. Determ in e the blt era ble vo latile(orga nl c)
technology" for wastewater treatment in that particular type of industry. If so lids of the sample in milli gra ms per Iil er.
industry discharges to a municipal wastewater collection system, the industrial 2-S Discuss the so urces and imp ac ts of tastes and odors in \\ ater suppli es.
waste must be pretreated 'so as to be compatible with the untreated municipal 2-9 Ho\\' arc 1,1stes and odors mea sured 0 ____ ____ __

wastewater. 2-10 \Vil,;t',,'r'e't i;~~~;lr~~'s ,;f' ; ~ ;l~ pe~;I; ~lr~ 'i;l~;~;;S~~ il;'; ,Iter l)~'(i;~~:' WI;,;ta~~ t l;~ impacts
The EPA regulations define receiving streams as either "effluent-limited" of eleva ted temperatures')
or "water-quality-limited." An eJjlue';I-limiled stream is a stream whi<;h will 2-11 Namc th e chemical parameters of concc rn 111 water -qu,rlity man;rgcment.
meet its in-stream standards if all discharges to that stream meet the secondary- 2-12 The reaclion of so da ash (Na,CO J) ,~rth calc ium su lfat e in water is represented by the
treatment and best-available-technol ogy s tandards. Municipalities a.nd indusrries follolVing chemical stat ement :
discharging to effluent-limited streams are as~igned discha rge permits under the
National Pollution Discharg!,! Elimination System (NPDES) which reflects tlie
secondary-treatment and best-available-technology s ta nd a rds. Assumi ng that this react io n is comp lete and that there. is 1:;3 rng,'L nf CaSO" init ial ly present~
A wacer-qualit),-limiled-sream would 11 0 1 m~et its proposed in-stream stand- what is tire ma ss of soJa ash that mu st be added \!) (II) I L of the lI'ater a nd (b) 10.000 m -
ards even if all discharges met secondar y- treatment and best-available-technology ol' the wat er to comp lete th e reac ti o ns.
criteria. Discharges to these streams may be required to meet effluent co ndition s 2- n How man y grams of CaO arc reqUired to he t he chemical eq uivalent of 246 g of
more stringent than secondary-treatment and best-available-technology. These Mg( HCO, );)
discharge limits are established on a case-by-case ba sis. . . 2-14 Express Ihe foll owin g co ncentrations of clem ents and compounds as milligrams per
Effluent standards. potable-water standards, al)d ill-stream standards are lit er ofCaCO,.
obviously interrelated. Enforcement llf eftluent standards. along with the COnlroi
of nonpoint sources of p o llution, s ho uld result in the attainmcnt o r in-stream
standards. The improvement of in-st ream quality s hould res ult in a better raw
water for potable supplies. However. it is impractical to expect surb ce waters. X7 mg. L " 'II" IX9 mg :L Na HCO ,
even if in-stream standards are mel. to meet all of the ma ximum contaminant

2-15 Express the fo ll ow ing mo la r co nce ntra ti o ns o f e lements a nd co m pou nd s as mi lli g rams 2-20 Draw a milli equivalent-per- liter ba r dia gram fo r the wa ter with the following common
pe r li ter of ('aCO). ion concentrati o ns.

10 - 2
mol; L /\1 3 1.8 x 10 - -' mo l ' L CaSO. 70 mg/ L M g2 ' = 28 mg/ L N a + = 124 mg/L
I X '

3 165 mg/ L SO / - = 173 mg/ L C I- = 202 mg/ L

J.5x 10 - mol; L SO/ - 2. 1 x 10 -' moli L Mg(CI) ,

32 x 10 - .I lll ol i L cr 3.5 x 10 J mol i L NaO H De termine tlie erro r in th e io n bala nce.

2-2 1 An an a lysis of wat er fr o m a su rface strea m yields the fo llowing results.
2-16 Determ ine the conce nt ra ti o n of the fo ll owing ions in solution at eq u ilibrium witll the
so lid al ~5 ' C . . Ca 2 + = 60 mg/ L H C O ) - = 11 5 mg/L

('a(O H ), Mg2+ 10 m ~\/ L SO/ - 96 mg/ I...

MgC0 3 Na + 7 mg/ L NO ) - 10 mg/L

CaSO. K + = 20 mg/ L CI - II mg/L

2-17 A was tewater con tai nin g Fe( HCO}h is discharged to a sur face pond. Ass u min): wmplete If an e rro r o f 10 percent is acceptable, sho uld the an a lys is be considered co mplete ?
ox id at ion o r t he Fe" to Fe} ' a nd s uffic ie n t 0 H for t he fo ll owi ng react io n to OCCLI r
2-22 What are the so urces and impacts o f di sso lved so~id s in water supplies?
2-23 How are di ssolved s o lid s measured? How are TDS measurements expressed?

d eter mine the concentratio n (mg/ L as CaC'OJ) of the Fe) ' remain in g dissolved in the pond 2-24 A so lids a nal ys is is to be co ndu cted o n a sample o f wa stewater. The procedure is a s
wat er. fo ll ows :
2-18 A sa m ple or water from a s urfa ce s t rea m is a nal yzed fo r the co m mo n ions with the I . i\ G och crucible a nd fi lte r pad are dried to a constant mass of 25.439 g.
foll ow ing resu ls 2. Tw o hundred millilite rs o f a well-sha ken sample of the wastewater is p assed through the
filt er.
Ca' > 98 mg/ L 3. Th e crucible, filt e r. pad . and rem oved so lid s a re dried to a constant mass o f 25.645 g.
C1 - 89 mgi L 4. O ne hundred millilit ers o f the filtr a te [ wa ter pass ing through the filter in (2) above] is
p laced in an evapora t io n dish that had been prewe ighed a t 275.419 g.
I-I Co., - = 317 ru g,il .. S"Tlie 'sartip!e'i'Ii'(4) IS' eViiporared to dryness and the dish a nd residue are we ighed at 276.227 g.
22 mg/ L 6. Bo th the crucible fr o m (3) and the evap o ra tion dish from (5) are placed in a muffle furnace
at 600"C for a n ho ur. Aft er coolin g. the mass of the c ru cible is 25.501 g and the mass of the
Na " 7 1 mg ' L d is h is 275.944 g.
S.04' 125 mg: L
De te rmin e th e fo llowi ng:

(a) W hat is the percen t e rro r in the catio n- a ni on ba lance ') (a) Th e filt erab le so lid s (mg/ L)
(h) Draw a bar diag ram for th e wa te r. '1
(h) The nonfi lterabl e solid s (m g/ L)
2-19 ,.\ s~lInp l e of wate r was a na lyzed fo r com m o n io ns with the res ul t show l1 beIcHI. (e) The to ta l so lids (mg/ L)
(d) Th e o rga ni c fr ac ti o n of th e fi lt erab le so lid s (mg/ L)
I-I Co., -. 30n mgL (e) Th e o rga nic frac ti o n o f th e no nfilt erab le so lids (mg/ L)
Na ' = liS mgL
2-25 Wh at a re th e mos t co mmo n co nst itu e nt s of a lk a linit y, and what a re their sources and
,- -- ~4() mg i L imp acts')
2-26 H ow is a lka hnit y meas ured :)
Mg " = 36.6 mg, L
2-27 Determ ine the a lk a linit y o f the waters descri bed in Pro bs. 2-1 8 to 2-2 1.
CI' = 71.D Ill): L 2-28 A 100- mL sa mp le o f wa ter is ti trated w ith 0.02 N H ,S 04 ' The initia l p H is 9.5. a nd
Ca ' ' = 100 mg L 6.2 mL o f ac id is req u ired to reac h t he p H 8.3 endpo int. An additional 9.8 mL is required to
reac h th e 4.5 endpo int. De termine t he spec ies o f a lk a linit y present and the co ncentra ti o n of each
Co ns t ruct a bar diagram in Illi ll lcquil a le n ts per liter ror this Will er. species.

2-29 A 200-mL sample of water with an initi a l pH o f 10.6 is titra ted with 0.02 N H 2 S0 4 , The 2-44 A BOD ana lysis is begu n o n Monday. Thirty (30) milliliters o f was te with a DO o f zero
sample reaches pH 8.3 after an addition o f 8.8 mL of th e acid . and an additional 5.5 mL is is Illlxed with 270 mL of dilution wa ter with a DO o f iO mg/ L. Th e samp le is th en put in the
required to bring the sample to pH 4.5. Identify th e spec ies o f a lkalinity present a nd det ermin e incubator. Sin ce t he fifth clay falls on Sa turd ay a nd lab personnel do not wo rk o n Saturday,
the concentrations (mg/ L) of each. the final DO does no t get measu red until Mo nd ay. the seventh day. The fin a l DO is mea sured
at 4.0 mg/ L. However. it is discove red that the incubator was set at 30C. Assume a k, of 0.2
2-30 The initial pH of a water sample is 7.5. A 200-m L samp le is titrated wi th 0.0 1 N H 2 S0 4 ,
The pH 4.5 endpoint is reached after the addition of 15 mL of th e acid. Determine the spec ies a t 20C and kT = k 20 1.05 T - 20. Determine the S-d ay. 20C BOD o f the sam ple.
:. 1
of alkalinity present and the concentration (mg/ L) of eac h. 2-45 Define nonbiodegradable orga nics. Give exa mples. discuss sources. and assess the impa ct
2-31 'Define "hardness" of water. note the two broad cla ssificatio ns o f hardness. and di scuss of nonbiodegradabJe o rga ni cs in water.
the sources and impacts of hardness . 2-46 Deline chemica l oxygen demand (COD) and tota l o rga nic ca rbon (TOC), a nd d iscuss
2-3'2 Would hard water be acceptab le in most drinking -wa ter supplies? Wh y or why not? how these a nd o ther tests a re used to quantify non biodegradable organics in water.
Would ha rd water be an acceptable coolant for an industrial plant') Wh y o r why not ') 2-47 Name the nutrient s required in great es t abundance by aquati c spec ies.
2-33 How is hardness measured? 2-48 Disc lj sS the so urces a nd impacts of nitrogen and phosphorus in water bodies.
2-34 Determine the carbonate hardness. n o ncarbo nate hardness. and to tal hardness o f the 2-49 . Ho w are nitruge n and ph os ph or us meas ured ')
water described in Probs. 2-19 through 2-21. 2-50 Define methemog lobinemia and discuss itas a water-rela ted illness.
2-35 Discuss the sources and impacts of flu o rides in drinking-water supplies. 2-51 Path oge ns arc not always bac teria. Name tw o pathogenic bacteria . two viruses. a nd o ne
2-36 Name the most common nonto xic meta ls fo und in wa ter supplies. iu entify their sources. p rotozoa n somet imes found in wa ter s upplies.
and discuss their impacts. 2~52 With which wa terbo rn e pat hoge ns are the fo llowing di seases associa ted?
2-37 Name toxic metals that may he dissolved in water. identify thei r principal so urces. a nu (a) Cholera (f) T yph o id fever
discuss their impacts. (n) Sw ine heru's ui sc Jse (y) Paratyphoid
2-38 Define biodegradable organics. Give exam ples. discuss so urces. and assess the impact of (c) Amebic dysentery (il) Infa ntil e paralysis
biodegradable organics in water. (d) Giardiasis (i) Infectio us hepatitis.
2-39 Define biochemical oxygen demand (BOD) and outline the s teps in the standard 5-d ay (1') Bacillary dysentery
BOD test. 2-53 What is an indicator orga ni sm ? Discuss the charac teri s tics of t he id ea l pathogen ind icato r
2-40 The 5-day BOD of a wastewater is 190 mg/ L. Determine th e ultimate oxygen d erna llu . and ind icate which organisms mos t near ly exhibit these characteristics.
Assume k, = 0.25 r '. 2-54 D iscuss t he use o f tota l co liform and fecal co li form tests in th e measurement of pathogens.
2-4] In a BOD determination. 6 mL of wastewater co ntaining no disso lved oxygen is mixecl Disc uss the memb ran e tiller technique and exp lain'h ow test results are reported wh en thi s
~ .. . .. ......... w~h 2.94mL0f cilution water<!>lltaining 8. 6'n1 &II..; of disso lved oxygen: After'a-S--'d<ty in'cubati oll technique is used .
at 20e. the disso lved oxygen content of th e mixture is 5.4 mg/ L. C alcul a te the BOD o f the 2-55 Di sc uss the multiple-tube fermentation test. What is a presumpti ve test ') A co nfi r med
wastewater. test ') How are resu lt s expI'essec!?
2-42 The 5-d 20C BOD ofa wastewater is 2 10 mgi L. What will be the ultimate ROD ') What 2-56 A sample o f wastewater is a na lyzed fo r co li form o rga ni sms hy the multiple-tube fer- the IO-day BOD? Hthe sample had been incubated a t 30 c C what wo uld the 5-day BOD men tati o ll method. The results of th e confi rmed test are as fo llows:
have been (k} = 0.23 d - ')?
Number of Number of
2-43 An analysis for BODs is to be run on a sa mple of wastewater. The BOD is ex pect ed to
Sample s ize . POSili\'e results ncgolive resulls
range from 50 to 350. and the diluti ons are prepared acco rding ly. In each case. a standard
mL. out of 5 tuhes Oll' of 5 lubes
300-mL BOD bottle is used. The dat a a re reco rdeu below.

Bottle Wastewa ter ,

DOt o
000 1
no. rnL DO, DO ,
I 20 8.9 1.5
000000 I ()
2 10 9.1 2.5
9.2 5.8
4 9.2 7.5 Determine the most prohable number anu range of coliform o rganisms per 100 mL at the 95
percent con fid ence le ve l.
(a) Determine the BOD s o f the wastewa ter. 2-57 Disc uss in-stream sta ndards. etn uent standa rds. and potable -wa ter standards. Who sets
(b) If yOU know that the oxygen utili z3 ti o n rate is 0.2 1 per day at 20"C, what will be the these standard s in the United Sta tes? Elsewhere')
BOD) if the test is run at 30C? 2-58 What is an eflluent-limitcd stream 'J



2- 1 A merlean Wat e r W or ks Associa tion: .. Quality Goals ror Publ ic Wat e r -- Statement or Policy."
JAW' W A. 60 : 13 17 ( 1968)
2-2 Berg. Gerald: Transmissioll oj Viru ses by llle WOl er ROlile. Wiley . New Yo r k. 1%5. WATER PURIFICATION PROCESSES
2-3 Camp. T. R .: Waler alld lis Impurilies. R einhold, New Yor k , 1973 .
2-4 En vironm enlol Quality, the Eighth Annual Reporr of Ihe Coullcil of Ellvirollmel/lal QlIalily. u.s. IN NATURAL SYSTEMS
Gov. Pr inting Office , Was hing lOn, D.C. , December 19 77,
2-5 Ge ldreich. Edwin E.: .. Water Bor ne P athogens," in Ralph Mitchell (cd .), Warer Polllliioll Micro-
hiology, Wiley, New York, 19 72.
2-6 Hahn . R oy W .. Jr . : F,mdomen{(l/'A>pecls of Waler QualilY Malloy emenr, Tec hnomic , West port.
Conn .. 1972 . .
2-7 M c Kee. J . E .. and H . W . W o lr: WOl er QualilY Criteria, publ. no.3-A, S tate Water R esou rces
Control Board, Sacramento, Calif. , 1971 .
2-8 IV1etcalr & Eddy. Inc . : Woslewoler Ellgille<'rinq: Treatmenr, Disposal, Reuse, 2d cd., M cG raw-Hili ,
New Y ork . 1979 .
2-9 M elhods for Chenllcal Analysis of Waler and Waste, EPA 600/ 4-79-020. U.S. EPA, Cincinnati,
March 1979.
2- 10 Milkr, J. c.: Nilralt COlllaminalioll of lh e iVoler Table Aquifer of Delo "'are, Report or In vestiga-
tions no. 20. Delawa re Geologica l Survey. U ni versity or De laware , 1972. Natural form s o f pollutants have a lways been present in s urface waters. L o n g
2-11 - - -. P . S. H ackenberry. and F. A. D e lucca : Groulldwoler Pollulion Problems in Ihe SOlllh- befo re the 'd awn of civi li za ti on , many of the impurities discussed in the previ o us
eastern Uniled Slares. E PA 600{3-77 -012. U.S. E P A, 1977.
chapter we re washed fr om the ai r, eroded fr om land surfaces. o r leac hed from the
2- 12 Sawyer, C. N .. and P . L. M cCarty' Chemistryfor EIII'irol/lllelllal Ellgil/eers, 3d ed .. McGraw-HilI.
New Yo rk . 19 78 . soi l a nd ultim a tel y fo und th e ir way int o surface water. With few exceptions, natural
2- 13 Schmidt. K . D .. "Nitrate in Groundwat er o f the Fresn o-C lovis Me tro po litan Arca. Califo rnia. " purificati on processes we re able to remove o r ot herwise render these materials
Groundlo'{tier. 10 50 ( 1972). harmless. Indeed, wi thout these se lf-cleaning processes, the wate r-dependent life
2- 14 Smit h , Alicc' !'v!icrobiology and Palhologr. M osby, St. l Ollis. 1976. o n ea rth cou ld no t ha ve deve loped as it did.
2- 15 Srandard Melhods for Ihe Examin alion 0/ WOler and W aS!elo'{tler, 15th cd ., American Pu b li c As civiliza ti on evo lved, human ac ti vit y increased the amount a nd changed
Health Association. Wa s hington , D.C., 198 1
the nature of polluiants entering watercourses. As settlements grew into villages,
2- 16 Steele. E . W . a nd T . J. McGhee : Wal er Supply and Se ll'erage, 'St h ed., M cGraw- H ili. New' Yo rk .
1979 . villages into towns, a nd to wns into cities. th,e quantity' Qf :-Y,"W~.p.r.od,ucts increased ... _.
2- 17 T od d, D . K . Th e Waler Encyclopedia, Wate r In ro rmati on Cc nt er, POri W as hin g ton. New York . until the self-purificatio n cap~lcit'y ' o flo~~ l wa ter bodies was exceeded . Smaller
1970 streams were a ffected firs t. with la rge r s trea ms and lakes ultim a tely becoming
2- 18 U.S . Departmenl or H calth, Educati on. and Wel rare ' Drinking Waler Srnndards. P HS bulletin polluted. Only in recent decades have po llution contro l prog ram s been initiated
no. 956, Publi c H ea lth Service. 1962 . .
in a n attempt to reduce th e co ntam inants discharged to these :-vater bodies to the
2- 19 U.S. Environmental Protection I\gency: "Na tio nal Interim Pr imar y Drinking Wat er Regula-
tion s. " Federal Re91.Her , pt. I V. D ecemhcr 24. 1975 . le ve l that th e na tural pur ifi cation processes can o nce aga in assimila te them.
2-20 Walk er . R odge r . Waler SlIpply. TreGtmn/l , and Dislribul ion, Prentice- H all. EnglewoOd CliO-s . The self-purificatio n mechani sms of natural water sys te ms include physica l,
N . J , 19 78 . chemical, and' biologica l p rocesses. The speed a nd comp leteness w ith which these c
2-2 1 Vesil lnd, P. Ai.lrne Ennronmenta/ Pollution lJnd Control. Ann Arh or Science. AJln Arbor. Mich ..
processes occur depend o n man y variables that a re system-specific. Hydraulic
1975 .
charac teristics s uch as vo lu me_ rate, and turbul ence of flow , physical character-
istics of bott om a nd bank ma teria l. va riations in sunlight and temperature, as
we ll as th e chemica l na ture o f th e natural wa ter, a re a ll sys tem va ri a bles th a t have
an influence'o n the natur a l purification processes. In na tura l waters, these system
var iab les a re se t by nature and can se ld om be a lt ered .
T he same physica l. c hemica l. and bio log ical processes that serve to purify
natura l water sy~ tems a lso work in engineered sys tems. In water- and wastewa ter-
trea tm ent plant s_ the rate a nd ex tent o f th ese processes a re m an aged by controlling
the sys tem var iables. A th oro ugh kn ow ledge o f the na tura l purificati o n processes
is thus esse ntial to the understanding of both th e ass imilative capacity of surface



waters and the operation of engineered systems. The self-purification of natural Example 3-1: Measuring dilution in streams A Irea ted wastewate r enters a s tream as
water systems is discussed in this chapter, while wa ter purifica ti on in engineered shown in th e accom panyi ng fig ure. The con cen tra tion of sod ium in the s tream a t poin t A is
systems is covereciinGhaps, 4 and 5.. 10 mg/ L. and Ihe flow ra te is 20 m 3 /s . The concentra ti on of sod ium in Ihe waste st ream is
250 m g/ L, and the flow rate is 1. 5 m) /s. D elermine the concentralion of sodium at
,-.o inl B <Jss uming Ihal comple te mixin g has occllrred.
Physical Processes
Stream B
The major physical processes invo lved in self-purification of watercourses are
dilution, sedimentation and resuspension, filtration , gas transfer, and heat transfer.
These processes are not only importan t in and of theITiselves,. but ani also of signi-
ficance in their relation to certain chemica l and biochemical self-purification ~

processes. d" S
~ ()j
1.) $
::; '-..J

Through the first decades of the present centur y. wastewater disposa l practices
were based on the premise that "the solution to pollution is dilution. " Dilution
was considered the most economical means of wastewater di sposal and as such
was considered good engineering practice. [3-5, 3-25J Early workers in the fi eld Sm. L'TIO N

devised mixing-zone concepts based on the lateral, vertica l, and longitudin a l

1. Writ e a mass ba la nce between poin ts A and B
dispersion cha racteristics of the receivi ng wate rs. Formulas predict ing space and
time requirements for diluting cert ain pollutants to preselected concentrations Mass in = Ma ss Ollt
were developed. Highly polluted water in the immediate vicinity of the discharge C"u Q,.n = c,. " Q,.A + CwQw
was tolerated as.inevitable, and little th o ught was given to the low levels of material Sin ce Q,.H is the sum of the other two fl ows
transported downstream.
Although dilution is a powerful adj unct to self-cleaning mechanisms of surface
" , ..0 '

waters, its success depends upon discharging relatively small qu an tities of waste '
into large bodies of water. Growth in population and industrial activity, with 2. In sert numeri ca l val ues a nd so lve for C,. /I
attendant increases in water dema nd and wastewater quantities, precludes the
use of many streams for dilution of raw or poo rly' treated wastewaters. In the 10 x 20 + 250 x 1.5
C D = - -- -- - - _ . _ _ .
,. 20 + L5
United States, legal constraints further limit use of water bodies' for wastewater
dilutiqn. Urider present regulation s, maximu~1 allowable loads are set ' indepen- C,.u = 26.7 mg/ L
dently of ~ilution capacity. Only when the standard maximum' load s result in
violation of in-stream water-quality standards is the dilution capacity considered,
and then only to determine the increment of treatment necessary. 3-2 SEDIMENT AnON AND RESUSPENSION
The dilution capacity 'of a stream can be calculated using the principles of
mass balance. If the volumetric flow rate a nd the concentration of a given material Sou rces of suspended soli ds. one of th e most co mmon water pollutant s. include
are known in both the stream and waste discharge, the concentration after mixing domestic a nd ind ustria l wastewater and runoff from agric ultura l. urban . or sil vi-
can be calculated as follows. cultural activities. As discussed in Sec. 2-2, th ese so lids may be'inorga'llic or organic
materials and/ o r li ve orga ni sms. and they may vary in size from la rge organic
(3-1 )
prticies to tin y, almost in visibl e, co llo id s. In suspen sion, so li ds increase turbidi t y
where C represents the concentration (mass/ vol ume) of the selected material, Q is (see Sec. 2-3). a nd th e redu ced ligh t penetrati o n ma y restri ct th e ph otosynthet ic
the volumeric flow rate (volume/ time). and the subscripts s, IV, and m designate activity of plant s, inhib it the vision of aquatic anima ls. interfere with feeding o f
stream, waste, and mixture conditions . T he following example illustra tes the use aquatic anima ls that obta in food by filtratinn. and be abra sive to respira;o r y
of this formula. structures sll ch as gills of fi sh. [3-27J

Sett lin g o ut. or sedimen tati o n. is nature's method of rem ov in g suspend ed

partic les from a wa tercourse. a nd most large so lid s will se ttle o ut readil y in quies-
cent wa ter. P a rticles in th e co llo id al s ize range C~ 1I1 sta y in suspen sio n fo r long
periods of time. though eventua ll y most of these wi ll a lso settle o ut. Gas
Thi s natu ra l sed im enta tion process is not wi th o ut it s dra wbacks. Anae robic c
.2 c::
co nditi o ns are likel y to develop in sed iment deposits. a nd a ny o rga ni cs trapped in 2
th em will dec o mpose, releasing so luble compo un ds into the stream above. Sed i-
0. V 8---
~ . ~
ment deposits can a lso alter the strea mbed by fillin g up the pore space and creating .D
-< 0'"
un suit a ble cond iti o ns fo r the rep roducti o n of man y aquatic o rga nisms. [ 3- IX]
Th e deve lopment o f bank s cl f sil r a nd mud along th e bott om o r strea ms ca n a lt e r
its co urse or haJl1rer nav iga ti o n activi ties. Sediment accumu lati o ns red uce reser- Lic;uid
vo ir storage capacities and silt in harbors. a nd increase flooding du e to channe l
fill-in .
Resuspension of so li ds is co rnm an in tim es or fl ooding or heavy runorf. In Figure 3-1 Gas-l iqu id contact with gas transfer
such cases. increa sed turbulence may res uspend so lid s fo rmerl y deposi ted along between the pha ses.
no rm a ll y quiescen t are;JS of a strea m and carry th em fo r cons iderab le di stances
dow nstrea m. Eve ntu a ll y they wi ll agai n se ttk: o ul. but not before th eir presence
has in creased the turbidit y of th e wa ters into wh ich th ey ha ve beeJl introduced. equilibrium is reached . At thi s po in t, the number of molecules leaving the liq uid
is equa l to the number of molecules entering it agai n, and the liquid is said to be
saru rat ed wi th the gas. Equilibrium in this case implies a dynamic steady sta te,
3-3 FILTRA TJO N not a static state in which a ll movement of gas molecules wou ld stop once satura-
t io n occ urred.
As la rge bil S of d ebriS w~ l s h al o ng a streambed. they uften lodge OJl Ieeds o r sto nes Two characteristics of the a bove process tha t are importa nt in wa ter are (J)
where th ey remain ca ught until high waters wash th cm in to th e main st rcam agai n. solubililY. o r th e ex tent to which the gas is so luble in the water (i.e., the concentra-
Sma ll bits of o rganic matt er o r Ill o rganic cla ys and oth er sediment s may be filt ered ti o n of gas in th e wa ter at equilibrium), a nd (2) lransfer rale , or the ra te a t which
o ut by pebb les o r rocks along th e sll'ea mbed. f\ S \\,lI er perco lates frum the surface disso luti on o r release occurs.
downward Into g roundwater aq ui fers. filtrati o n of (J mu c h more soph isticated type
. ...
" ~ . .. . .
. OCCO l'S: ;:intl.if the soil1:iye( s 'a re' ckcp .eli 6 i.igh ~i Ii'd' Tin'e' 'e'li ollgll: ienl o \;ill'of s li s_
pended material is essentiall y co mplete by th e tilll e wate r ente rs the aqu ifer. Solubility
Man y stream s Interc hange freel y w ith the alluvia l aquifers und ernea th them . so
th e filt ered wa ter may reent er the strea m at so me poi nt down stream . The so lubility o f a gas in equi librium with a liquid is quantified by Henry's law
and is expressed ma th ematically by


X= - (3-2) .'
The transfer of gases int o and o ut of wa ter is a n impo rt a nt part of the natural
purifi ca tion process. The repleni shment of oxygen los t to bacteria l degradati o n
o r o rga nic was te IS Jcco mrli shed by th e transfer of oxygen from the ~1Ir Into th e
in wh ich x is the equilibrium mole fract ion of the dissolved gas at 1 aim or
wa ter Converse ly. gases ero l\ed in the wa ter hy c hemica l and bi ologica l processes moles of gas (ng)
X= -__-
ma y be t ransferred fr o m the wa ter t (1 t he a t mos phere. A k now ledge o r the princi pi es. mo les of gas (n g) + moles of liquid (n l )
of gas transfer is esse ntial to understa nd ing these natural processes.
Cons id er the simple sys tem s hpw n in Fig . 3- 1 ill whic h it co nta lll er of li quid
is sea led wi th a gas a bove it. If th e liquid is initiall y pure Wi th n;spect to the gas.
II is tbe ' coeffic ient of absorpt io n (H enry's coefflciene , which is unique for each
gas-liquid system), and P is th e pressure of the gas above the liquid. Other factors r
mo lecules o f gas wi ll migrat e across Ih e gas-liquid int er face an d beco me disso lved
in the liquid . Alth ough some mo lecu les o f gas will beg in leaving th e liquid <tllli
re turnin g to gas ph ~ l sc . th e net rC,lc ti ull \Vii i be to\\al'd th e liquid ulltil a stat e of
that affeci x are temperat ure (the so lubility increases as temperature decreases)
and the concentra ti on of oth er disso lved gases and so lid s (the solubility decreases
as ot her di sso lved material in Ihe liquid in creases). r
.L ~
L .. ; 68 WATER

If the space above the liqu id is occupied by a mi xture of gases, each gas wi ll 3. The saturatio n concent ration is
ha ve its own equilibrium mole fracti on. According to Dalto n's law, each gas in a C, = 1.287 X 10 - 3 gm o ljl x 28.9 glgmol x 10 3 mg/g
mixture exerts a parti al pressure In propor ti on to its percentage by vo lum e in :0 37.2 mg/ l
the mixture; th at is.

The so lubility of a ir can also be found by usin g its components and Dalton's law. Th e
PV = (PI + P2 + P3 + ... + fln)V or P = LP; compo nents of air by vo lume are approxima tely as follows:
Substituting into Henry's law, we see that x for the ith gas in a mixture is
, ii p; N, ~ 79 %
Xi = - (3-3)
, !
H; 0 , ~2 i %
in which x;, H;. and p; are, respecti ve ly. th e equilibrium mole fraction; abso rptio n
coefficient , and partial pressure of"the ith gas.
4. Th e molecular mass of nitr oge n is 28 g/ mol a nd H from Table C-2 in the appendi x is
Absorption coefficients for seve ral gases co mmonl y fou nd in natural wa ters
5. 29 x 10"
are given in T a ble C- 2 of the appendix. The coefficients are seen to vary substan-
tially with temperature. Although th e tota l disso lv ed mater ial a lso affec ts the so lu- 0.79 _5
bility, the effect is insignificant in the range of dissolved material us uall y found in
XN = = 1.49 x 10
, 5.29 X 10'
fresh water. To be precisely acc urate, the partial pressure of water vapor mu st
lIN , - 1.49 x 10 - ' nN , = 1.49 x 10 - 5 x 55.6
be accounted for in Eq s. (3-2) and (3-3). Co nve rsion of the eq uilibrium mole
\_- - fraction x to an equilibrium concentration Cs is illustrated in the fo llowi ng ex- = 8.3 x 10 4 mo l/ L
ample. e. = 8.3 x 10 - gnlOl/l x 28 g mol x 10 3 mg/ g

= 23.25 mg/ l
Example 3-2: Calculating the solubility of air in water Calc ulat e the so lubilit y of air in
water at OC a nd I atm press ure. Assume o th er d isso lved ma teria l is neg li gi bl e. 5. The equi li brium concentrations for 0 , and CO , can be found similarly and are 16.65
and 0.02 mg/ L. respec tively.

I. From Table C-2 in the appendix. Henry's cons tant for air at OC is The equ il ibr ium concentratio n of air is
23.25 + 16.65 + 0.02 = 39.92 mg/ l
........ . .. .... .. ' .. ... ....... .. f!. .7.. 'U2. x. 10."..alm/mE>1 fra.:! ion ,L
, Th e discrepancy is acco unted fbr by the rounding off of the percentage of N, . 0, _ and
at I atm pressure. The mo le fr ac ti on o f a ir in wa ter is found by Eq. (3-2).
,..~. CO, in air. .

1.0 atm Transfer Rate

= -. - _._--
-132 x I04 ~11;~;I~lOli~,;~'iio-n Th e rate of gas transfer is an important parameter in aera ti on. The rate of transfer
= 2.3 I x 10 " mo l fracti on is governed by severa l factors and is mathematically expressed as
2. One liter of water contains dC/dt = (C - C)k"
1000 gi l where dC/dl is the instantaneous.rate of change of the concentrati on of gas in t he
- - - = '''6 g llhl l. L
18 g/ mol "' - liquid. C and C are the saturation co nce ntrati on and the ac tu al con centrati o n,
and respectively. and k" is a constan t related to give n physical co nditi ons. lt should be
noted th at desorption of the gas occurs when C is greater th an C The magnit u de
2.3 1. x fo - .5 = __ .r~~. _ .. of k" is known to depend upon the 'temperature of the system. the interfacial ar ea
11 9 + 55.6
avai labl e for gas transfer. and resistance to movement from one ph ase to th e oth e r.
n. - (2.31 x 10 - ' n.) = 2.31 x to - ' x 55.6 While the effect of tempera ture ca n be predicted by the van't Hoff-Arrhen i us
II. = 1.287 x 10 - 3 g . Il1ol.' l ~. ru le. the other va riables are system-spec ific. Th e int erfacia l area a vai lab le for gas


transfer is measured by the total contact surface between the gas and liquid. The driving force causing mass transfer is the concentration gradient, C s - C.
Larger interfacial a rea per given volume will result in greater opportunity for gas Resistance to mass transfer must be overcome for the process to occur, and each
transfer. one o f the steps lis ted above is likely to exhibit a different level of resistance. The
The resistance to movement between the phases is most often explained by the step which offers the most resistance to the movement of gas molecules becomes
two-film theory of mass transfer initially postulated by Lewis and Whitma n in the rate- limiting step. In stagnant situations (i.e .. no internal movement of the
1924. According to this theory, the interface is composed of two distinct films , bulk phases). movement of gas molecules to and away from the interface depends
one on the gas side and one on the liquid side, that serve as a barrier between the to tally upon diffusion , and the process is verysfow. However, if internal movement
bulk phases. This system is shown graphically in Fig. 3-2(1. In order for a molecule of the bulk phases occurs, molecules of gas are transferred to and away from the
of gas so mewhere in the interior of the gas phase to be transferr:ed into the interior interface by turbulence and eddy diffusion. and the rate of mass transfer is most
of the liquid phase. it must move through the bulk gas to the interface, across likely to be governed by one or both of the films.
the gas film , across the liquid film, and, finally, away from the interface and into
the bulk liquid. In systems where the liquid is :supersaturated with respec t to the
gas, movement of the gas molecule will be in the reverse direction (Fig. 3-2b).
In most natural water. sufficient agitation of the bulk phases exists, and the
film s become the limiting factors. In general, gases that are highly soluble in water,
such as ammonia, encounter more resistance in passing through the gas film and
the process is sa id to be gas~jilm-conlrolled. Conversely, slightly soluble gases
suc h as oxygen and nitrogen encounter more resistance in the liquid film , and the
system is liquid-film-controlled with respect to these gases. Gases of intermediate
so lubi lity. such as hydrogen su lfide. encounter approximately equal resistance
., Bulk
g as
through the two 'films and the system is said to be mixed-film-controlled.

~ tI - - - -
Gas film
~ O~ ______________~------------ 3-5 HEAT TRANSFER

~ ! / Li",," "'m Bodies of water lose and gain heat much more slowly than do land or air masses,
. and under most c ircumstances. water temperature is fairly constant and changes
Bulk grad ually with the seasons. Consequently. aquatic plants and animals have not
dcveloped s u fllcien t bi l.ilY 1.0 ..dei\l. \Vil.~. aI:>ru pI . ch.ange~ . in .. r~., ............ .
C" >C r
a nd only 'ti~~' mo st hardy species survive such changes. Thus, heat increases tend
to decrease the number of species of aquatic plants and animals. [3-17J Further-
.Concentration -
more, increases in water temperature affect ionic strength, conductivity. dissocia-
tion constants, so lubility, and corrosion. potential, all factors associated with
. water quality.
Given constant meteorologic conditions. water theoretically requires an in-
v Bulk finite time of exposure to attain equilibrium after a heat load. Furthermore. an "
tnfinite surface area would be required to cool warm water introduced into a .
ro t ~----ll.:---_
__ river or basin to the equilibrium temperature. However. because temperature
"' . Gasfilill decline is nearly loga rithmic , equilibrium can be closely approached within prac-

., !
2 0 ~------------~~------------

.~ I-----"'~
Liquid film "'"
tical limitations of time and su rface area. Many meteorological variables-plus
o ther factors suc h as channel characteristics (depth, width. surface area), channel
volume, etc. - affect the rate of heat transfer in bodies of water. For streams
Bulk heated by solar radiation over several miles of ht;at-Ioad area. cooling begins only
liquid in shaded areas or at night and may proceed much more slowly than cooling in
C, <Cr
Figure 3-2 Twofilm model of the
streams which receive their heat load in one discharge.
interfa ce between gas and liquid: (Ill In temperate zones. heat transfer in reservoirs and lakes where the influence
Concentration - absorption m ode and (h) desorption of turbulence and current is negligible is controlled by a phenomenon known as
(h) mode . {iIennal sWlijic(I{ion. Fresh waters reach their maximum density at 4C (39F),


with density declining as water moves toward the freezing point or grows warmer. 9C OC 4C
(See Fig. 3-3.) Thus, during warm seasons and in impoundment s of suffic ient
depth, water divides into an upper layer of warm , circulating water known as the
epilimnion and a lower layer of cool, relatively undisturbed water known as the
hypolimnion: These two layers are sepa rated by the th ermoclin e, or meralimnion , a
Vertica l
l ee

Ver ti ca l
region of sharp thermal gradient. This stratification is shown in Fig. 3-4a. circu la rion cireu la t ion

Stratification is usually interrupted in autumn (Fig. 3-4b) as surface waters

cool and begin to sink. Wind action can then cause circulation throughout th e
entire body of water so that turnover in the lake's strata occurs, stratification
DJr k.
sUgnan t ,
cooler Hypolimnion
t! tl
disappears, and the body of water reverts to a uniform temperature throughout its water

depth. In cold regions, surface waters freeze over as winter sets in. Waters at 2 e
(36F), being denser than the colder waters above. form a layer a long the bottom , 9C ~oC
a layer in which the aquatic ecosystem survives as long as s ufficient oxygen is a va il- A ugust November January
able, despite the freezing of the lake's surface (see Fig. 3-4c). In spring, the process (0) (b) (el
is reversed as ice melts and turnover occurs (Fig. 3-4d), and summer stratification
Figure 3-4 T emperalure profi les of a deep lake. show ing (a) thermal strat ification, (b) autumnal
begins as surface waters are warmed by increased solar radiation. [ 3-27J circu lalion, (e) winler stagnalio n. and (d) spr in g ove rturn. (Adapted/rom H ammer [3-8].)

1.000 I Water The nature and extent o f stratification varies. depending upon the size, depth,
Ice I configuration, and terrain of the body of water. area-vo lume-stage relations,
1.00 ,-r--~
orientation of prevailing wind s, and hydrologic (or induced) inAo w and outAow
characteristics. as well as with seaso nal variations in temperature. [3-25J


0.95 Chemical Processes

Na tur a l wa terco urses co nt ai n man y di sso lved minerals and gases th a t in teract
i'7 . c hemi ca ll y with o ne another in complex and varied ways. Oxidation-reduction,
.~ 0.9990
dissolution-precipitation. cwe! o th er chemical conversions ma y alternately aid o r
obs tru ct natural purification processes o f natural water sys tems .
0.9 ci L -L..L-L---'-----'-_
- 10 0 10 20 30

II\~ Strict ly speaki ng. mos t of the oxidat ion-red uction conversions that playa part in
se lf-pLmtica tioll of Ilat erClllll'SeS are biochemically mediated and w ill th e refore
t- be discussed in subsequent sect io ns of this c hap ter Be\<Iuse the so lid s dissolved
III 1\~Jt er Me esse lltlal to the metabu li c and reproducti,ie activities o f th e m icro-

4 6 8 10 12 14 16 18 20 2~ . urga ni s ills th ~lt degrade ane! stabili ze o rganic wastes. man y' of th ose processes a re
di rectly o r Indirec tl y Intlu enced by the dlssl,lutio n-prec ipit ation convers ions t ha t
OCc ur in th e watercollrses. /\s ce rtain min e rals pass Into and o ut u f soilitiun. they
become Illore or less I'eadil y availab le to the m icroo rganisms th ~Jt re ly upon them
Figure 3-3 C hanges in the den si ty of (a) wa ler and (bl ice wilh changes in lemperalure. (From Warr ell
for the success ful completion of th eir life processes.


Nitrogen and phosphorus are usually considered the most essential nutrients which living organisms assimilate and use food for subsistence, growth, and re-
found in watercourses. Other materials me equally important to growth of micro- production is called metabolism. The metabolic processes and the organisms
organisms and plankton. though they are needed ill lesser amoullts. Iron. mangan- involved are a vital part of the self-purification process of.naturalwater systems.
ese. copper. zinc, molybdenum. and cobalt are micronutrients lIsually present in
water Natural chemical conversions th:11 may take place ill water call change
these materials into a form thai is soluble and therefore usable by various aquatic
~ Chemical conversions that occur in reservoirs and deep 1:lkes play an imponant
The biochemical reactions involved in metabolism are extremely complicated
role in the accessibility of ph'lsphorus. Phosphorus may enter the body of ,vater
and are not yet completely understood. It is 'known, however, that two types of
attached to particles and settle to the bottom with these particles. Phosphorus
may also enter the water as soluble orthophosphate and become incorpoTated in processes, each involving many steps, must occur simultaneously. One process,
biomass that eventually settles to the bottom. When ferric iron IS also present called catabolism, provides the energy for the synthesis of new cells, as well as for
the maintenance of other cell functions. The other process, called anabolism,
the fo1l0wmg reaction occurs.
provides the material necessary for cell growth. When an external food source is
Fe."" + PO .. " (3-4) interrupted, the organisms will use stored food for maintenance energy in a process
called endogenous catabolism. Each type of microorganism has its own metabolic
The insoluble ferric phosphate IS precipitated and settles to the bottom. There. in pathway, from specific reactants to specific end products. A generalized concept
the relative absence of oxygen. the iron is reduced tpthe ferrous form and the lOllS of metabolic pathways of importance in natural water systems is shown in Fig. 3-5_
go into solution. During spring or fall turnover. the phosphorus IS lllixed through- Enzymes playa major .role in biochemical reactions. Enzymes may be consid-
out the entire depth of the lake. With some of it being used by plant life and some ered as organic catalysts that influence reactions without becoming a reattant
of It recombining with ferric Iron and reforming the IIlsoluble ferriC phosphate themselves. In biochemical processes, enzymes lower the activation energy neces-
compound. with that precipitate again settling to the bott()m to await reduction. sary to initiate reactions. The enzyme th'en reverts to its original form for reuse.
[3-19J A model of enzyme-substrate (food) reactions is shown in Fig. 3-6. Enzymes are
Chemical con\ersions th:lt take place in streams :llld lakes Gin heir tll stabilize complex protein compounds and are very specific in terms of the reactions that they
the pH of those bodiesofwater. For example.lilllestune and other furms otcalciulll support. A microorganism thus needs specific enzymes for each reaction in its
carbonate (CaCO}) dissolve readily in water containing CO 2 , [3 -2oJ
'H';6'f'C(5~" ~'~" 1-1 2 C0 3 *

H 2 CO)* == H+ + HCO:;

The hydrogen ions thus formed react with slightly soluble calcium carbonate to
yield highly soluble calcium and more bicarbonate ions.
CaC0 3 + H' == Ca2+ + I-ICO.J + Endogenous
The bicarbonate acts as a bufTer to protect a stream from pH fluctuations that can
be harmful to aquat ic systems.

Biochemical Processes

Many of the 'chemical reactions II1volvecl Il1 the self-purit\catIOIi process must be
biolo-gicallv mediated. These chemical reactions are not spontaneous but reqUIre
an ex~ernai suurce uf energy for initiation. In the case of biodegradable organics Waste Organic
heat residue
and other nutrients. this activation energy can be supplied by microurganisms
Figure 3-5 Generalized metabolic pathway.
that utilize these materials for f(loci and energy. The sum total of the processes by

Enzyme +
s,,',,"," ~ /
L' ~ l rbon~l ct'ou~
slill'urolls --.........
f /Sl''' ' I tJ ,
Enzyme- pro le lns } LI V I NG \)
~ <3 I NITI A L
{Tam mol~
. H)
s ubs trate
",<-; w cr: PRODUCT S CO 2 --
(o mpkx -
...- C0 2
"'I ClO .
' t
1,12 S

. I I '
protein, } I c {nitrr tes NO~
Enzy me + Prociu ct I"t s LI V ING ~~ INTERM ED I A T E . CO __ -

Figure 3-6 Enzyme reacti o n mod e l.

...- 0 ,
- C0 2
carbohyd rat es PLANTS

~SU lfurs

\ ",t,-alc, NOj
metabolic pathway, The fact that enzymes are not used up in the metabolic pro-
cesses is indeed fortunate, as this frees the microorganism to devote its energies and "'-- CO,
- - - - - stl ll:ll ," SO.;-
resources to the building of new cel1ular material rather' than to the constant
rebuilding of em,ymes,
Microorganis ms are equipped with enzy mes that a re especia l1 y wel1 suited' 1l11rn~l' 1l 0u:,

l" drboIlJ Cl'OLJ S

to the use o f partic ular types of organic m a tter. When these e nzymes are a norm a l
part of a particu la r microorganism. th ey are ca lled co ns tiltlti vl:, Ce lls produce -----.......,.
special enzy mes. ca ll ed adoptive enzymes. when they are ex posed to unu suaL even
tox ic. substances, This accl imati o n occ urs natura ll y. th o ugh at a relatively slow \
o rg;Jl1ll' Jell.!::-
rate. In m a ny cases. th e continued presence of a tox ic Subst:lIl ce w il1 lead to th e INI TI.,\L CO , ~
gradual development of a specific bacteria capab le of decom p os ing and utili zing H )S ~

th a t toxic compound, For example. phenol-splittin g bacter ia are ofte n fo und in

"" ' '' ''''s"t"ream'sHi:iCliave' j:eceived 'di sdiiiiges bf phen o li c wa ters, [ 3-1IJ
Energy is transferred from th e cat<lbo lic reaction to the anabo lic reaction
INTt RMEDI '\TE l' Jillill on;" N H ; ___
thr o ugh high-energy phosphate bo nd s, The remova l o f hyd rogen or the splitting PRODUCTS CO ) - .
of the carbon - carbon bond in the catabo li c process releases e nergy, A sizeable 'i'ulfllk, ~"

fr ac ti o n o f thi s energy is used to add a ph os ph a te atom to adenosine diph os phate
(ADP). converting it to adenosine triph os phate (ATP), The ATP is transferred
to the anabolic reaction where the ex tr a pho sp hate a tom is removed. re leasing
the sto red energy to th e sy nthesis reactioll, The resu ltin g AD P is then trans ferred
back to th e catabolic re ac ti o n to be reen ergized to ;\ TP. a nd th e cycle is repea ted.
Thi s process is s how n g raphical1 y in Fig, 3-7. Thi s descr ipti o n is overs imp lified.

ATP ( iI)

Fi gll'" .I-X NIII')~C " . "ar hnn , " " d su llur c\'cles (II) aerobic and (h ) ""aerobiC , (Fro m Vesrl/lld I 3-~6J-) ,

'- .

ADP + I' Figure 3--7 Energy transfe r mod e l.


a s there are man y s teps in th e process. eac h be ing m ediated by its own se t of Like matter, energy can be neither created nor destroyed. Energy released in
enzy mes. The read e r is referred e lsewhere fo r a mo re co mplete coverage o f the th e catabolic process is transferred to the cellular material synthesized in the
s ubjec t. [ 3-14. 3-20, 3-7J anabo lic process, s tored in the waste products o f catabolism, o r released as
Ca tabo lic processes in vo lve e ithe r the oxidati o n or the redu c ti o n of mat e ria l Ilea t or mec hanical energy. The relative quantities dispersed in these ways depend
in th eslibst rCll e (food su pp ly). Iffree mo lecula r oxyge n is a va ilable, it will be added up o n the na ture of the reaction . as depicted in Fig. 3-9. The end products o f aerobic
to th e s ubstr a te anq t he waste produ c ts will be ox id ized co mpo und s. I n the absence catabo li sm are low-energy, s table compounds, with most of the energy being
o f fr ee oxyge n. bo u nd oxyge n may be rem oved from oxygen-bea rin g com po un d s sto red in the cellu lar materi a l. By co ntrast. m os t of the energy released in a naerobic
a nd hydroge n added to e lement s o f the substrat e. Th e result is was te produc ts cataboli sm remains in the waste product s.
co mposed of red uced co mp o und s. Oxida ti o n reac t io ns are m ore efficie nt because
th ey release g rea te r a m ou nts o f energy . Con seq ue ntl y. ae ro bic metabo li s m pre-
do min a tes when oxyge n is ava il a b le. Th is is fo rtunate becau se the ox idi zecl p rod- 3-8 MICROORGANISMS IN NATURAL WATER SYSTEMS
uc ts o f ae ro bic processes are less objec tion a ble in na tur a l water sys tem s than the
redu ced produ cts o f ana e ro bic processes. H owever. anaerobic metabo lism d oes C lassical no mencla ture divides living organisms into two major subdivisions or
play a n impo rtant role in was te ass imilati o n in oxyge n-d epleted wat ers and sed I- kin gdom s, plants and a nimals. Th e term protista is often used to classify organ-
ment. is ms in which there is no cell speciali za tion ; th a t is, each cell is capable of carrying
Severa l interm ediat e ste ps ma y be in vo lved in th e metabo lis m o f orga ni c o ut a ll of th e functi o ns of that organ ism. Members of the protista group are caUed
ma ter ia l. Eac h int e rm edia te step ha s its ow n end pr od ucts, some o f whi c h may protists and may belo ng to either the pla nt or anima l kingdom under the classical
beco me s u bs tr a te in s ubsequ en t reac ti o ns. Thi s is illl1 strat ed by th e nitr oge n. no mencla ture. Most of th e o rga ni sms of significance in natural purification
ca rb o n. a nd sulfu r cyc les s how n in Fig. 3-8. processes .....: bac teria. a lgae. a nd protozoa - are protists.

B1 0lllJ SS

Bacteria are the primary decomposers of orga nic material. Bacteria are single-
ce ll protists th a t utili ze soluble food. Although bacteria may link together into
Aerobic Availabl e chai ns or clusters, each cell is an independent ..orga.f)j~m .capable.of ca.Hying out ... .. .... .. .
p rocesses ellt..' rgy
W aSlc' hC'al
all t he 'necess a ry 1ifHlt"rii::ti6 iiS.T3-(4J 'the' structures of bacterial cells typical of
na tural wa ter syste ms are illu strated in Fig. 3-IOa. A listing of the relative abund-
a llce o f the element s comprisi.n g the ce ll is presented in Table 3-1. The chemical
formula fo r bacterial cells is assumed to be C 5 H 7 O 2 N. [3-1 SJ
Energy fo r bac teri a l grow th and reproduction may be derived from the
Wa s.! e
prod uc t s
biochemical ox idation of inorganic or organ ic compounds. or from the reduction
o f these co mp o unds. A few bacteria are a ble to utilize ultraviolet energy from sun-
Biomass li ght. M a terial so urces can be derived from either organic or inorganic compounds.
Bac teria are often classified accordi ng to the energy and material sources that
th ey require. Organisms that derive both energy and material from inorganic
so urces are called al.ltotrophs. while bacteria th at obtain both energy and material
from o rga nic comp ou nd s are called li eterotrophs. Pliotorroph s. bacteria wh ich
AJ1~le r obir Available
utili ze sunlight fo r an energy so urce and in o rganic substances for a material
processes ene rgy
so urce. pla y an ins ignificant role in the natural water purification processes.
He ter o tr o phic bacteria are 'the mos t important species in th e degr adation of
o rgan ic material. Aerobic hel erotroplis require oxygen in their met a bolic processes
whil e eIl/uerobic liet emtroplis utilize o rgan ics in the absence of oxyge n . A third
Vv:I Slc pr o c!u . . . l\ g ro up. ca ll edjacu/tative het erotroplis. functi o n as aerobes when oxygen is present
Fi gure 3-9 Energy balance III mel~b,)li,m U/ler Slrele (lnd ,1/ ciiiJel' [3221 ) but sw it c h to a na ero hi c processes when oxyge n becomes unavailable. A maj o r


Cytoplasmic membrane Cy toplasm , con taining Table 3-1 Bacterial cell compo-
regu la tes transport of ribonucleic acid ( RNA ). sition
Ce ll wa ll food int o and was te produ cts contro ls anabo li sm, manufa c tures
gives shape to out of ce ll. and recycles enzymes, Elemenl Dry weig ht . ~~
ce ll and preven ts
stores food.
destruction by
. shear forces: may Carbon SO
be 10-50% o f Oxygen 20
ce ll weight. Nitrogen 14
H ydrogen 8
o . '.0
Ph osphoru s 3
0 '" .'0 '0.' 0' ..0' '.'0
: '.
-'0 .
00' . 0 0 ., o Pota ssi um
, 0 ,.".0 0 ",
Sodium 1
Calcium OS
Ma gnesi um 0.5
Nucleus, a
Chlorine 0.5
S lim e layer of si ngle stra nd of
o rgan ic poly m e rs deoxyribonucleic acid I ron 0.2
va ries in thi ck ness (DNA), co nt ains ge n e tic Allolhers 0.1
with "age" of t he ce ll code: w ith RNA regulates
and o th er env ironm e nt a l metabo li sm . ,<Jour('(': r-rom Gaudyanu Gaudy
co nditi o n s: sto res food [ 171
aQd bi nd s food and o ther
bac te ri a int o floes.
funct ion of auto t rophic bacter ia is t he oxida ti on of nitrogen and sulfur compou nd s
to stab le end prod ucts.

Like bacteria, protozoa are Single-ce il orga nisms that rep rod uce by binary fiss ion.
Unlike bacteria, protozoa ingest sol id orga nics for food. Si nce protozoa are one
; to two orders of rTla!;llit LI CIc: .largertI1Cll1.pac;te.ri a..lhe prot ozoa d iet often includes
.. ~.
'b~ctc'l:iai' ce(l s' ,is we ll as co ll o idal organics. There are many aquat ic species of

~ protozoa. most of which are strict aerobes. Lik e heterot rophi c bacteria , they obta in
f both energy a nd material for growth and reproduction fr om th e same orga nic
food so urce.
The mo st Important pro tozoa l gro up in natural wate r systems is th e ciliata.
Th ese orga ni sms are charact erized by hairlike appendages called ,ilia and may
be either free-sw imming or stalked (attached to a so lid particle). as illu strated in
Fig :\-1 1. The free-swimming protozoa use <l rapid movement o f their ci li a to
prope l themselws through the water in sea rch of food. The stalked pro tozoa use
f. their cilia tll bring food in frnlll the surro unding water. Prot ozoa are vO f<lci ous

i" Cons umers of organic material and are impor tan t members of th e aquatic com-


(b) Algae arc auto tro ph ic. photosy nth etic organ isms anu . eve n th o ug h they uo not
utili7e orga nic compounus directly. playa significant role in th e natllral purification
Figure 3- 10 (a) Generalized struclure of a bacterial cell; (h) photomicrograph of fre,hwatn bacteria
attached 10 a su rface. Threadlike materials a re ex tracellu lar polymers that hind Ihe organisms togelher prc>cess. In the presence of sunlight. :J!gae metabo li ze th e waste pruduct s of hetero-
;\Ild 10 the surface (photo courlesy"j W . C . Chararklis) . trorhll' hacteri:1 (C0 2 , 0 , . PO.,-'- . etc .) wh il e obt:lining energy from sunl ight.

Response of Streams To Biodegradable Organic Waste

Th e self-purification of naturalw a(er systemsisac()mplex process that ()ften

in vo lves physical , chemical , and biological processes working sim ultaneously.
C hemical and biochemical re ac ti o ns a re conversion processes rather than re-
mo va l processes. The nature, a nd perhaps phase, of the waste may be changed, .
but t he produ cts remain in th e water until phys ica l processes remove them from
suspension by sedim entation or b y transfer to the a tmosphere. This isillustrated
by the reaction in Eq. (3-4). Here chemical processes combine iron and phosphate
into solid form. and the physical process of sedimentation removes it from sus-
pen sion. Another example is the metabolism of organics by microorganisms.
Bi ochemical reactions convert the organics to biological solids and other end
products that may be recycled several times (Fig. 3-8) before ultimately being
incorporated into bo tt o m sed iments or released as gases to the atmosphere,
both by physical processes.
The self-purification processes can be modeled , provided the waste character-
is ti cs and th e system var iables of the water body are known. The modeling process
is co mplicated in lakes and estuaries by dilution and dispersion characteristics
that are va riabl e with time. A complete discussion of water-quality modeling is
be yo nd the scope of this text. Ho wever. some examples will be used to illustrate
th e interaction of the physical, chemical, and biochemical processes described
Figure 3-11 Ph otomicrograph of a stalked protozoan: n o te haIrlike cli la used in the food-gathering ear lier. The examples chosen relate to the assimilation of organic material by
process. streams and the res ulting effects.on the oxygen balance and the ecosystem . Al-
th o ugh these topics are the o nes most frequently covered in the literature on natural

. " . . . .. . . On.e'Is\e.PJ(xlnctsoflhis.reaclionisox.ygen.When s unligh t is no t a va ilable.

purification processes. the reader should be aware that other self-purification
processes, with respect to other contaminants, may be of equal importance.
the algae catabolize stored food for energy a nd use oxygen tn the process. This
diurnal nature o f alg a l ca tab o li sm is an important factor in the oxygen balance o f
natural waters that a re nutrient-rich . , --
Th ere are lite ra ll y thousands of species o f algae of va ri o us sizes. s hapes, and
co lors. Algal ce ll s ma y be fo und in clusters. in lo ng filaments a ttach ed to ba nk s or Disso lved oxygen is o ne of the m os t important constituents of natur~1 water
bottom materi::li. or may rem a in as single ce ll s suspended in wa ter. So me spec ies sys tems. Fi sh and o th er aquatic animalspecies require oxygen, and a stream
of algae can ha ve negati ve effect s on water qua lit y becau se th ey produce o il y mu st have a minimum of abo ut 2 mg/ L of dissolved oxygen to maintain higher.
s ubst ances th a t cause t::tste anet Ddor pro blem s. life for ms. At least 4 mg/ L of disso lved oxygen is required for game fish and some
s pecies lllay require m ore. In addition to this life-sustaining aspect, oxygen is
impo rtant beca use the end products of chemica l and biochemical reactions in
Other Organisms anae ro bic sys tems often pro duce aes theti ca lly displea s ing co lo rs, tastes. and odors.
in water.
Other microorganis ms may a lso play important ro les in the natural. pur ification
When biodegradabl e o rganics are discharged to a stream con tai ning.dissolved
process. R o {ij l'l"S anet uu.\"(ucca are 'Iower -o reie r a nim a ls th a t. prey o n bacter ia.
oxyge n. mi croorganisms beg in the metabulic processes that convert the organics,
prot oz()i!. Li nd al gJe. The\' flelp to maintain a baLtnce In th e p(ipulations ofprlln;t ry
along with the disso lved oxyge n, int o new cells a nd' ox idized w:\ste product s.
producers ;lI1d sc n e as an impo rt ant link in th e chai n by which o rgani c m ate rials
Th e q uantit y o f oxyge n required fo r thi s conversion is the biochemical oxygen
a re passed o n to hi g her-o rd e r animals. SI1IlCj(' worms s uc h as tublfex a ncl bl ood-
demand discussed in Sec. 2- 13. The rate ;It w hi c h the dissolved oxygen is used
worlllS. a s we ll as u th c l' helminths and in sect la rvae. feed o n sl ud ge depos its and
will d epend on the quantit y of tli e organics. the ea se with which they are bic-
help to brea k down and s() lubilize th e part icu late organics.
degraded .. and th e d iluti on ca pac it y of the stre am .


The di ssolved oxygen that is used from the stre a m must be replaced o r a n aer- bac teria l metabo lism. major a lgal ac t ivit y usua ll y occurs downs t ream fro m . rather
o bic co nditi o ns will devel o p. Two mech a nism s a re kn o wn to co ntribu te oxyge n tha n with in, t he area o f grea tes t bac teria l ac ti vit y w here t he oxyge n is needed th e
to surface wa ters; (I) di ssolu\io n o f o xyge n fro m th e a tm osphe re, o ft en ca lled mos t. Also, in th e abse nce o f li ght. a lgae o bta in ene rgy fr om e ndoge n o us catabo l-
rea era ti o n, and (2) producti o n o f oxygen by a lga l ph o tosy nth esis. ism represented by th e fo llowing reactio n.

T h is reac ti o n contributes to the oxygen de m a nd ra th er th a n to th e oxygen sup p ly
Th e princ iples bf equilibrium b et ween wa te r an d gas in cont ac t wi th eac h o t he r of th e stream.
a re desc ribed in Sec. 3-4. Equilibrium co ncent rati o n s o f oxygen in wa ter a t vario us The difference in a lga l catabo li sm d urin g li g ht a nd da r k p e ri o d s res ults in
tempe ra tures a nd salinit y va lu es are g ive n in T ab le C-3 o f th e a p pe nd ix. Whe n diurnal variations in the dissolved oxyge n in strea ms wi t h heavy alga l g row ths.
co ncentration s of disso lved oxygen drop below th e equili b rium va lue. th e n et T he dissolved-oxygen concentration often peak s arou nd 2 to 4 P.M., wit h t he lowes t
m o vement of o xyge n will be . fr o m th e atm osph e'r e into th e wa ter. The diffe rence levels occu r ring j ust before sunrise. U nfo rtu nate ly, th e excess oxygen gen era ted
between the equilibrium co ncentra ti o n a nd th e ac tu a l co ncent ra ti o n is ca lled du rin g t he d ay can no t be sto red fo r use du ring th e ni ght , as it is ex pe lled to the
th e oxygen deficit a nd is represented m a them a ti call y b y at mosphe re to m a in tai n equil ib riu m. In _cases w here th e a lga l g row th is heavy,
D = Cs ~ e (3-5) the endogenous catabo lism may de pl ete t he di sso lved oxygen to t he point w here
fish ki ll s occur.
whe re D is th e di ss o lved o xygen d efi c it a nd C, and a re th e equilibrium co nce ntra - Because of tli c variability o f photosy nth eti call y p ro du ced oxyge n, reae ra tion
ti o n a nd ac tu a l o xygen c oncentrati o n , respec ti ve ly. T he units o f a ll th e terms a re is co ns idered th e Ill os t dependab le source o f di sso lve d oxyge n. "t may be necessary
milli g ra ms pe r liter o f oxyge n. F or co n sta nt eq u ili b riu m co ndi ti o ns. i.e .. C d oes however. to Inc lu de p ho tosyn t hetic oxyge n in a d isso lved -oxygen mode l for wa ters
no t cha nge. th e ra te o f c h a nge in th e d e fi c it is where algal growths are heavy.
dD de (3-6)
ci l dt
T he d eficit thu s incre ases a t th e same ra te th a t th e o xyge n is used up.
The di ssolved oxyge n d efic it is th e dr iving fo rce for reae ra ti o n. Th e g rea ter t he
Most a ll of the di sso lved-oxyge n mo d e ls in c u rre nt use rela te in some way to the
de fi c it , th e g rea ter the ra te o f reae ra ti o n. It fo ll ows, th en, fro m Eq. (3-6) that the
model de\e loped hy S tree ter <lI1 d Phe lps in 1925. T hi s m odel.predic ls.c na n ges in
rate o f reaerati o n in cre ases as th e co n ce ntra ti on o f di sso lved oxyge n d ecreases.
t he deficit as a fun ctio n of BOD exertion a n d st ream reaera ti on.

Algal Photosynthesis
Rate of Ox ygen Removal
In t he presence o f s unli g ht , a lga e me tabo li ze inorgan ic com po u nd s, wi t h one of t he
was te product s bein g oxygen. The fo ll ow in g fo r m ul a is a sim p li fi ed represe n tation The rate at \Vhich disso lved oxygen disappears from the stream coincides with the
o f thi s reac ti o n . . rate of BO D exert ion. Therefo re

(3-7) dy de
(3-9 )
~' - III dl
algal Substituting into Fl] . (1-6)
til' dD
T he oxygen thu s re lea sed is immed ia te ly ava il ab le to reple n is h t he di sso l\ ed (3- 10)
oxyg(': n in th e wa ter. In th e presence of excessive nu t rien ts and hr ight su nli ght. III cil
a lgal me tabo li sm m ay produ ce S(l muc h oxygen t ha t th e water hecomes s u per-
l'onlirlllil1g th~lt :111 increase In tlie r:lte of BOD exertion results III an incre:lse in
sa tura ted . Th a t is, > C, a nd th e defic it has a nega tive v:t1u c. th e ,:lle "f ch: ll1 gc ()f (}.\:gcn delicit . III Sec. 2-1). It was s hown tha t
Ad\ erse fac to rs associa ted wit h excessi\'e a Iga I gn)w t hs (li'ten (lut we igh the
be nefi ts o f the oxyge n th ey prod uce. Because algae use the waste produc ts from I' = L. o - L,

. L


Because Lo is the ultimate BOD a nd therefore a fixed va lue.
Table 3-2 Reaeration constants
dy dL,
tit dl (3-11 ) Ranges of k, at 20'C.
Water body
base e
Recalling Eq. (2-20)
Small ponds and backwalers 0. 1- 0.23
dL, = -kL, Sluggish st rcom s and large lakes
Large s!reams of low velocily
0.23 - 0.35
dl 0.35- 0.46
Large streams of normal ,e loci ty 0.46 - 0.69
Swift streams
a nd making appropriate substi tuti o ns in Eqs. (3-11) and (3-10). the following 0.69- 1.15
relationship is obtained . Rapids and waterfalls
Grealer than I 15

dD Source: Afler Melcatf& Eddy, Inc. [3 - 15)

-- = kL
ill ' (3-12)

which states tha t the rate of change in the dissolved oxygen deficit at time I due opposi te effects on the deficit. This is shown gr;tphically in Fig. 3-12. The rate of
to the BOD is a first-order reaction proportional to the oxygen equivalent of the cha nge in the deficit is the sLIm of the two reactions
remaining o rga nics. A more convenient form of Eq. (3-12) is

rlJ = kiL,. (3-13)

where r D replaces the differential form as the rate of change in the oxygen deficit
due to oxygen utilization. The reaction rate constant k, is th e same parameter (3-15)
described in Sec. 2-13 and is derived from laboratory tests on the wastewater. The
The actual oxygen concentration (e, - D,) has a c haracteristic dip as shown in
rate constant is adjus ted for temperature changes. but is not usually adjusted for
other effects of dilution wit h the st ream water. Fig. 3-12. resulting in the term lixYif'1/ sag ClIIT', commonly used to describe the

Rate of Oxygen Addition

As no ted in Sec. 3-9. the rate of reaerati on is a first-order reaction.withTespecl. . .~~ .

to the magn ituci e uf the oxyge n deficit This is expressed mathematically by Cl'"

J. Equilibnuln .::onlcnlr"~~~ _ _ _ _ _ _ _ _

where r R is the rate at which oxygen becomes disso lvell fr o m the atmosphere. {) is _J"
the oxygen deficit defined by Eq. (3-5), and k2 is a re;ler~ition rate constant that is
sys tem-specific. The nega t ive sign reflects t he fac t.t hat an increase in t he oxygen
s uppl y dlle to reaeration reduces the oxygen deticit. Factors atlec tin g kl illclude ...=1.
>, C ,
stream turbulence (a fun ction of velocity and channel characteristics), surface 6
area. water depth. and temperature. Temperature corrections are mad e by Eq. 'tJ
c; --+,-
(2-23) with a value of 1.016 fo r () being most common. Several models are available f"
I "-
- I
for determining numerical values for k 2 [3-16. 3:4], the development of which is C;
beyond the scope of this text. A range of\a lues typically found aprlicable to various I
flow regimes is given in Table 3-2. I
The Oxygen Sag Curve

The oxygen deficit in a stream is a function of both oxygen utili z;lIion and re;ler;l-
Tiull'. day~
ti on In spectlun of b.Js (.3-13) and 13- 14) s hows th"l these two processes ha\.c
Figure .1-12 CharacteriSlics u f the o'ygen sag cuneo

The oxygen deficit, and therefore the oxygen concentration, at any point in The fina l so luti on becomes
time after the discharge can be determined by integrating Eq. (3-15). This is not,
however, a straightforwa rd operation. Recalling from Eq. (2-21) that
Dekll = kILo ( e1k'- k,)r + Do - ~)
k2-kl k2-k\
L, = Lo e- kll or
and rearranging Eq. (3-15), the following equation is .obtained
dD .. '
Tt + k2D = kILoe - k" (3-1 6) and in final form
k L .
which is a first-order differential equation of the forr~ D = \ 0 (e - k" _ e-k, ,) + Doe-k" (3-20)
k2 - ki . .
-d + Py = Q In thi s equat ion. t represents the time of travel in the stream from the point
x of discharge and is the on ly independent variable in the equation. The time of
where P and Qare functions of x, [3-1] The use of the integrat ing factor ex peS P dx) travel from the point of discharge to any given downstream 'point is:
ISnecessary for the solution of this type equation. For Eq. (3-16). the integrating X
t =- (3-21 )
factor is u
where x is the distan ce along the stream and II is the stream velocit y. The units
of 1 must always be days. Substituting va lues for t, or x/u. into Eq. (3-20), will
Multiplying both sides .of Eq . (3- 16) by the right side of Eq. (3-17) yields result in a va lue of D for that point in the stream.
The mos t important point on the oxygen sag curve is often the poin t of lowest
ek" _dD + k Dek" = k L e(k, - k,)1 (3-18) concentration because this point represents the maximum impact on the dissolved
dc 2 I 0
--.\ oxygen due to wastewater discharge. This point is called the cricical deficit Dc> and
The left side of this equation can be factored as follows the time of travel to this point is termed the critical cime tc' Recognizing that the rate
of change of the deficit is zero at the maximum deficit. an expression for Dc can be
ek" _ + k Dek" = _ Dek"
d ..fou l1 cl f.r ornEq. U,\ 6) ...
. . .. ..... dt ..... 2 . .. .. (/t .... ..... . ...... .

Separating variables and integrat ing or

JdD ek" = kiLo Je(k,-k,}! dt

The. integration of which yields
The solution of thi s equa tion depends on a numerical va lue for cc' which is some-
what more ditfic ult to obtain. First, Eq. (3-20) is differentiated and set equal to
The constant of integrati on C can be determined from known boundary condit ions,
zero. again because Df is a maximum at cc:
that IS, D = Do at ( = O. Therefore
. k L . k c
~. o= k-=--~ ( - kie - k",. + k 2e - k" c ) - k 2 Doe- "
,t 2 \

Dividing throu gh by e- k" c


rea rra nging b. BOD [Eq. (3-1)]:

y,Q, + y",Qw
'y'mix. = .. .
Q, + Q",

3.0 x 0.5 + 40 x 0.17

and 0.67
k k - k
" _ f) ~ _2 _ _1 l2.4mgj L
2 II kI La
Convert to ultimate BOD. (Assume kl = 0.23 for mixture')
dividing through b~ k I ami taking the logarithm of both sides
= .In (k- 2 - k, k2 -- kI) y. ;= Lo = 1 - e k
(1,. - k )1 D ) -- - - - -
2 I, "I 'q Lo
_e- O. 23 )(5
or in more convent ional form

I, Do /" - - -k I)J (3-23 )

= 18.2 mgj L

"I L o c. Disso lved oxygen:

Equations (3-22) ane! U-23) can be used to determine the critical oxygen le vel in 8.0 x 0.5 + 2,0 x 0.17
DO m ;, = 0.67
the stream and the position ~It \\ hich it OCClIlS. Th e procedure is illu strated in the
following examp le. = 6.5 mgj L

Exa mple 3-3: Appl yi ng the BOD sag curve .- \ municipal wastewater-treatmcnt plant
dischargcs secon dary cfJ-lucnt to a surl"ace stream . Th e wo rst co nditi ons arc known to 22 x 0.5 + 25 x 0. 17
occur in the summer month, whell stream tlow is low alld water tempera ture is hi gh. Tmix = 0.67
Unda the se conditIOns. mea surcmClll S arc made in the laborat o ry and in Ihe tield to
deterrTllne- 'rhe- 'cha ra cleri'sl it~; (if' ihl'" \\':l~ ie\\' :!kr' and , Irea III fl ows. The waslewalcr is
I"ound 10 have a maximum flow rai l' \)1" 15.000 rn J;uay. a DOD , 01" 40 mgiL , a dissolved
2. Correct reaclion constants for temperature_
oxygen concenl r,lIion of2 mg L. and a Ic mpcra lu re o f2 5 C Thc stream (upslreal11 from
a. BOD reaction rate [Eq . (2-23)J:
Ihc puinl of wa<lewaler discharge) i, round 10 ha\'c a Illillilllum t1 0w rale 0 1- 0.5 m J/s , a
BOD , of 3 l11g ' L. a dl sso h'cd n\\gCIl concenlralion 0 1' 8 Illg/ L. and a Icmper~!lure of k" .8 = k 20 ( 1.047 12 .8 - 10)
22 ' ('. Complcl c mixin g o f Ih c \\'aslc\\"aler and SlrC:lm "almos l in"lanlaneo us, and Ihc
= 0.23 x 114
\'elocilY of Ih e Il1IXIUI"C IS 02111 " . l- rol11 Ihe 11(1\\ rq!llllc. Ih(' reacr~!li\)n cunSlanl is
cstimaled 10 be 0.4 ua) - , for 2(1 (. cundili,1I1'> .
Skclch Ih e disso h'cd O\ygcl1 IH o liie a IOO klll reach of Ille , Ircam bel o w Ihe dls-
eha rge. /J. Stream reaeration rate

k 22R = k 20 (I.01612.8 - 10)

= 0.4 x 1.05
I. Determine'c haracrenstics l)f \\'aste\\"~'ler-Slrealll mixl;,re. );"22" = 0.42 d . I = k2
I d I Il I min
( I. Q:, - IS.noo m' d X X X ---- 3. Determine initia l oxyge n deficit Do
2<1 h (,() min 60 s
(J. At T = 22.8. the eq uilibriul11 concen tration of oxygen in fresh water is 8.7; therefore

= 11 . 17 Ill J S
J Do = 8.7 - 6.5 = 2.2 mg/ L
Qrnlx = 11.17 + n .) = n.b7 Ill , S

4. Determine the critical deficit and its location. These point s are connected by a smooth curve as show n in the accompanying figure
to yield the desired oxygen profile of the stream.
a. I, = _I_In[k2 (I _
k,-k, k,
Dok, -
k')] (3-23)

= I In [0.42 ( 1 - 20.42
2 -- -0.26)J
- --
- - -- - - - ----------------
0.42 - 0.26 0.26 . 0.26 x 18.2
8 .
1, '= 2.5 d . Do
k, C
b. Dc = - Loe-k'tc
k, c 6
0.26 18.2e - 0'
= _ .6 X '.5 o
= 5.9 mg/ L .~
c. This condition will ~ccur at a distance of

x = 0.2 m/s x 86.400 sid x 2.5 d {c :::. X/II

= 43.2 km downstream from point of discharge
75 100 125
5. Determine the deficit at points 20, 75. and 100 km from the point of discharge. o
Di st3n cc downstream, km
(I. 1= - - -
u km/d Bot h th e position and magnitude 6r the critical deficit ar e related to t he sys tem
Ikm86.400 s variabl es (/'1' " 2, L o, Do. and u). The time o f travel to the c riti ca l defi c it (rJ is
u = 0.2 m/s x - - - x - - - = 17.3 km/d innuenced more s trongl y by th e va lues of /.:.1 and /.:." . while the magnitude of the
d 1000 m
deficit is m os t affec ted by th e L o va lu e. N o t o nl y do heavier loads resu lt in greater
1'0 = 20/17.3 = Ll6d defi c it s. but th ey extend th e inAu e nce of th e waste farther down s tream H eavy
175 = 75/17.3 = 4.3 d loads of organics may result in th e' developmei1t 'of'a'I1ae-rubic condiriooS.Und'er
t hese conditions, o xygen is tran s ferred in a t a high rate [Eq. (3-14)J but is used up
1'00 = 100/ 17.3 = 5.8 d
by facultative o rga ni s m s that may also be utilizing the organic material produced
b. The deficits at these times are: by a naerobic m e tabolism. In a deep s tream , true anaerobic organisms may Aourish
k L near thebottom. Only after the strength of the waste has been sufficiently reduced
D = _ _ '_0_ (e - '" - e-"') + Doe -'" (3-20) .
k, - k, . will aerobic condition s be re sto red. Since anaerobic metabolism is a siow. process,
recovery of an overloaded st rea m will be slow and the oxygen sag will extend far
D - 0.26 x 18.2 (e'
-0 ,6x II 6 _ e-O .42Xllb)+2.2e - 0.42XI.'6 downstream. - "
20 - 0.42 - 0.26
= 5.1 mg/ L
D 75 = 5.2 mg/ L Limitations of the Oxygen Sag Curve
D,oo = 4.1 mg/ L
Th e limit a ti o n s o f the oxyge n sag c ur ve s hould be at o nc e appare nt Th e rate o f
.6. The dissolved-oxygen concentrations at each po int are found to be: d eoxy gen ~llion and th e ra te o f reaeration a re each affected by many va ri ab les fo r
C 20 = 8.8 - 5.1 = 3.4 Illg!L which the mod el mak es no a ll owance . .

C n2 = 2.8 mg/ L BOD variables Th e eq uati on is ba sed on the a ss umption that th ere IS one source
of BOD w hen there m ay actually be seve ra l diffe re nt point or n onpoin t so urce s of
C 75 = 3.5 mg/ L BOD. Additional di sc harges can be tak e n into cons ideration by s ubdi vidin g a
C'oo = 4.1 mg/ L ri ve r into short reache s, each feci by a single p o int so urce. If tributaries empty int o

the m ains tream , any di scharge they may have recei ved mu st al so be tak e n Illto and their products grea tl y influence th e ecology (th e relationship between living
co nside ra ti on, a s we ll as th e in crease in flow o f th e rece ivin g stream. organis m s a nd th eir envir o nm en t) o f th e strea m. Lik e the oxyge n b a la nce the
E ven when care is gi ven to co ns id er all o rga ni c lo ael s intro du ced at di sc har ge ec; logical balance of a s t ream rece ivi ng a biodegradable organic discharge c;n be
POlll ts, the bi o chemica l ox ygen demand ora str eam ma y be affected by o th er fac to rs mod e led. M os t of the model s a ss ume t ha t t he organic waste is com p osed primaril y
no t app ro ximated by t he k I co n stan t. A lga l re spira t ion in th e absence of s unlight, of municipal wastewa ter and d o es n o t conta in s ign ifica nt quantities of mat.eri a ls
nitrificati o n processes that in c rea se ox ygen d e m a nd , and the presencc o f slud ge that wo uld be toxic to t he flora a nd fauna of th e stream.
d e pos it s in pool area s can al l in c rea se a str eam's BOD. [3- 5, 3-8J In s hall o w Ecologica l modeling usually involves divid in g th e strea m int o reaches, o r
s treams, masses of m icrobial growth attach ed to th e strea mbed lIlay be more zo nes, in w hi ch certain species or certam processes predominate. The model mos t
e tncient at utili z ing o rgani cs, and con sequ entl y co nsum e more di ss ol ve d o xyge n common ly used in the United States is the o ne devised by Whipple, Fair, and
th a n the s us p ended micro o rgani sm s used in th e laborat o ry BOD tes t. [3 -2 IJ Whipp le. Thi s model d ivid es the stream into four zones labeled the zones o f
This fac t, though recognized and va lu ed in engineered tr eatment sys tems, is o ften degradation, active decom position, ,:eeaver)', and clean water. A summ a ry of th e
ig nor ed in self-purifica ti o n stu die s. pllyslcal, c hemica l, a nd biological c haracte ri stics o f each zo ne is presented in
Table 3-3.
Reaeration variables R ep lacement of o xygen is al so affected by man y fact o rs M a n y o f the ph ysica l c haracteristics described in Table 3-3 may be n o ted b y
not taken int o considera ti on by the _form ula s used t o derive oxyge n sag curves , the casual o bserve r, but the chemica l c ha rac te ri st ics (w ith the exception of th e
notably the reaeration co ntribut ion of algae p h ot os ynthesi s . F u rt he r, th e math e- presence of highly od o rou s H l S) ca n be determi n ed o nly thr oug h samp ling and
matics assumes stead y-sta te condition s all along a ri ver c ha nn e L Becau se such laborator y test in g. Biol o gical s pecies and numbers are mark edly d ifferent from
steady-stat e condi tions wo uld indeed be rare , m o st streams must be s ubdiv ided zone to zo ne, and spec ies d ive rsity is a prim ary means of establishing zone bound-
and a k c va lue assigned to each reach. Even with subdivisio n into reach es, det e r- ari es. The change in species and number s of o rganisms in each s pecies is illustrated
mination o f the kl constant is probab ly th e one area most prone to error in ,. in Fi g. 3-1 1
oxygen -sag-curve wo rk, becau se n o theoretical as sumption of flow characteristi cs 1
Th e food supply is a primary fac tor in determining the type o f o rga ni sm s that
- channe l formation, obstacl es, pool s , effect s of impo undments , and othe r such predom inate. Nea r the po int o f discha rge, bacter ia, protozoa, and molds predom-
var iables - is like ly to fit anyone particular stream perfectly. inate. Bac teria fi nd an abu nd a nt food supply in the form of carbo hydrates, pro tein s,
Addi t ion s ha ve been made to the bas ic Streeter - Ph e lps model that incorporate and fats. As th ese microor gani sms decompose organic was tes, they co nvert them
the diurnal effec t o f alga l ph o tosy nthesis, th e nitrifi cati o n process, and th e sedlm en- into nutri ent material s suc h as nitrates, p h osphates, a nd carbo n dioxide. The
tation-resuspension of organic material. Th ese model s a re present ed e lse wher e In bac teria l populati o ns flouri s h until di ssolved o xygen and lor th e fo od su pply is
the lit erature [3-22J and require a much more sophi st icilted.llat a ba sefo r use: . . . . ex ha us ted. Bemuse bacteriaprovrdefoodfor . prOHizCia: ci liat es, ro tifers, and
"r '
cr ustacean s, th ese higher fo rm s of life diminish as bac ter ia die o ff.
Confirmation of the Oxygen Sag Curve Th e abundan t sup ply o f nutri ent materials made avai lab le by th e bacteria!
decom position of o rganic m a tter brings abo ut still furth er changes. About midwa y
The di ssolved- o xygen pro file o bta in ed fr o m ma t hemalica l mod e ls s ho ul d be through the zo ne of ac ti ve decomposition, w here miner a l nutri en ts (notably
con firm ed by ac tu a l field mea s u rements. Id eall y, th e re s ho uld be a co m p reh e ns ive n it rat es ) abou nd, a lgae beg in a ra pid inc rea se. Blue-gree n (Phorl11idillm, Lyngbya,
samp lin g und e r condi ti on s of kn ow n waste load s and rivt:r hydr o logy. A peri o d a nd Oscil/atoria) and g reen alga e (Spirogyru and St ig t'oc/uniul11), a n d diatoms :,
o f warm weat her a nd lo w flow s is desirable, and dail y samp lin g fo r I m o nth fo r all (GulIlrhon ema and Nit zschiu) may be present in thi s zo ne. [ 3-3J ..
param eter s is prefe rred. Once the DO d e ficit a nd th e time tll th e c ri t ica l () 2 In the zo ne of rec over y. a lgae g ro wth peak s, then declines, w ith a lga l p op ula-
concen tr a ti on have been verified by a deLl il eci \ vat e r-qllality sline y. oxygen sag t iu ns III th e clean zone beginnin g to appr ox imat e th ose found in the predischarge
c ur ves ca n be used to fo reca st stream co nditi o n s th a t ca n he ex pec ted fo r g i\T n purtions of the stream. Blue-gree n (f\llicrocys Lis and Anabaena), pigmented
Ila s te lo ad s and s tr eam fl o ws. Ila gellates (Euy lenu and Pando rina ), g reen al gae (Cladorlrol'u and Ankistrodesmus),
and di a tom s (l'vl f' ridio/'l andCrc/o tella) are s pecies fo und in the zoneof recovery.
[ 3-3J . .
3-1 I ORGANIC DISCHARGE AND STREA iVI ECOLOGY . i As nutrient lo ad s dec lin e, BOD decrea ses, an d DO levels r eturn to th ei r
p redi sc har ge le vels, alga e and ba c teria po pulation s return to their clea n- water
In :lddltl o n to \ :Hia t i;) ns In th e o .\v ecn cn ncc n tr at i, )n s. lll ;lll .\ ,' II ,e l piIysiul. statll S, and clean-wa ter invertebrate a nd \ertebrate fauna again popu late th e
che mi cal. and bi o log ica l c han ges o:c~l r ill streams ;I fl n tiJ e disciI:t r!,!e "r hi,, - str eam. At thi s puint, the s tream 's natural se lf-purifi ca ti o n pro cess ha s esse nti a ll y
d eg rad a h le o rgani c maleri :Ii . T oge liJ n ", ilh Ihe \' .\\gC ll "I lppl\ . Ih es<: I' r<lcc'ssc.' bee n co mp leted, but u nl y Ill so far as biod eg radabl e o rg:ll1ic wa stes a re co ncerned.
:lIi' 96 WATER
-- Table 3-3 Whipple, Fair, and Whipple model for zones of stream self-purification Table 3-3 (continued)
Physical Chemica l Biologica l Ph ysica l Chemical Bi o logica l
Zone characteri s tics characte ri s tics characteri sti cs Zo ne cha ra cl eri st ics characteristics characteri s tics
Degrad a ti on The water is turbid ; Oxygen is redu ced to Fish and gree n algae a re Recovery \V aler IS clearer.
(Zone 2 Di sso lved oxygen Pro tozoa, rotifers, and
there are sl ud ge about 40 ~~ o f declining ; litt o ral forms o f (Zone 4 co nte nt move s crustaceans ap pea r . Fun g i
in Fig . 3-13) deposits a nd sat urat ion. gree n and blue-green a lgae in Fig 3- 13) upward fr o m 40 :%. a re prese nt to a lim ited
Roating debri s are trailin g from or sa tur at ion; degree . A lgae ap pear 111 the
frequent ly wetted stones. nitrates are prese n t. .. fo ll owing o rel er:
These includ e Cyanoph ycaea,
SIi.qeoc/onium, Oscil/Moria, Chlo rophycaea. and
and Ulolhrix. Bo tt o m forms dialoms. Large plants
in slud ge include reddish (sponges, bryozoans)
worms (Tubilic idae) si m ila r ap pear. Bottom o r ga n isms
10 ea rthworms. s uc h a s include Tuhife x. mu sse ls,
Tuhifex and Limnodrilus. snails, and insect larvae.
Wat e r fungi a re typical ly Ca rp, s uc kers. a nd m o re
whit e. o live green, putt y resistant forms o f fish
g ra y, r usty brown . occur.
Sphacro/i/us norOIlS,
Clean wafer '!atLJrirI ')Irl'am D isso lved oxyge n I S Ma yflies (Ephemerupleria).
Lep lOm ilus, a nd A chlya
(Zo nes I cl)l1dlll l )nS {{ I t' close to sa turatIOn . s to ne fl ies (Plecoplera).
appear , as do ciliated
and 5 in rt';..iored. caddis fli es (Trichoptera).
protozoa or ciliata such as
Fig . 3-13) and gamefish arc fou nd
larchesium. PI.'ily/is. and
Active .\Ollrc~' : r\c.i:Jplc..'d rrnm r1 ahbltl. ["-2]
Wat e r is grayis h and Oxygen leve l moves Bacter ia flora fl our ish;
decompos ition darker t ha n in be tween 40 ~,~ o f a naerobes di splace aerohes ,
(Zone 3 in degradati o n zone; sat urat ion and zero; whic h eappear toward the
Fig. 3-13) SC um may form. then as active lower e nd of t he zone.
septic condition s decomposi t ion Pro tozoa follo\\; course of
may have set in . . .di n:inis hes" ,?xy.&e.n.. .... ae r.Qbic .baCle ria , fir", ..
co nl ent ri ses. diminishing and then
Methane, hydrogen. reappeanng. Fungi fOllow a
a nd s ulfide a re simil a r course, di sappearing / Popu latIOn o f indiVIdu a ls
given off. unde r true septic co ndition s
a nd then reappearing .
Organisms are thre adlik e
---, /--
In eac h s pecIe

a nd develop pink.. cream,
and grayish tints . Algae are I /
present to a ve ry slight \
exten t a t the lower end o f
the zo ne. TUbifex are
prese nt on ly at th e uppe r _ _ _ - J, ", ""-- Di sso lved
<l nd lowe r ends of the zone.
Psychoda (sewage fly) la rvae
--- /

are present in al l but th e Distance downs tream _

mos t se ptic stage. Rattail
maggolS (EristaiJis) and
mosquito larvae (Clilex) are Wa s tcwa te r
found . There is no fi s h li fe. dis c ha rge

Figure 1-13 Changes In POplIl<tllon o f macroo rganis ms caused by waste d isc harge into a e le" n s tream
(COl/lil/lIcd) [3-1 UI
(hulII ""l11l1l1'r . )

Shou ld an;lerob ic condi ti ons de ve lo p in th e zone o f ac ti ve deco mpos ition, a th e liquid . Removal o f gases that are in low co ncen trations in the atmosphere'is
drastic change in both materials and fl ora a nd faulla wo uld be observed. Reduced enhanced by m axim iz in g contact between th e water and air, a n operation often
co mp o und s, rath e r th an oxi dized e nd prod uct s, wo uld appear, and aerobic spec ies used to strip undesirab le gases from water intended for potable use. Oxygen, a
would g ive way to a naer o bic and facultative o rga ni sms that , wi th o ut co mpe titi o n major co nstituent of the a tm os phere, may be ad d ed to wastewaters by much the
fmm th e a e robes. wou ld flouri s h In g reat numbe rs. sa m e principle. The addi ti o n o f gases such as carbo n dioxide and chlorine to meet
s pecific treatmen t objec ti ves (recarbomi ti on a nd di sinfection, respectively) is
us ually accomplished in cl osed pressurized sys tem s.

Application of Natural Processes in Engineered Systems

Many o f the ph ysica l, c hemical, and bio logica l processes that fun c ti on in n atu ral 3-13 CHEMICAL PROCESSES
wa ter sys te ms have been in co rp o rated into eng in eered sys tem s fo r wa ter a nd
was tewafer treatment. By carefu ll y contro lli ng th e syste m va riabl es, the rate at C hem ica ls a re used in m a n y wa ter- and wastewaier-treatment processes. Chemicals
w hi ch th e processes occ ur is maximized a nd th e tim e required for pur ification is Ill ay be added to a lter equilibrium conditions and cause precipitation of undesir- .
minimi zed. Rea c,tions may thu s be ca rri ed to co mpletion in engi neered sys tem s a ble spec ies. An examp le is the addit io n o f lime to precipitate hardness in potable
in a fraction of the tim e and space required for similar e ffi ciencies in natur a l wate r water treatm ent a nd to precipitate phosphate in wastewater treatment. Often
sys tem s. The fo ll ow in g secti o n gives an ove rvi ew of the applicat io n o f natural the c hem ical adjus tm ent of pH is necessary to effect the desired precipitation.
processes in en gi neered sys tem s whilc Chaps. 4 and 5 prov ide a more co m p lete Ox idi z ing agents may be used if reduced compounds are to be removed. For
coverage o f th e eng in eered sys tems. exa mple, p o ta ssi um permanganate may be' added to oxidize so luble forms of
iron and m a nga nese to forms that precipitate. Chlorine is sometimes used as an
ox idi z in g agent as well as a disinfectant in both water and wastewater treatment.
C hemi ca l coagulation, ofte n used as an adj unct to sedimentation or filtration,
3-12 PHYSICAL PROCESSES co nditions sma ll particles and co lloids so that they form large, sett leable flocs.
In a dditi o n to the above, many other c hemicals may be used for special
T he physica l processes fr eq uently lI sed in e n g in ee red systems inclu de sed im en ta- purp oses in water and was tewater trea tment. ~gain , it should be kept in mind that
tion, filtration, and ga s tran sfer. Th ese are the basic re mo val processes and m ay c hemical processes a re conversion processes and that actual removal is accom-
be used to remol'e mat eria ls in raw water or was tewa ter o r m ay be used to re m ove pl is hed by physica ll y sepa ratin g the solid, liquid, or gaseous products of the
the products of c hemi ca l or biological processes. chemica l rea c ti o n s. . .............. . . . .
...5ed i.n1entatio to re mo ve particles and co lloid s fr o m b o th wa ter and
wastewater. This term is often used sy n o n ymous ly with c larifica tion , a lth o ug h
there are su btle diffe rences in their meaning. In wa ter- and was tewate r'treatment
systems . sed ime ntati on is ca rri ed o ut in la rge basin s o r tank s in wh ich the fl ow 3-14 BIOLOGICAL PROCESSES
IS di spersed unifo rmly to minimize turbulence th a t often keep s particles suspe nd ed
in n a tur a l water sys tem s. When particles arc too small to se ttl e in a reaso nable Bi o logical processes have fou'ndlittle use in the treatment of potable water supplies
len g th of tim e. che mic a ls may be add ed to coagulate them int o larger ma sses that becau se of the low levels o f biodegradable orga ni cs in the raw water. However,:)
Ivi II ~e tlle m o re qu ic k Iy. The se t t led so Iid s. or slut/qt'. is rn echa n ica Il y rem oved fr om bio logical processes arc used ex ten sively in was tewa ter treatment to convert :'-
the bo ttom o f the tank to prevent accumulation . biodegradab le organics and o th er nutrients into a more managea ble form. Bio-
Like sed ime nt a ti on. filtr atio n is used as a su i id s-remova l ope rati on in wa ter log ica l pi'ocesses for m th e ba s is fo r seco ndar y treatment in which dissolved a nd
and . less co mm o nl y . wa~ t ewate r tr eatme nt. Th e filt er mat erial mo st co millonl y co ll(lidal organics a rc co n verted into biomass that is subsequentl y separated from
useci is a gra nul ar medium s imilar to th e sa nd a nd g r<1 ve l enco unt e red in man y (he liquid stream. Secondary treatment sys te ni s are designed to op timize contact
str eams and aquifer s. The mat el: ial. is sized to o ptillli ze filtrati o n rat es and partic le be t wee n m icroorga ni sm s and o rganics uncl er t he most favo rab le environmental
remo va l. and m ec hani s m s ar e pro vi ded for periodica ll y removing th e impulities co ndltiull s. .
t rapped by thdi lt e r. In mod e rn practice. filtrati o n is o ft en a po lis hin g step fo ll ()\I- Ollce sep;i rated,. the b iomass becomes a concentra ted was te stream that must
Ill g se ttlin g o p e ra ti o n s that removc th e bu lk o f th e so li ds. he dealt wi th promptly. l3iological treatmellt o f thi s and ot her orga ni c wastewater
Gas-transfer operat io n s ma y be lI sed in buth \Vate r a nd Ilastcwate r tr e:ltm ent. s ludg(;~, ca lled silldy e digestion. is one o f th e most impor ta nt, and m os t difficult,

Depending on th e tr ea tment ob lcctll"CS. ~ases may be removed fn llll o r added tn rll"ocesses in wastewate r treatm ent.

3-5 An indu strial wastewater is discharged into a municipal wastewater sewer. The character-
DISCUSSION TOPICS AND PROBLEMS istics of the two wastes are as follows:

3-1 Name and briefly describe the majorphysicalprocessesinvolvediil self:purification of

watercourses. Indu strial. Muni cipa l
3-2 Two streams converge as shown in the sketch below. Determine the flow. temperature.
Fl ow = 3500 m' /d Flow = 17,400m' /d
. and dissolved oxygen in the merged streams at point C. BOD , = 1200 mg/L BOD , = 210 mg/ L
PO~ - = 140 mg/L pol - = 2.3 mg/ L
Flow =0'
. Temp =') Determine the characteristics of the mixture.
(DO =') 3-6 Di sc uss thermal stratification and its importance in temperature o f streams and lakes.
3-7 What are three major chemical processes that may a ltern ately aid or obstruct na tural
Flow = 3.7 m}/s / C Stream C purificati o n processes of water systems?
3-8 Calculate the solubi lity of hydrogen sulfide in water at 20
DO = '4 .5 mg/ L
3-9 Determine the solubility o f the components of air in water at 20C and 1.5 atm pressure.
B 3-10 Wh at is the so lubility of me than e in water at 20C?
3-11 Define (a) metabolism ; (b) catabolism: (e) anabolism; and (d) endogenous catabolism.
\ Flow = 2.5 m}/s
3-12 What are adaptive enzymes? What rol,e do they play in natural purification processes of
Temp = 17 C
bodies of water?
DO = 7.5 mg/ L 3-13 Define (a) autotrophs. (b) heterotrophs. (e) phototrophs. (d) aerobic heterotrophs.
(e) a na erobic heterotrophs. a nd en
facultative heterotrophs

3-14 Exp lain the role of rot ifers. c ru stacea. and s lu dge worms in natural purification processes
3-3 Effluent from a wastewater-treatment plant is discharged to a surface stream. The character-
of bodies of water.
istics of the effluent and stream are as follows:
3-15 What a re the two mechanisms known to contribute oxygen to surface waters?
I: Effluent Stream
3-16 What is the oxygen deficit o fa st ream and how is this deficit represented mathematic a lly ?
3-17 Write a simplified 'formula' fonhe -photosynthetic' process by which algae' popula r iDns '
Flow = 8640 m'id Flow = 1.2 m'/s ma y repleni sh oxygen in a body of water.
BOD, = 25 mg/ L BOD, = 2.1 mg/L
I Ammonia = 7 mg/ L
Nitrate = 10 mg/ L
Ammonia = 0 mg/ L
Nitrate = 3.0 mg/L
3-18 Write a formula for the endogenous catabolism by which algae popUlations may contri-
bute t.o oxygen demand. .
~19. A wastewater-tr,9tment plant disposes of its effluent in.a surface stream. Characteristics
Chloride = 15 mg/ L Chloride = 5.0 mg/ L
of the stream and effluent are shown below. .

Determine the stream characteristics after mixing with the waste has occurred. Wastewa te r Stream
3-4 Cooling tower blowdown from a power plant is discharged to it surface stream. The
Flow. m'/s 0.2 5.0
characteristics of each are given as:
Di sso lved oxygen. mg/ L 1.0 8.0
Temperature, OC 15 20.2
Stream Coo ling water BOD , at 20C, mg/L 100 mg/ L 2.0 mg/ L
K, at 20C, d - 1 0.2
Flow = 10 m'; s Flow = 40 m' / min K , at 20C, d - 1 0.3
Temperature = 15' C Temperature = 28"C
TDS = 125 mgjL TDS = 2520 mg/ L
Chromate = 0 Chrom<lte = 0.9 mg/ L
(a) Wh a t will be the dissolved oxygen co ncentration in the stream after 2.0 d ')
(b) What will be the lowes t dissolved oxygen concentration as a result of the waste
Determine the characteristics of the stream after mixing.

3-20 A municipal was te wa ter-treatm ent plant discharges 18.925 mJ / d o f treated wastewater ,.
to a s tream . The wastewater has a BOD s o f 30 mg/ L with a k I o f 0.23 d - '. The temperature o f
the wastewater is 27 e
and the d issolved oxygen is 2.0 m g/L The s t ream just above the po int o f r
wastewat er di scharge flows at 0.65 mJ! s. has a BOD s of 5. 0 mg/ L, and is 90 percent satu rated t
3-1 Amirlh"r~iah . A.: by personal commun ication, 1982.
.'i '
wi th oxygen . The temperature of the s tream is 23 e e.
After mixin g, the stream and wastewater 1-' Ba bbill, H . E. and E. R. Baumann' Sewerage and Se,rage Trealmelll , Blh ed., Wi ley, New York.
1952 .
, fl ows a t a ve loci t y 0. 5 m /s a nd the reae ra ti o n co n s ta nt is 0.45 d - ' .
i I 3 3 8 arlsc h. A. F .. ami W. M. In gram : Biology of Wal eI' Po I/lil ian, U.S. Dept. o f Int e ri o r W a te r
(a) What is th e oxyge n le ve l of the st ream after 2 d ')
'J Po lluli on ('on!ro l Adrninislra lion, 1967. '
: j (b) What is th e c ritical oxyge n leve l in the s t ream and how far downstream w ill it occur')
3-4 Churchi ll. M . A., H . L. Elm o re , and R . A. Bucking ham: "The Prediclion.of Stream R eae1:ation
;1 '
3-2 1 A wastewater-treatment plant discharges to a sma ll s trea m . The characteristics o f the Rales," WaleI' Polllliion Research , vo l. I , Perga m o n, Londo n, 1964.
\vastewate r and th echaracteri s tics o f s tream are give n be low. .1-5 Clark. John W .. Warrcn Viessman, Jr. , and Mark J. Hammer: WaleI' Supply and Pol/ulion Conlrol
3d eel .. Ha rper & Row, New York, 1977. '
3-6 ~oin. The"dore C.. J r .. [(olo.qical Srslems and Ihe Enrironmenl. H oughlon Mifflin, Bosl.on. 1976 .
Siream Waste .,-7 (laudy. A. 1- .. Jr .. "nd E. T. Gaudy: Microhidlo.lJy./or EIIl'ironll1 l'lJ lal Scien li.H.I and Engineers.
t '" McGraw-HilI. New Y o rk. 1980.
~' ' Flow = 10,000 m' Jd
<I Flow = 0.4 m' /s .1-k Hammer. Mark J .' Waler and Was le- WaleI' Te chnology, Wiley , New York, 1975.
BOD = 2.0 mg/ L DO = 0 ms/ L 3-9 Hvnes H B N : Tlw Biololj)' of' Pol/uled WaleI' , Li verpoo l University Press . Liverpoo.l , 1960.
DO = 90 % sat uration Temperature = 21 C 3- 10 Kemmer . Frank N.: The NA LCO Waler Handbook, M cGraw- Hili , New York, '1979.
Temperature = 24 C k, =O.23d-' 3- 11 K lei n. LOlns: IIiI'''' POlllllion II . Causes alld E(fecls, Bullerwo rlh , Lp ndon , 1962.
'"' = 0.45 d - , 3 12 Lewis. W K and W . G . Whilman : .. Pr inciples o r Gas Abso r plion. "Ind. Eng. Chem., 16 ' 12 15
: ( 1924)
:i .1- 13 Lind sley. R . K . and J . ll. Franzini: Waler Resources Engineering. 3d cd .. McGraw-Hili , New
I York. 1979.
Determ ine the m axim um BOD s (20 "C) tha t can be discharged if a minimum of 4.0 mg/ L o f
1 3-14 McKinney. R . E.' Microhioloq),/or Sanilary Enqinee r.,. McGraw-HilI. New York, 1962.
.11! 'I oxygen mu st b e maintained in t he s trea m .
3-22 A milk-produc ts industry discharges a wastewate r t o a s tream . Characteristics of the
3- 15 Melcalr 8.: Eddy. Inc . W{fSlelJ'fI/er Engin eerinq.- Tr ealmenl and Disposal, 2d ed .. McG r aw- Hili .
New York. 1979 .
:1, wastewater and the s tream a re s hown below. 3- 16 OConnor. D . J .. and W. E. Dobbins: "The Mechani sms or Rcaeralio n in Nat ural S i rea ms"
,! (a) If no treatment a t all is given to t he wastewater. what will be the lowest oxygen level J San Enq /)ir. AS.C.E.. 82 :S A6 (1956). '
in the s tream as a result of the discharge" .1- 17 Park er. F. L .. an d P. A. Krenkel Thermal Polllliion .- SWillS vf lite AN, Dep\. Environmenlal and

I! Parameter \\'a stewatcr Stream

Reso urces Engineering. Vanderbill Univcrsily. Nashvi lle, December 1969.
3-18 Palrick , R.: .. EITecl or Suspe nded So lids, Organic Mall er and T oxic Malerials o n Aquatic Life

! Flow 1000 m ' /d 19.000 mJ id

l t,
... in. R,iver~, .... .I:Valer. a!"1 ,~~IJ:ngf. W91:k~,.f.el? ru ary 1968. p . 90.
3- 19 RU liner. Franz. FllIlllanll'lIlals o/ Limnology, 3d ed" D . G . Frey and F. E. J. Fry (!rans.) , Uni -
ve rsily of Tornnlo Press. Toronlo. 1963.
BOD , a ' 20' C 1250 mg/ L 2.0 mgj L t
3-20 Sawyer. C. N .. a nd P. L. McCariy' Chem islry'/or EnvirollmenlOl Engineers 3d ed ., McGra w- Hili .
DO o
mg/ L 10 .0 mgj L New York , 1978.
Temperalure, ' C . 50 10 3-2 1 Srinanlhakumar. S., and A. Amirlharajah: "Organic Carbon Decay in a Slream w ith Biofilm
k,a I 20C 0:35 d - '
K inelics." 1. In t'. Eng .. ASCE, 109( 1): 102 (February 1983).
I., a120C 0.55 d '" :1-22 Slee!. E. W .. and T. J . McGhee' WaleI' Supply and Sewerage. 91h ed. , McGraw-Hili, Ne\'-, York ,
3-23 S!recler, H . W .. and E. B. Phelps: U.S. Pub. Health bullctin no. 146, 1925.
(b) If the s trea m is a trou t fi s hery and the s tream s tan da rd s require a minimum D O o f
( .1 -24 Tsi vogloll. E.c.: hacer Mea suremenl of Slream Reaerulion. u.s. Dept. or Inl er ior , Water T
5.0 mg/ L what is the maximum B OD, (20 C e) that can be discha rged by t he indus tr y? PoliUlion Con lro l Adntinislr<I1ion. Wa shington . D .C. . J une 1976 .
3-25 Velz. Clarence. J .: Applied Sire/in' SanilOlion, Wiley Inle rsc ience. New Yo rk, 1970.
3-23 Write a comp uter progra m to model th e Streeter - Ph e lps equati on. Repeat P robs. 3- 19.
3-20. a nd 3-2 1 u si ng the computer.
3-24 What a r e the fo ur zo nes in th e W hipple. Fair. and Whipple model '! Define the zo nes by
exp la in in g wha t happens in each.
.1-26 Vesilind. P. Aarne: Enrironmenlal Pol/ulion and Conlrol, A nn Arbo r Science, Ann Arbo r, Mich .,
1975 .
:1-27 Warre-n , Ch arb E.' Biology and WaleI' Pol/ulion COl1lr.o'l, Saun de rs. Philade lphia, 197 1.
3-28 Whq'pk. C. c.:The Microscopyo('Drillkinq WaleI'. 4th eel ., rev. by G. M. Fair and M. C. Whi p ple .
Wiley. New York; 1927.
3-25 Mos t oft he nat ura l purin ca t ion rrocesses discussed III thi s char ter have t heir co unt e rpart s ~
in ~ng in eered processes for the treatme nt of potable water supp lies or th e t rea tment of was te -
waters. Di scuss bri e n y the ways in which the follow in g na t ura l processes a re utili zed in ,~
engineerin g systems: (a) scdimenta l ion. (h) filtration. (e) gas tra ns fe r. (d) precipitation. and
(~) microbial ac t io n .


data are no t presently ava ilab le , to predict the consequences of in ges tin g smal l
qu an titiesof chemicals ove r long periods of time. It is ironic that the high stand a rd
of living that allows ind ustriali zed nation s to provide bio logically pure water to
ENGINEERED SYSTEMS FOR WATER ~ the majority of th eir popUlations a lso res ults in the discharge o f chemical waste
~ th a t may eventually have more deleterious effects on human health than th e d o-
I mest ic waste .th a t helped sp read t he plagues of past centuries.


The treatment of water int e nd ed for human consumption is a very old practice .
f; Baker [4-6J report s references in Sa nsk rit literature dating back to 2000 B.C. to
~ s llch practices as the boiling and filtering o f drinking water. Wick siphons tha t

tr a nsferred water from one vesse l to a no ther. filtering out the suspended impurities
in the process. we re pictured in Egyptian drawi ngs of the thirteenth century B. C .
f, and were refe rred to in ear ly Greek and Ro m a n litera ture. The fact th at these
~ practices were recorded in the medi ca l documents of the times indicates th a t the
An adequate supply o f pure water is absolutely esse ntial to human ex iste nce. Th e ~ connection betw een water a nd health had been observed. In fact, Hippocrates
(460- 354 B.C.). co nsidered to be the father o f mo dern medicine, wrote that " ... who-
con'sequences of a contaminated water s upply can be illustr a ted by co nditi o ns ~
soever wishes to investiga te medicin e properly should - consider the water tha t
prevalent during the industrial revolution in E u ro pe when large numbers of the inhabitants use - for water co ntributes much to health ." [4-6J
peasant s were attracted to the cities where th ey crowded together with little or :
These ea rl y wate r-trea tm ent devices were used in indi vidu a l hou seholds:
no sanitary facilities. Human waste. or " night so il" as it was ca lled, was tossed int o
th ere is no indication o f co mmunit y wa ter supplies bt;ing treated until around the
the streets or emptied into pits in common courtyards, often near t he s ha llow wells
first ce ntury. Some of th e R o m a n aq ueduct s had settling basins a t the head wo rk s
that served as the neighborhood water supply. Seepage into these wells and runoff ~
a nd incorpora ted" pebble ca tch ers" in the aqueduct channeL These aqueducts
into nearby streams provided a direct link in the infection cycle. and o nce an out- ~
suppli ed a few priva te ta ps and prov ided fou ntains'o r reservo irs for us~ by th e
" ........ ... .br.eak.:oLdis.ease usually .spread . lhwu&h.. L!:J.e. community,. The ...... ..
ge ne ral public. The city of Venice. situated o n isla nds with no fr es hwate r reso urce.
resultmg loss of lIfe and suffering left scarcely a famil y unt o uched during several
channeled ra inw a ter fr om roofs a nd courtyards into elaborate cisterns thr o ugh
centuries prior to the 1900s.
sa nd filters surro undin g the reservoir. Tl~e fir st of these cisterns was built arou~d
. The development of effective water-treatment method s has virtually elimin a ted
the fifth century A.D . and provided private and public water suppli es for abou t 13
major waterborne epidemics in developed countries. Thi s is no t to sugges t. how-
ce nturies. [4-6J
ever, that the problem of waterborne diseases has bee n e liminated . Developing
Water-treatment practice appare ntly lagged during the Middle Ages, with a
natIOns. where treated water is not available to a ll the p o pUl a ti o n. still experience
renewed interes t emerg in g in the e ighteenth cen tur y. Seve~a l patents were issued
occasIOnal epidemi cs of cholera and typhoid . as we ll as manv o utbr ea ks of less
for filtering d evices. primarily in France and England. As in ancient tim es. however,
severe disease. Even highl y developed countries. including 'th e United States.
th ese devices we re for use in pri \a te households. institutio ns. ships. etc. It was n ot
where public wat er s upplies are almost universall y tleated. are no t to tall v immun e
until the beg inning of th e nineteenth century that th e treatment of public water
from an occasional o utbreak of gastrointestinal illnesses tra cea ble to bi~logically
supp li es was a tt emp ted on a large sca le. The c it y of Paisley. Scot la nd . is gene rall y
contammated water s upplies.
credi ted with be in g th e fir>! c it y w ith a treated wa ter sup p ly. That sy'ste m consis ted
Chemical contamination of water s upplies has become a co ncern in more
bf.sett ling opera tion s followed by fi ltra tion and was put in se rvice in 1804. [4-6J
recent times. Industrial facilities in developed countries produce and use literally
ThiS practIce slow ly spread throu g h Europe and by the end of th e ce ntur y. most
thousands of chemica.l compounds. Along with a n ab undant arrav or household'
major municipal wate r s upplies \vere filtered. These filters were th e "slow sa nd"
a ndagricultural chemicals. these materi a ls often find th eir way int o 'water suppli es.
type described in Sec. 4-8 . .
WhIle some of these chemical compounds are known tl)xicants. mut age nt s. or
The development o f wa te r tr ea tm ent in America lagged behind the European
carcmogens. the health effects o f many others are no t prese ntl y kn mv n . Sufllcicnt
1JI'Clctice. The first a tt empt a t filtration was made a t Richmond. Virginia. in 1932.
104 Thi S project was a failur e. :ll1d seve ra l ye ars interve ned befo re anot her significan t
106 WAT ER

e O'o n \vas ma d e. [ 4-6J After th e C ivil War. o th e r a tt e mpts we re m a d e to fo ll ow 4-2 WATER-TREATMENT PROCESSES
the sa nd filtrati o n pra ctice o f Euro pe. few o f whi c h were successful. Apparentl y
the nature o f the s lls pe nded so lid s in America n str ea m s was s ignifi ca ntl y difTerent Past practices in America have often been to obtain the purest possible source,
fro m t hat o f th e so lid s in European streams. and t he slow sand process was no t even at the expense of transpor ting water over long distances, and to deliver it to
as e ffec ti ve. The d eve lo pment of th e hydraulica ll y c leaned rapid sa nd filt er durin g the consumer with litt le or no trea tment. Some ci ties sti ll own large tracts of land
the latte r par t o f th e nin eteenth centur y p rov id ed a m o re wo rkabl e p rocess. and near the headwaters of stream and restrict activi ties on t hese watersheds
to minimize contamination. Although the benefits of source protection a re recog-'
by th e e nd o f the ce ntur y its use was widespread.
Dur ing th e fir st two- thirds o f th e nineteenth ce ntury. filtr a ti o n was prac ti ced nized as a " first line of defense" in preserving water quality. a ll na t ural waters
will require so me degree of treatment in order to meet modern drinking-water "
to improve th e aes th e ti c qu a li ty o f th e drinkin g wa te r. An unkn ow n be nefit was
the re m ova l o f mi c roo rgani s ms. includin g p a th oge ns. w hi c h mad e th e wa ter standards. The nature and exten t of treatment w ill, of course, depend upon the
m o re w ho l.eso me a s we ll. Th e acce ptance o f thi s fa ct in th e last quart e r o f the cen- na t ure and ex ten t of impurities . .
tur y spurred th e co nstru c ti o n o f the filt er plant s thr o ug ho ut E uro pe a nd Ameri ca .
Ch emica ts Waste
At th e tu rn o f th e century. filtrati o n was the prim a ry defe nse aga in st wa ter bo rn e
Process added stream
d isease.
Acce ptance o f th e ge rm th eo ry o f di sease trans mittal led to the di s infecti o n Raw
l) f p ubli c wat e r s uppl ies. First used o n a temp o rar y basis. di sinfec ti o n w ith bleac h wat er
powd ers and hyp o chl o rites was used in iso lated cases in th e e ig ht ee n-nineti es.
T he fir st pe rm a ne nt in stall a ti o n for c hl o rin a tin g wa ter was m ad e in Belg ium in
1902. Th e p rod uc t io n o f liqu id chlo rin e began in 1909 a nd was fi rs t used fo r wat er Aeralia n . Rem oves u nd esir abl e gases and /o r
ox id a tion of iron a nd m anga ne se.
d is infec tio n in Philadelphia in 19 13. [4-6J Ot her m ea ns o f di sinfec t io n. no ta bl y
ozo nat io n , we re d eve lo ped s imu ltan eo us ly but did no t find wid es pread use. Th e
dr a sti c reducti o n in d ea ths du e to wa terbo rn e di sea ses as a res ult o f di s infec ti o n S ludge removed and
Lim e disposed of ; possible
led to the w ides pread c hl o rin a ti o n o f publi c wa te r s uppli es.
So/ref/ing: Removes ca lcillm a nd /o r m ag nesiu m Sod a recovery and reuse
Othe r wa ter-trea tment pro cesses d eve lo ped m o re s low ly and less dr a matica ll y. 2 o f lime.
ha rd ness; ma y be d o ne in o ne o r two s tages. ash
Coag ul a ti o n a s a n adjunct to se ttlin g was d eve lo ped a lo ng with th e' ra pid sand
." .. . .. . . . .. . . . .. .. . . . . .... .
filt e r in Am e ri ca. So ftening o f ha rd wa te rs w as de m o nstrated in E u rope durin g
.. ... ..... . .the. nineteenth centur y but did no t find w id es pread li se in public wa ter suppli es
until we ll int o th e twe nti e th ce ntur y. The capa c it y o f c harco al to re move di sso lved Bac kwas h wa teT
F il lrario n : Re moves re.sidual CaCO J c ry s tal s d ecanted ; sludge
o rga n ics was obse rveu by early e xpe riment e rs in fi ltra:ti o n but d id no t find ap - Chl o rine
an d Mg(OH) 2 Ooc le ft a ve r fro m so ft e ni ng; 3 combined with
pli ca ti o n in p ubli c wa ter s uppli es. Th e improve me nt o f thi s m a terial int o" ac ti - disi nfec tant may be add ed to preve nt . . sludge from 2
\',lI ed ca rbo n " a nd it s use in wa ter-t rea tm ent p la nt s is a recen t occ tlfrence. as is biological grow th o n rilt er medium . above .
th e use o f sy nth e ti c m e mbran es fo r hype rfiltr a ti o n to re m O\'e di sso lved in o rga ni c
m a teria l. .
D isin/eCiia n . Des t ro ys pathoge ns; en o ugh Chlorin e
M o re prog ress ha s bee n mad e in wa te r purific ati o n in th e la st ce ntury th a n
added to prov ide a resi dual in th e
III a ll o f th e p revio us ly re co rd ed hi sto ry. With few exce pti o ns. trea tmen t p rocesses dis tri buti o n sys tem .
deye loped 111 th e abse nce o f sc ientifi c kn ow led ge cO llce rnin g the bas ic p rinc ip les
UpO Il w hi c h th ey o pe ra te. and o ft en w ith little mea ns to quantitat ive ly assess the ir
Sro rage: Provid es con tac t time for
effec ti ve ness . Onl y within the last 30 to 40 years has the bod y o r sc ientifi c know -
d is infec tio n and s tores wat e r for peak
led ge ca ug ht up w ith the practic e o r wa ter puri fic ati o n. It is int eres tin g to no te de ma nds.
tha t the d e \:e l o pn~e nt o f a th eo ry base has resu lt ed in few c han ges in the basic
processes 'o f wa ter purifi cati o n. U nde rsta nd in g o f sc ientifi c p rinc iples has. how-
e\er. led to refi ne m e nt s o f processes. d eve lo pm e nt o f be tte r eq u ip ment , and a ll dis tribution
oye ra ll in c rease in o perating e ffici e nc ies in wa ter treatment. Th e fo llow ing sec ti o n system
!l i\'es a ll ove r view o f m o d e rn wa te r-t re atm e nt p mcesses. w hil e th e remainin g
Figure 4- I Typ ica l plan t trea ting ha rd groundwa ter.
~ections o f th e c h a pt e r co ntain a d eta iled d escr ip t il) 1l o f th e ind ivid ua l processes.

Th e processes se lected I'or th e trea t ment of potable wa ter depend on the qua lit y
Chemica ls Wast e
added streams of the r:lw water suppl y. Most grou nd wa ters are clear a nd pat hogen-free a nd do
no t co ntain significa nt am o unt s of o rga nic materi a ls. Such wa ters may often be
wa te r used in potab le systems with a minima l dose of chlorine to prevent contamination
in the distribution sys tem. Other grou ndwaters ma y con tain la rge qu a ntiti es of
disso lved so lid s or gases. Wh en these include excess ive a mount s of iron , ma nga n-
Presidimentation: May be necessary if water Sludge removed
periodically and
ese, or ha rdn ess. chem ica l a nd ph ys ica l trea tme nt processes may be requ ired .
comes from fast-flowing streams. Removes
larger suspended solid s. Chem icals may be disposed of by Treatment systems co mm o nl y used to prepa re po table water fr o m gro undwater
ad ded to oxidize organics o r to arrest their Ammonia spreading on land : are show n in Fi g. 4 ,1 . .
biologica l oxida tion. Surface wa ters o rten cont ilin awide r var iety of co ntaminant s th a n grou nd -
water. and trea tment processes may be mo re complex. Most surface waters
Sludge removed conta in turbidit y in excess of drinking-wa ter stand ard s. Although fast-moving
Alum conti nuou sly ;
Mixing. flocculation. se ttling: Removes streams may carry larger material in suspension , most of the so lids will be co ll oidal
tur bidity by coagu lating coll oids and disposa l by
Polymers 2 land fil ling or
in size and will requIre chemi ca l coagulat ion fo r rem ova l. Dependin g on the geo l-
se ttling them o ut ; may also remove
colo r caused by large organ ic molecules. o ther sui table ogy of the watershed. hardness mayo r ma y not be a problem in surface waters. If
means aft er ' low levels of color and o th er orga nic mat eri a l are present, adso rptio n ont o surface-
dewatering .
ac tive m::Jte rial, a process not s ignifi cant in natu ra l water systems, ma y be neces-
sa ry. A wide vari ety of microo rga ni sms. some of which ma y be pathoge nic, are
Ba ckwash wa le r a lso co mmon co nstitu en ts of surface wa lers. Treatm ent systems co mmonly useci
Filtration: Polishes to remove re maini ng C hlorin e deca nt ed, and in treatin g surface W;lIers al'e shown in Fi g. 4-2.
tur bid ity; d isinfec tant may be added to dewatered sludge
p reven t biologi ca l gro w th o n filter medium . dispose d of wi th
tha t from 2 above.
Water-Treatment Processes: Theory and Application
Adsorption : May be necessary if wa ter S tea m fro m cleaning
contains dissolved organics; may co nsist o f It is genera ll y co n\'en ient to grou p human use of water int o two broad ca tego ries
cycle co nd e nsed and
ac tiva ted ca rbo n co lu mns o r ac t-ivated disposed of. depending upo n th e locatio!l of th e use re lative to the so urce. In -place use of water
ca rbon may be added in powdered form in . in cl.ud~~ .\l.iWig'lt ion. rCl:rCllt ion , .wi ldlife t io n . .and. the . d~lutio n , .ass imi.J.a- ..
opera tion sim il ar to 2 above.
li on, and transportatIon ll f was tew ater. Alt ho ugh hydroe lectric powe r ge neratio n
Disinfection: Destroy s pathogen s; enough requi res brief dive rsion of waler thro ugh turbine pen stocks, this use is a lso co n-
added to provide residua l in the dis t ribution sid ered an in-place use . Quantilati\e ly. in-place use is a nonconsumpti ve use and
sys tem. wil l no t be cove red III this tex!.
Storage : Provides contac t time ro r d isin fec ti on For irriga ti o n and Indu strial u se. and fo r indi vid ual and public domesti c
and stores water for peak demand . supp li es, wa ter mu st be \\ ithdra wn frc)m streams, lakes. o r aqu ifers in Ih e natural
hyd ro log ic cyc le. Th e po llutant s mos t de leterio us to cro ps (inorga nic sa lt s and
metals) are diflic ult and ex pensive to remove. The vas t quantit y of irrigation wa ter
to . used a nd the low of proli l assoc ialed with fa rmin g virt ually prec lude a ny
diqributi o n
tl'ea tmenl of thi s waler. Wat er not su ited for irrigati o n is simpl y a band o ned . and
sys tem
avadab le ca pit a l is used in ste:ld to secure an alternate so urce of acce pt a ble qu a lit y.
Figure 4-2 Typica l pl an l Ireatin g lurbid ~urfac~ waler wilh organ ics. Man y industries wilh nccds 1'01' sm;t11 ::tmou nt s o f essentially potab le wa le r o btaill
th eir s upplies fr o m puh lil: sys tem s. SL)me Ill d usiri a l water su pp li es. such as bCl iler,
ked \V;lter. tlla y require a c hcm ica l purity an o rd er nf magnitud e g rea teT than
po tab le wa ter En gi ll eer ing dcsi!!n fo r treatm ent of o ther types of in dustria l \\',ll e r
supplies Illa y al s\ ) hc neceSS; 11 y. ( '\Jo ll ng wa ter. parti cu lar ly th at used on ly o nce
;Intl d isc har!,cd h;lc k III II <tlurc. 1t; 1; Ie\\' qualit y UlIl str;lint s Indi\idu ;ll d OIl1 cs tic
suppli es ;lrc l1 SII ;III 1' dr;1\\ 11 ft'Ulll \\ ells P I' sprin gs of accep table qualit y <lnd se n 'c

In Eq. (4- I), Fe goes from the + 2 .to the + 3 oxidation state and in Eq. (4-2)
individual ho mes or farmstead s. Such systems are seldom engineered but are
M n goes from the + 2 to the + 4 OXidation state. In both equations the free oxygen
installed and operated by the home owners, perhaps with the advice of the well- (0 J IS reduced, and the anion ongmally :tssociated with the ferrous and mangan-
driller and the distributor of ho me water-treatment unit s. OtiS Ions recombin es With other cations in the solution. In both cases, the pH of the
Public water supplies, while only a fraction of th e to tal wa tel' us e, require
solution IS lowered by the production of hydrogen ions.
by far the larges t amount of efTort expended by environmental engineers in the Iron and manganese are found in appreciable amounts only in groundwater
water-treatment field. The remainder of this chapter will be devot ed to the prin- and in water from the hypolimnion of strailfied lakes where anaerobic conditions '
ciples of water purification for potable' supplies. The processes involved are exist. Aeration of this water provides the oxygen necessary to convert both elements
discussed first from a theoretical standpoint and then from an applications to t he insoluble form. Chemical oxidants, such as potassium permanganate, can
standpoint. also be used for this purpose. They are sometimes used in connection with aeration
to speed up the process. When aeration is lIsed to precipitate iron and manganese,
additional treatment will be required to remove the precipitated solids.
4-3 AERATION Both degasification and oxidation are governed by the principles of gas trans-
fer that were presented in Sec. 3-4. Subtle differences in liquid-gas contact systems
Aeration is a process sometimes used in preparing potable water. It may be used can have a pronounced effect on the overall gas-transfer process. An understanding
to remove undes irable gases disso lved in water (drgasijicalion) or to add oxygen of gas-transfer principles is essential in aerator design, and the student is en-
to water to convert undesirable substances to a more manageable form (oxidCl1ion). couraged to reread Sec. 3-4 before proceeding into the following discussion.
Aeration is more often used to treat groundwater, as most surfa ce waters have
been in contact with the atmosphere for a sufficient period of time for gas tran sfer
to occur naturally. Liquid-Gas Contact Systems
Groundwater may contain appreciable quantities of gases slich as carbon Liquid-gas contact systems are designed to drive the water-gas mixture toward
dioxide (C0 2 ) and hydrogen sulfide (H 2 S). Thcse gases arc biological waste equilibrium as quickly as possible for degasification purposes and to provide'
products from bac terial decomposition of organic matter in the so il or by-pr6ducts supersaturation of oxygen for oxidation purposes. These goals may be accom-
of reduction of sulfur from mineral deposits. Excessive carbon dioxide concentra- plished by either dispersing the water into the air or by dispersing the air into the
tion results in a corrosive water. High carbon dioxide levels may also interfere water.
with other treatment processes. Hydrogen s ulfide imparts an unpleasant taste When water is dispersed into the air, as depicted in Fig. 4-3, the interfacial
and odor to water, even in small concentrations. Altlwugh these gases are only "a re;Lper..yo.lume .of..wate.r. is maximized by minimizing the drop size. This will
slightly soluble .at .atrn(),.groundw'Lter.may contain considerably inc rea se the desorption rate for supersaturated solutions (Fig. 4-3a) or increase
higher concentrations under pressures commonly fou nd in deep aquifers. Aeration the absorption rate for undersaturated solutions (Fig. 4-3b). In general, this ap-
of water supersaturated with these gases serves to speed the release toward equili- proach works better for desorbing gases than for absorbing oxygen, although the
brium conditions. latter can be accomplished for undersaturated waters.
Although volatile liquids such as humic; acids and phenols ca n be removed
. from water by aeration , the removal rates are too'slow for the process to be practical
except in extreme cases where excessiw quantities must be reduced to more
manageable levels. ( ;as
Iron and manganese are common elements widely distributed in nature. fo"n ~

In the absence o f oxidizing agents, both of these clements are soluble in w:tter.
Forming compounds with other so luble ions. hoth iron and man ganese are
2 Bulk
so luble in significant quantities o nly in the + :2 oxidation sta te, i.e" Fe' , and Mn +. gos
U pon contact with oxygen, or any other ox idizin g agents. both ferrou s iron and
manganese are ox idized to higher valances, forillin g new io nic compkxes that are
not soluble to any appreciable extent. Thu s. the jron ancl manganese may be
. removed as a precipitate after aeratiun. Chemically. these reacti ons may be Lo q uod
wr itten as fo llows.
ra) rb)
4Fe 2 ' + O~ + IOH 2 0 41e(OH)., 1 I- 8 1-1 > (4-1 )
Figure 4-3 Water dispersed in air: (a) desorplion and (h) absorplion.
2Mn2 ~ + O2 + 2 H1 0 :2 1\'1nO 2 ~ ~ .:j H 0 (4-2)

In water purification plants, water-in-air systems may consist of fountains,

cascade towers. o r tray towers. F otln tains consist of a piping grid suspended over
a catch basin. Nozzles located at the int ersection of the pipes are fixed to direct
the flow of water upward. Once its kinetic energy is dissipated, the wa ter falls
bac k into the catch basin where it is recovered. portions of the fl ow perhaps being
recycled . The height of the spray, and therefore the water-air co ntact time. is de- Bulk Bulk
liquid liquid
termined by the pressure in the pipes, whi le the d ispers ion pattern is determined
C, <C, C, >C,
by the nozzle characteristics. Nozz le size may vary from 2 to 4 cm in diameter.
While smaller nozzles result in finer sprays. which yie ld greater surface-to-volu me
.ratios, freq uent clogging of small nozz~e s ca n resu lt in hi gh maintenance cost.
. Design parameters for spra y ae rators includ e system pressure, nozzle spacing.
and flow rates per nozzle. Pressures of aro und 70kPa ( 10 Ibj in 2 ) are commo n and Liquid Liquid
film fi lm
prod uce fl ow rates offrom 5 to 10 Ljs through each nozzle. Grid spac in g may vary (a) (b)
from 0.6 to 3.5 m depend in g on the distance necessary to prevent extensive over-
lap of nozz le discharges. A typical design may consist of 2.54-cm nozzles on 1.25-m Figure 4-4 Air dispersed in waler' (a) deso rplion and (b) absorption.

centers operating at 70-k Pa pressure. resulting in an -area requirement of ap-

proximately 10 m 2 /(50 Ljs) o f water treated (or abou t 100 ft 2 j(Mgal/d. Another meth od or ae rating water is to disperse th e air into the water. Again.
Cascade lowers consist of a series of wa terfalls th at drop int o smal l pools. bo th absorp ti on and desorption are enhanced by maximizing the interfacia l area ,
In this case the water is no t dispersed as droplets bu t is exposed to the atmosphere in this case by minimizing th e size of the air bubble. Figure 4-4a can be used to
in thin sheets as it cascades down each step. Each step in a cascade tower is usually illu strate the situati o n for a supersa'turated water (desorption). and the process
abo ut 0.3 m in height. and as many as 10 steps may be emp loyed. The number of for an undersaturated wa ter (absorptio n) is shown in Fig. 4-4b. In genera l. thi s
steps det erm ines t he con tac t time between the wa ter and t he air. Head loss th rough approach work s better for absorption th an for deso rp ti on.
th e system is simpl y th e height of the topmost step. The cascades may be arranged Air-in-water systems mo st o ften consist of tanks fr om 2.5 to 5.0 m deep thro ugh
longi tudinall y like stair steps or may be arranged in a ci rcle, wi th the steps extend ing which th e water /l ows. Air is then injected th(Ough a porous bo tt om or through
concen trica ll y outward from top to bot tom. Area requirem ent for cascade aera tors spa rgers near th e bottom. Since the energy-for this system is expended on the air,
ranges from 4 to 9 m 2/(50 Lis) (40-90 ft 2/(Mgal/d, depending upon t he number of not the water, smaller. less complicated equipment is requ ired. Blowe r capacity
_ steps used. [4-50J . need on ly be sufficient to deliver the requ ired air vo lu me at the pressure determined
.. . . .. .. ... " . .. Tra J Tt1IVi-i r.n't(e 'si'ril'i laY 'iii 'ifit ll're' i 0 'c'a~;cai:le' t'o\\':e'rs"iii "t'I;,it i i1e"\~a ic'r is lift ed by head loss through the distribu tin g mechanism, plu s the depth of th e wa ter.
and allowed to fall to a lowe r eleva ti o n. Instead of being intercep teu in poo ls, Thi s type of aerat ion dev ice has fo und -grea ter 'use in was tewa ter treatm ent th an
tray towers int ercept the flow with solid surfaces over which the water mus t pass in potable water treatment.
in its downward journey. The so lid surfaces may be a series of redwood slat Severa l varia ti ons of this process may be employed. Ca rr yi ng ou t the process
tra ys which break the fl ow of the wa ter or a ser ies of porous-boltom tra ys contain- in an enclosed tank with a positive pressure in the atmosphe re above the liquid
ing stones, ceram ic sp heres. or oth er porous packing. In any case. tray material wi ll speed th e absorption ra te. although.i t will also decrease the desorption rate.
prov ides large sur face areas ove r which th e fl ow is spread in thin fi lm s. Po rosit y An impeller pla ced Ju st above the poi n't of air injec ti on will break the a ir flow in to
of the system must be sufficie nt to ensure circulati on of air around the surfaces. slIla ller bubb les and enh ance mixing patterns. As in th e case of water-in- air
Tray towers are most oft en used for oxida tion of iron and manganese. Usua ll y sys tems, there are several proprietary dev ices which make unique app li ca tion of
the tray packing wi ll be large chunks of coke wh ich have been precoa ted with a the basic princip les discllssed here.
st rong oxidant such as potassium permanganate to help initiate th e ox idation All aera ti o n operati ons must be we ll ventila ted to prevent the buildup of
process. Films of iron and manganese solid s are deposit ed on the' surface o f the gases which ma y be tox icant s or asph ixa nt s.
medium. and th ese film s se rve to ca ta lyze the prec ipit at io n. reacti on. Manganese '
prec ipit ates very slow ly be low a pH of about 9. and it may be necessary. t6 raise
the pH to thi s le vel in orde r to speed the react ion. 4-4 SOLIDS SE PAR AnO N
In addition to the above operations, there are lIlany proprietary devices on
th e marke t wh ich make use of' one or more of the basic princ iples just discmsed. The terms sedilllelllolioll and ('fliriliclil ion are co mm only used interchangea;l ly
Informatio n on these dev ices may be obtain ed fr om curren t lit erature or from th e with regard to prcp;II';ilI OIl llf j)'ltable \\,;ltCI' ..\lthough there ,II'C some suhtl e
manufac turers o r distribu tors. t1i1lcrcllces in the Cllll ll otatlllllS t'f the two word s. th ey hoth co nvey the id e~t of

physically separating solid material from water. Separation may occur by flotation where CD is the coefficient of drag, Ap is the cross-sectional area of the particle
if the water is denser than the solid matter. In the preparation of potable water, perpendicular to the direction of movement, and v is the velocity of the particle.
virtually all of the solids requiring removal are heavier than water; therefore, Because the drag force acts in the opposite direction to the driving force and in-
sedimentation with gravity as the driving force is the most common separation creases as the square of the velocity, acceleration occurs at a decreasing rate
technique. until a steady velocity is reached at a point where the drag force equals the driving
Sedimentation may be classified into various types depending upon the charac- force:
teristics and concentrations of suspended materials. Particles whose size, shape;
and specific gravity do not change with time are referred to as discrete particles. (4-3)
Particles whose surface properties are such that they aggregate, or coalesce, with
other particles upon contact, thus changing size, shape, and perhaps specific For spherical particles,
gravity with each contact, are called flocculating particles. Suspensions in which
the concentration of particles is not sufficient to cause significant displacement of
water as they settle or in which particles will not be close enough for velocity
field interference to occur are termed dilute suspensions. Suspensions in which the Substituting into Eq. (4-3)
concentration of particles is too great to meet these conditions are termed con-
centrated suspensions. These differences result in significantly diflerent settling (4-4)
patterns and require separate analysis. Settling in dilute suspensions is discussed
Expressions for CD change with characteristics of different flow regimes. For
below. Since concentrated suspensions are most often encountered in wastewater
laminar, rransitional. and turbulent'flow, the values of CD are:
treatment , that discussion is presented in Chap. 5.
24 . (4-5)
CD = - (Iamll1ar)
Type-l Settling
Discrete particles in dilute suspension, type-I settling, is the easiest situation to = -24 + - 3- 2 + 0.34 ( ..
transItlOna 1) (4-6)
Re ReI !
analyze. If a particle is suspended in water. it initially has two forces act ing upon it:
(I) the force of gravity = 0.4 (turbulent) (4-7)

where Re is the Reynolds nUITI.~~r ............. ............................. . .. . . . . . . . . . . . . . . . . .

in which Pp is the density of the particle, g is the gravitational constant, and Vp is the VrPw d (4-8)
Re = - - -
volume of the particle; and (2) the buoyant force quantified by Archimedes as J1
Reynolds numb'ers less than 1.0 indicate laminar flow, whil values greater than
10 indic;lte'turblIlcnt flow. Intermediate values indicate transitional flow. The
where Pw is the density of the water. Since these forces are in opposite directions. shape factor is added to correct for lack of spherosity. For perfect spheres, the
there will be no net force when Pp = p".. and no acceleration of the particle in value of is 1.0. For laminar flow, substitution of Eq. (4-5) into Eq. (4-4) yields:
. Tchtion to the water will occur. If, however. the density of the particle differs from g(pp - p,Jd 2
= - - - -- (4-9)
that of the water, a net force is exerted and the particle is accelerated ~n the direc- V
r 18 J1
tion of the force:
which is known as the Stokes equation. Terminal settling velocities for the trans-
fnel = (p p - P,Jg Vp itiunal flow involve simultaneous solutions ofEqs. (4-6) and (4-4). Use of the above
This net force becomes the driving force for acceleration. equations in determining the terminal settling velocities of discrete particles in
Once motion has been initiated, a third force is created due to vi scous friction. dilute suspensions is illustrated in 'the following example.
This force, called the drag force, is quantified by
Example 4-1: Finding the terminal settling velocit)' of a sphere in water find the terminal
sell ling \'e!Ocil y or a spherical particle with diameter 0.5 mm and specific gravity of 2.65
, cliling Ihrou gh WOll er al 20Ve

SOLUTION Wat er lev el

I. Assume laminar flow; from Eq. (4-8) with p .. = 998.2 kg/m 3 and J1 = 1.002 x 10 - 3

N s/m 2 at 20C

Vt = 18 x 1.002 x 10':3 N s/m2

(Recall that the units of N are kg . m/s2)

v, = 0.22 mls
2. Check Reynolds number:
0 .22 m ls x 5 x 10 - 4 m x '998.2 kg/ m 3
Re = - - - - ' - - - - - - , - - - - . , - - - = -
1.002 x 10 - 3 N . s/m2

= 112, which indicates tran si tio nal flow

24 3
. 3. CD = ill + 112 1/2 + 0.34
= 0.84 - ~
S"mpllng [lort

4 (2650 - 998.2) 5 10 - 4
V,2 = - x 9.81 x x
4. 3 0.84 x 998.2 Figure 4-5 Setll in g column for analyzing lype- I sus pen sion .
v, = 0.11 ml s
Observing that the tim e of travel is equal for the two particles. it follows that
5. With v, = 0.11. repeat steps 2. 3, and 4.
Re = 55 Zo Zp
10 = - =- and
CD = 1.18 t'o L'p

v,. = 0.1 0 mls '" 0.11 m/s (see step 4) Some ge nera li zed statements can be made based o n th e above equation .
. Direct application of Eqs. (4-4) through (4-9) is se ld om possible in water
treatment because the size of particles must be known and a correction fac to r
.J. ' All'particles With dianiet'elsequa iio~~'g~~~t~;; i1~;1do,s~~h 'that their se ttling
velocities equal or exceed l 'n . will a rri ve at or pass the samp ling port in time co
to account for departure from sphericity has to be determined. An indirect method
2. A particle with diameter ell' < do will have a terminal set tlin g velocity vI' < Vo
of measuring settling velocities of discrete particles in dilute suspensions. and of
and will arrive at or pass the sampling port in time 1o . provided its o ri gi nal
determining settling characteristics of a suspension, was devised by. Camp. [4-11 ]
position was at , or be low, a point Zp .
A settling column is constructed as shown in Fig. 4-5. The suspension to be tested
3. If the suspensio n is .mixed uniformly (i.e., all particle sizes are randomly dis-
is placed in the column and is mixed comp.letely to ensure uniform di stributi on
tributed from top to bottom of the co lumn), th en the fracti o n o f particles of
of the particles. The s\lspension is then allowed to se ttle. quiescently .
size el p with settling velocity 1'1' which will arrive at o r pass the sampling port
S.uppose that a particle is just at the surface at time t;:qual zero and its set tlin g
in time 10 will be Z p/Zo = l' / l'O' Thus. the removal efficiency o f any size particle
velocity is such that it arrives at the sampling port at a later time, say I = 10 , Now.
from suspension is the rati o of t he sell ling ve locity o f tha t particle to the settling
the averaging settling velocity of this particle can be calculated as
ve locity Vo defined by Zo/Io
distance traveled Zo
Vo = - time of tr avel 10 These principles can be used to determine th e settleabi lit y o f any given s us~
pension . An apparatus simi lar to th ;\t shown in Fig. ~- 5 is fi lled with the'suspen sion
Suppose also that another particle is initially suspended at a distance Zp above the to be tested. Theoreticall y. the depth of the water column IS not a factor ' in the
sampling port a nd that its te~minal se ttlin g velocity. less than Vo , is suc h th a t it analysis. but practical considerations dictate a depth of about:2 m. The s uspens io n
arrives at the port at the same time as the previous par(.icle. (ts se ttlin g velocity can IS mixed complete ly to ensure an initially uniform di stribution of particles. A
be calculated as suspended-so lid s tes t is rliF on a sam ple of th e comp lete ly mixed suspension. a nd
di stance traveled Zp an initial concentratIOn CO IS determined . After the sus pensi o n is a ll owed to se ttle
v = - - -- -- - = -- for a tim e I, a second sample IS then drawn o O'a nd an o ther concentration C t is
p time o f travel 10

determined. All particles comprising C j must have settling velocities less than Example 4-2 : Settling column analysis of type-I suspension A settling analysis is run on
a type- I suspension. The column is 1.8 m deep, and data are shown below.
Z 01II l' Thus , the mass fraction of particles with V I < Zo/t I is
C j Time, min o 420
x = --
Cone, mg/ L 300 27
The process is repeated several times with Xi a lways being the ma ss fraction o f
particles with Vi < ZO/Ii' When these values are plott ed o n a graph, as shown III What will be the th eo re tical rem ova l efficiency in a settling basin with a loading rate of
Fig. 4-6, the fraction of particles co rresp o ndin g to a ny settlll1 g ve loc it y can be 25 m 3 / m 2 d (25 m id)? .. .

o bt a ined. SOUJTION
For a given detention time [0, an overall percent removal can be o btained .
All particles with settling velocities grea ter than lio = Zol lo wi ll be 100 .percent l. Calculate mass fraction remaining and corresponding settling rates.
removed. Thus, 1 - xo fraction of particles Will be removed co mpletely Il1 time
1 , The re maining particles will be remo ved accord ing to the rati o vJvo, corre- Time , min 60 80 100 130 200 240 420
sponding to the shaded area in Fig. 4-6. If the equation relatlllg V and X IS kn ow n,
mass fraction remaini ng '0.63 0.60 0.56 0.52 0.37 0.26 0.09
th e a rea ca n be found by integrat io n :
xo [' . u, x 10 2 , m/min .I .55
3.0 2.5 2.0 1.0 0.83 0.48
x = J - Xo + -~ Jx (4- J0)
o Vo

whe re X is the total mass fracti o n rem oved by sedimentation. In most cases, 2. Pl o t mass fr act ion remaining vs. settling velocity.
it is simpler to int egrate by finit e intervals as demonstrated in th e following ex -
amp le. 1.0r-----------------~------,

1.0 0.9


0. 7
0. OJ)
VI c.
S 0.5
t. x = 0.06 c
0.4 E
~ t.x = O. I E
,; N

0.3 0

6.x = 0.06 ~~.JL-

6.x = 0.06 1....l--..l_..L...L...L-..L........:L-....L---.JL--------.JL-----.......;

Seltling ve IUCIII"s." = - S; 3.0 4.0
I I, ~ ~ ~ 1.0 ~ 2.0
o 00 .
Fi gure 4-6 Co ll ection efficie ncy as a funeli ol1 of se ttli ng velocity . Ve locity, m/ min X 10- 2
3. Determine Vo = 25 m J / m 2 d = 1.74 X 10 - 2
m/ min .

4. Determine Xo = 54 percent.
5. Determine ~x . v, by graphical integration.

D.x v, llx . fl
0.06 1.50 0.09
0.06 1.22 0.07
0.1 1.00 0.10 E
.~ 0. 1 0.85 0.09 c
0.1 0.70 0.07 E
0.06 0.48 0.03 0
0.06 0.16 0.01
. ~

LD.X '", = 0.46

6. Determine overall rem ova l efficiency.

" tJ.x . v,
X = I - Xo + L --

= 0.54 + -- Figure 47 Isorernova lli!leS rrorn sell ling anal ysis.

= 0.46 + 0.26 given isoremova l line is the instantaneous veloci ty o f the fracti o n of particles
=72% represented by that line . .
It should be noted that the velocity becomes greater (I.e., the slope of the
.- . Type-2 Settling isoremova l lines beco mes steeper) at grea ter depth. Thi s common characterIstIc
of flocculating sllspensioI1s reflects the increase in particle size a nd subsequent
Type-2 settling involves flocculating particles. in dilute suspension. Flocculating increase in settling veloc ity because of con tinued collision a nd aggregatIon WIth
suspensions cannot be generalized in the same manner as discrete particle sus-
other particles.
pensions. Th'e Stokes equation cannot b~ u~~q.!:?~"l!-u~e flocculating particles are For any predetermined de tenti on time. the overa ll percentage removed can
. ...-.. ........... continually 'changing 'ifniie: sh'<ipe: 'iiiiCi, 'if a large aggregate of particles collect , be obta ined as illustrated in the example below.
specific gravity because of entrapment of water in the interstitial space. So many
factors contribute to the flocculation process that it has been impossible to develop Example 4-3: Settling column analysis of flocculaling particles A co lumn .ana lysis of. a .
. .., I ., 1 ' 1 be low . The inilial
flocculallng SLl spen slo n IS run In tIC appdf3 tu s s lOWI
so lids concen
a general formula for determining settling velocities. .
tration is 250 mg/L. The resulting maHix is sh o wn be low What Wi ll be the .overa ll Fe-
An analysis of the settleability of a flocculating suspension similar to the analy-
moval efficiency of a settling ba sin whi c h is 3 In deep with a detention time of I h and
sis for a discrete particle suspension just described can be made. The settling
column must be altered somewhat to allow for sampling at several depths . As 45 min?

in the previous analysis. samples are drawn off at several time intervals and an- Time of sampling. min
alyzed for suspended-solids concentrations. These concentrations are then used Dep lh.
III 30 60 90 120 150 180
to compute mass fraction removed (instead of the mass fracti on remaining)
at each depth and for each time. 0.5 1:1 3 83 50 38 30 23
1.0 180 125 9} 65 55 43

(4-11 ) 93 70 5~
x 100 U 203 150 II
2 13 168 135 110 90 70

2. 0
2.5 220 I () 145 Ii } 10J 80
where xij is the mas~ fraction in percent tha t is removed at the ith depth at the ~
1 8~ 155 I ,} 11 3 95
3.0 225
.--., jth time interval. These values are graphed as shown in Fig. 4-7, and a family of
isoremovallines is drawn similar to a contour map. The slope at any point o n any Result s or sll spen ded so lid s les t on sample C,' mg L


I. Determine the rem ova l rate at each depth and time . 0.Q7 2.6 0. 18
0. 1 1.8 0. 18
0.1 1.2 0. 12
X;j = (I - C;)Co) x 100
0.1 0.8 0.08
0.1 0.45 0.04
Tim e of sampling. min 0.1 0. 15 0.0 1
Depth. LIVZ; = 0.6 1
m 30 60 90 120 150 180

0.5 47 67 80 85 88 91 tJ.,z
5. Determine the removal efficiency, R = '0 + r --'
1.0 28 50 63 74 78 83 zo
1.5 19 40 53 63 72 77
2.0 15 33 46 56 64 72 0.6\
2.5 12 28 42 51 59 68
= 0.43 +-
3.0 10 25 38 47 55 62
= 63%

2. Plot isoconcentration lines a:; s hown in th e accompanying figure. 4-5 SETTLING OPERATIONS
3. Construct vertica l lin e at 10 = 105 min.
4 . From the figure. approximately 43 percent 01' the so lids will reach the 3-m depth 111 10 ,
The sed imentation process has ma ny applications in the preparation o f potable
The y wlil pe 100 percent removed. Some percentage of the remaining particles will be
wa ter. Materials that may be remo ved by sedi menta ti on include suspended solids
removed. Working upward along t he 10 line, tktermine increments of rem oval and
depths to the midpo int of these increme nt s.
or igina lly present in the water or dissolved so lids which have been precipitated
in the course of other treatment processes. S uspensions in water-treatment plants
are ass umed to be dilute, a lthough some zone settling may occur near the bottom
of settling basins.
Cr iteria for desi gn o f settling basins have evolved as much from practice as.
fro m theo ry .. S.ettling .. l:.~~i~s ..employed. J()r . s.o li~~ . rernoyal,in . \!penL ........... .
plants are classified as either long-rectangular, circular. or so lid s-contact clarifiers.
Although these are all continuous-flow systems, the settling theory for batch analy-
sis discussed in the previous section can be applied_

LO'ng-Rectangular Basins
::J E
cC> Long-recta ngu la r basins are commonly used in treatment plants processing large
0. fl ows. This type of basin is hyd rau lica ll y more stab le, and flo w contro l thro u g h
c" large volumes is easier with this configuration. A typical long-rectangular tank
is shown in Fig. 4-8. Typical designs consist o f basins whose length ranges from 2
to 4 times their width a nd fr o m JO to 20 times their depth. The bottom is slightly
sloped to fac ilitat e slud ge scrap ing. A slow-moving mechanical sludge scraper,
usua ll y redw ood slats o n a ch a in drive. continuously pulls the settled material
int o a sludge hoppe r whe re it is pumped o ut periodically.
A long-rectangular settling tank can be divided' into four different functional
zo nes:
I. The inlet zone in which baffles intercep t th e incoming water and spread the
Tim e. IllIIl
flow ulllfo rmly both horizontally a nd vert icall y ac ross the tank


Settling zone '*
Sludge I
scrapeJ I
..... I
" I

o I,
out (u) Figure 4-9 Di sc rete pdrl icle removal in Ihc se tlling zone o f a I,lng-rectangular setlling basin.

particles fallm g Ihrou gh the settling co lumn wtll n(lW have two co mp o nents of
velocity. the vertical co mponent.

and the ho ri zont<li component. that is. the \elocity of fl ow through the se ttling

\;,het:e:4 ;stli ec ; oss~sect;;';li ,il ~i;,e;1.~;;

ii~ e\\; i(Jiiitlm esthedepih.the sl.liTi of these
velocities is th e absolute ve loc it y of th e particles.
No\\' cO ll sid er th e panicle In the b<ttch ,1Ilalysis for type-I settling whi ch was
Initially at the surl'ace an d se ttled tilr ough th e depth of the column Zoo in the tim e
In II' 0 also correspond s to the time required for the colum n to be car ried ho ri-
(/J) zonta ll v across ihe se ttlin g zonc. then th e particle will rail into the sludge zo ne and
Figure 4-8, Lo~g-rectangular settling basin: (a)diagrammatic sketch and (b) view or interi o r sh ow ing
be rCllloveci from suspension at th e pOint ;It \\'hleh the co lumn reach es the end of
sludge scraper arrangemenl. (PholO courtesy oj Em.irex Inc., 0 Rexnord Companv,) the se tlling zo ne. ,\5 in th e batch anal ys is. a ll parllcles with 1', > 1:0 wil l be removed
from suspens ion at some poi nt along the settlin g zone. Now consider the particle
with settling vc loclty < l'o. lft helnitialdepthnfthisparticlewassuchthatZ p !u, =
2, The outlet zo ne in which water flows upw3rd and over the ou tlet weir
I". thiS particle wtll ,liso be removed. as sho\\n in the b~ltch anal ysis . Therefore.
3. The sludge zone. wh ich extends from the bottom of the tank to ju st 3bove the
the rem ova l of suspe nd ed particlcs pa sslllg thr u ugh the settling zone wil l be in
scraper mechanIsm
proporti o n to the ratio of the Incli\idual settling \'eloet ties to the settl ing ve locir-y
4. The se:tlin g zone. which occupies the rcmaining vo lum e of the. tank t
Anot her poi nt ca n bc mad e by this analysis. The lim e 10 corres ponds to the
. Although a'II four zones musi function properly for efficient sol id s removal.
retention time in the seltltn g zone.
pmr:ary a ttentIon here will be focused on the settling zone. Assume that the
. colu mn Ifl F'Ig. 4 - 5 IS
. sllspended 111
. the flow of the settling zone as shown in I' LZ n IV
In =
Ftg. 4-9. The column travels with th e flow across the settli;lg lone. Discrete Q Q

A lso


LZ oW . Q
and !o =I w
"0=- (4-12)
w here As is th e surface a rea o f the set tling basin . Thus, the depth of the basin is
not a factor In determining th e size par ticle th at can be removed co mpl etely in
the settlIng zon e. The determining factor is the quantity Q/ As' which has th e units
o f ve loc It y and IS refe rred to as th e ove rfl ow rate qo This ove rflow ra te, expressed
as cub IC meters per squ a re-meter hour (or ga llo n s per sq ua re-fo ot day), is the design
fac tor fo r settlIng baSInS a nd corres p o nd s to the terminal sett lin g ve loc it y of the
partIcle that IS 100 percen t removed.
If a similar co mparis on of flocculating particles is made be tween batch Figure 4-10 In board weir arrangement to increase weir length.
se ttll!l g and continuous se ttlin g in lo ng-rec tan gul a r ta nk s, th e path of the falling
partIcles wIll not be a straIght lIne . As determined in the batch ana lysis, average Large weir overflow rates result in excessive velocities at the outlet These
velOCItIes of flo cc ulatIng partIcles increase w ith d ep th. Since the paths of particles ve locit ies extend backward into the settling zone, causing particles and floes
tend to curve d ow nw a rd as illustr a ted in Fig. 4- 7, d epth is a factor in fl occ ul a nt which would o therwise be remo ved as sludge to be drawn into the outlet Overflow
se ttlin g. Therefore, the batch analysis mu st be p erfor med in a col umn of the same rates ranging from 6 m 3 j h per meter of weir for light flocs to about 14 m / h per
depth as th e basi n which it is to model. meter of weir for heavier discrete-particle suspensions are commonly used . [4-44J
. Settling basins designed for di sc rete particles are usuall y from 2.5 to 3 m d ee p, It may be necessar y to provide special inboard weir designs such as the one in
wh Ile those for flocculating p art ic les are usuall y 3 to 4 m deep. [4-44J From a Fig. 4-10 to acco mm o date the '!owe'r we{r
over'flow' rates. . .. . . ' ................... , .... . . .
practIcal standpoint. w idth s in excess of about 12 m crea te problems wi th s lu dge The design of long-rectangular settling b as ins i"S illustrated in the following
removal equipment ; thu s length s a re usually kept to less than 48 m. Multiple un~s
examp le.
III paralle l are used to o btain the vo lume and retention tim es need ed for large
flows. In fact , It IS always good practice to have at least two unit s so one can co n- Example'4-4~ Designing a long-rectangular settling basin for type.- 2 settling A city mu s t
tinue fun c tio ning while the ot her is down for repairs or routine maintenance. treat about 15,000 m) /d (4 Mgal /d) of water. Flocculating particl~s are prod uced 'by
F o r dilute suspen sion s, overflow rates for di scre te particle set t liu g usuall y range coagulation, and a colum n analys is indicates that an ove rflow rate of20 mid will produce
satisfactory remova l at a depth of 3.5 m. Determine the size of the required settling tank .
from 1.0 to 2.5 m / h (0.4 to 1.0 ga l/ ft 2 . min), wh ile ove rfl ow ra tes for fl occ ul a ting
suspensIons range from 0.6 to 1.0 mi ll (0.25 to 0.4 gal /ft 2 . min). Detention times
range from 2 to 4 h for discrete particles :1I1c1 from 4 to 6 h for flu cc ulating suspen -
s ions . [4-44J I. Compute surface area (provide two tank s at 7500 m /d each).
Alth ough se lec ti on of the overflow rat e and the detention time determine Q = qoAs
the size o f the basin, o th e r parameters also have to be co nsidered. These include
.7500 m 3 /d = A , x 20 mi d
th e horizontal ve loc ity Vh and th e weir over f~ow rate (/"'. 2
The motion of the s lud ge scraper may momentarily res uspe nd li g ht e r particles A, = 7500/20 = 375 m
a nd fl ocs a few ce nt ime ters above the sc raper blades. Since excess ive horizo nt,d 2. Se lecting a length -t o-width ratio of 3/ 1. calcu late surface dimensions.
ve loc ities wou ld m ove this material progress ive ly toward the ~lIt lct zo ne where It w x 3w = 375 m'
wou ld be los t in the overflow, horizontal flow veloc! ty s hould not exceed 9.0 I1l/ Il Width = 11.18. say 11 m
(0.5 ft/ mlll) for hght fl occulent sll spensions or about 36 mi ll (2 ft / min) for hea vier.
Length = 33.54, say 34 m
discrete-partIcle suspen s io ns. [4-44J

3. Check retention time. It is essential that the weir plates be precisely level. since a ve ry sli gh t differ-
ence in elevation will result in considerable short circuiting (dIrect channe lltl g
volume II m x 34 m x 3.5 m
(= - - - = from influ ent to effluent). Uneven distribution and wltld currents can also cause
flow rate Id
7500 mid x - short circuiting. These fa cto rs make flow con trol more difficult Itl cIrcular bas ll1s
24 h
than in lon g-;ectangu lar ones . Because fl ow-con trol problems become m o~e
= 4.19 h difficult to co ntro l as tank size increases. it is usually adVIsable to lImIt cIrcu lar
4. Check horizontal velocity. tank diameters to 30 1Tl or lcss. .
Design of circu lar sett lin g basins is based on overflow rates and detentIon
, d
Q 7500 m Id x -24- h times. Th e limit s presented for long-rectangular tanks are app lIcable to cIrcul ar
t', = - = - - - - - - - := 8. 1 mi h tank s. For obvious reaso ns. neith er horizontal ve lOCIty. nor weI r overflow rates
A, II m x 3.5 m
are a consideration in th e design of circlllnr settlIng bas1l1s. " .
5. Check weir overflow rate. If simple weir is placed across end of tank, overflow length The following exa mpl e illu s trat es the ciesign of cIrcular se ttltn g bas1l1s.
will be II m and overtlow rate will be
Example 4-5: Designing 3 circular settling basin Using the data in Ex a mplc-4-4. deter-
m' I dIm' mine the diameter required fo r circu lar se ttling baslIl s.
7500 -- x ~- x - - = 211 A - -
d 24 h II m h .m
Five times this length will be needed . Design weir as shown in Fig. 4-10.
6. Add inlet and outlet zones equal to depth of tank. and sludge zones as shown in the Aga in pro vid in g two ta nks. the surface area is cal cu lated as befo re.
accompanying figure.
,4 , = 375 m'

34.0 2. The tk"lIn eter is ca lculat ed by

/. ./ rrtl' , -I = 375 m '

3.5E Outlet
=:J 35
Dep th of
se ttling .
3. Inlet. outlet. and sl udge 70nes afC
tI = 2 1.85. say ~2 m

pro\ .1d ed as,'110"-1' 1 in the accompanyin eu fl!!Ur

~ e.
Slope Iii 00 zo ne plus
0.5 fre eboard
plus 0.5 for
. ............. AlI.dime-nsions in meters slud ge Zone
.... . .... . ....... . .................. . .

Scrtllllg 101lt.;
Circular Basins

Circular settling basins have the same functional zones as the long-rectangular
basin, but the flow regime is quite different. When the flow enters at the center and

1-''''''''"' '

Inkl 71 lilt'
4 .0 ) - - - - -

--- 4.0


is baffled to flow radially toward the perimeter. the horizontal velocity of the water
is continually decreasing as the distance from the center increases. Thu s. a discrete
.,./ ~
particle with a settling velocity Vo is continually undergoing a change in its absolute
velocity due to the decrease in ho rizontal velocity. Thus. the particle path in a

circular basin is a parabola as opposed to th e straight particle path line in the lo ng-
rectangular tank.
Circular t.anks have certain advantages. Sludge' removal mechanisms are
simpler and require less maintenance. [4-57]. Excessive weir overfl ow shou ld
never be a problem because the en'tire circumference is used for overfl ow. In fact.
I --=--


to prevent extremely thin sheets of water from being drawn off. overflow weirs Solids-Contact Basins
on circular tanks usually consist of V-notched met a l plates which reduce the effec-
.' ICI'.dII
. I 1'I0'cr Cll nstl
." !th ough sll lid s-cLl ntaCl b:t~tns ) : fl"')ll1 either CIrcular or Illng-
tive overflow area. These strips are bolted onto the collection trough and can be I .
rectan gular , . t Ile\ Stll
h:lsins with respec t 1(\ ll oll' regll11es. 1 nnk , c use of th e rrlnctples
adjusted to correct for differential se ttling of the basi n after construction.

of sedimentation previously discussed . The upward veloci ty of the flow in solids- As a factor of safety, the unit is usually sized so that the upflow velocity at a
contact basins works contrary to the settling velocity of the suspended particles. point 1.5 m below the top of the cone is one-half of the settling velocity of the particle
Referring to Fig. 4-11 the vector sum of velocities for any given particle is its that is to be removed . [4-1 J Generally speaking, upflow velocities of about 1 m/h
terminal settling velocity minus the upward velocity of the flow at the level of the at the liquid-so lids interface for flocculent sludges and about 2 mlh for nonfloccu-
particle. At high upward velocities (near the bottom o f the cone), vir tually all lated slurries are adequate. Solids concentration of approximately 3 percent by
particles and floes are swept upward with the flow. As the cross-sectional area weight for flocculated sludge blankets and approximately 5 percent by weight
of the cone increases, the upward velocity of the water decreases, and the vector for nonflocculated slurries s hould be maintained in the solids blanket. Since
sum of the velocities reaches zero; the particle stops and is suspended at that height horizon tal velocities are to be avoided in this process, overflow weirs should be
in the cone. At this point, a particle is considered" removed" from the water. arranged to ensure essentially vertical flow. Horizontal flow distances should not
Obviously, larger particles with greater sett ling velocities become suspended exceed the depth of the clarified zone by more than a factor of 3. [4-44J
nearer the bottom of the cone where upflow velocities are higher. Particles whose
settling ve locity is exceeded by the upflow velocity at the top of the cone are swept
on upw ard and into the overflow of the tank.
Particles collect at positions dictated by their settling velocities until a so lids
Virtually all surface water sources contain perceptible turbidity. Some particle
blanket is formed . creating a concentrated suspension. even if the original sus-
sizes common to most surface waters are listed in Table 4-1, along with their
pension was dilute. The creation of the solids blanket is an importan t part of
terminal settling velocity (assuming quiescent conditions and specific gravity of
upflow clarification. Very small particles. which would normally be swe pt out of
2.65). From these values it is obvious that plain sedimentation will not be very
the clarifier. mu st first pass through the concentrated zone. In flocculating sus-
efficient for the smaller suspended particles. Under conditions normally encoun-
pensions, the chances are excellent that enmes hment in the sludge blanket will
tered in setiling basins, efficient removal of particles less than 50 pm in diameter
occur so th~t even very small particles or floes win be removed. Thu s. the blanket
cannot be expected.
acts similarly to a filter for solids removal.
Agglomeration of particles into groups, increasing the effective size and there-
The elevation of the sludge blanket in the cone is determined by the concen-
fore the settling velocities, is possible in some instances. Particles in the colloidal
tration of the solids in the blanket. higher concentration resulting in a greater rise.
size range, however. possess certain properties that prevent agglomeration. Surface
The concentration, and thus the elevation, of the solids blanket is controlled by
waters with turbidity resulting from colloidal particles cannot be clarified without
drawing off excess sludge once the desired concentration and height have 'been
special treatment. A knowledge of the nature of colloidal suspensions is essential
reached ..
At section bb,
the upflow
velocity is equ a l to the
. XO .tbis removaL.. ......................................................... . ............................. ..

Colloidal Stability
se ttling velocity of the
particle . Th e net ty
Cylindrical is zero, 3nd all particles Colloidal suspensions that do not agglomerate naturally are called slable. The
section with ihis settling velocity. most important factor contributing to the stability of colloidal suspensions is the
remain suspended in the excessively large surface-to-volume ratio resulting from their very small size,
flow at Ihis point-.

Table 4-1 Settling velocities of various size particles*
Coni ca l
section Particle Size
Upflow Settling
diameter typical Settling
velocity ve loci ty
a- mm 01 velocity
of particle

At sect ion aa, the upflow velocity 10 Pebble 0.73 In iS

Uptlow Settling Ntt
exceeds the sett lin g velocity of the
velocity velocity vdocity
Coarse sand n.n Inf'

particle. The net velocity of the 01 Fine sand 1.0 x' 10 - ' m!s (0.6 m / min)
particle is in the directio'l of flow. 01' p3.ticl e
001 Silt 1.0 x 10 4 m /s (R.6 m /d)
and the particle is swept upward at O.UOOI Large collnid 10 x 10 - ' Ill !, (0.3 In/ yr)
the net velocity. OOOOUO I Small colloid 1.0 x 10 \J Ill is (3 m / million yr)
------- --------- --
Figure 4-11 Principles of upAow clarification. . . Srhcrcs With srecific gravi ty or 2.65 in water cit 20"('

Surface phenomen a predominate over mass phenomena. The most impo rtant Wh en two coll oids come in close proximity there a re two forces acting o n them.
surface phenomenon is the accumulation of electrica l charges at the particle The electrosta ti c potential created by the " ha lo" of cou nter ions surrounding
surface. Molecul a r a rrangement within crys tals. loss of atoms due to abrasion of eac h colloid react s to repe l th e pa rti cles. thu s preventing contact. The second force.
the surfaces, or o ther fac to rs may result in th e s urfaces being charged. In most an attracti on forc e ca lled th e mn der Wau/s[orce, supports co nt act. This force is
surface waters. colloidal surfaces are negatively charged. in verse ly proportional to the six th power of th e distance between the p a rticles
Ions contained in the wa ter near the colloid will be affected by the charged and also decays expone nti a ll y with distance. It decreases more rapidly than th e
surface. A negatively charged colloid with a possible configuration of ions around electrostatic potential. but is a str o nger force at close distances. The sum of th e
it is shown in Fig. 4-12.The first layer of cations attracted to the negatively charged two fo rces as th ey relate to o ne coll oid in close proximity to ano ther is illustra ted
surface is " bound " to the colloid and will travel with it. shou ld displacement of the in Fi g. 4- 13. As noted in the figure. th e net force is repulsive at grea ter distances
colloid relative to the water occur. Other ions in the vicinity of the colloid arrange and becomes attractive on ly after passing thr o ugh a maximum net repulsive force.
themselves. as shown. with greater concentrations of positive. o r co unter. io ns ca ll ed th e eYler9.1' harrier. at some distance between co lloid s. Once the force becomes
being closer to th e co lloidal surface. This arrangement produces a net cha rge attrac ti ve. con tact betwcen t il e particles tak es pl ace.
that is strongest at the bo und layer and decreases exponentially with distan ce fr o m /\. means of overco min g th e ene rgy barrier mu st be ava ilable before agglomer-
the colloid . ation of particles can occur. Brown ian movem ent. th e ra nd o m movement of sma ller
co ll oids becau se of molec ular bombardment. may produce enough momentum
'- - for particles to nvercome the ene rgy barrier and thu s co llid e. Mechanical agitation
+ + " \ of the water ma y impart eno ugh moment lim to la rge r particles to move them
+ \ across the energy barrier. Th ese processes are too slow . howeve r. to be efficient
+ \
+ \
+ \

+ I

B:;/ + +

+ ......... ....... . . ......... . .

~ ~
' 0"

o ~----~~------~=---~~------------ be t ween
co ll o ids

Net rorce (Lcta - va" dcc Waal s)

- - - - - - - - -~::a---r-

Diffused layer
Di stance from particle
Figure 4-12 Charge sys tem in a co ll oida l suspen sion. Figure 4-1 3 Force fields b,,,ween (plio Ids of like charge.

in water purification. and neither results in collisions of medium-sized colloids.
Thus. other means of agglomeration must be used. In water purification this is
generally accomplished by chemically coagulating the colloids into clusters. or
flocs. wh ich are large enough to be rem oved by gra vit y sett ling.

Coagulation Theory
In water-treatment plants. chemical coagulation is usually accomplished by the '-
addition of tri va lent metallic salts such as AL 2 (S04).1 (aluminum s ulfate) or
FeCI ] (ferric chloride). Although the exact method by which coagulation is ac- "
complished cannot be determined, four mechanisms are thought to occur. These Z
include ionic layer compression, adsorption and charge nel tralization , entrap-
ment in a flocculent mass, and adsorption and interparticle bridging.

Ionic layer compression The quantity of ions in th e water surrounding a colloid

has an effect on the decay function of the electrostatic potential. As illustrated in
Fig. 4-14 a high ionic concentration compresses the layers composed predomi- Diffused
nantly of counter ion s toward the surface of the colloid. If this layer is sufficiently layer
compressed, then the van del' Waals force will be pred o minant across the entire Distance from particle

area of influ ence, so that the net force will be attractive a nd no energy barriers will (a)
exist. An example of ionic layer compression occurs in nature when a turbid
stream flow s into the ocean. There the ion content of the water increases drastically
and coagulation and settling occur. Eventually, deposits (deltas) are formed from
material which was originally so small that It could not have se ttled without
coa~ulation. Although coagulants such as aluminum and ferric salts used in water
. treatmenl 'iDn ize ; 'at t he 'conce'ntrarion 'co ttjmtiiilY''tfsed''fhey \vQuld not increase
the ionic concentration sufficiently to affect ' ion layer compression.
Adsorption and charge neutralization The nature , rather than the quantity, of the o
ions is of prime importance in the theory of adsorption and charge neutralization. '"
Although aluminum sulfate (alum) is used, as in the example below, ferric chloride "
o"~N ~~~~~~~~~~ __________~~
behaves similarly. U. ~ Distanc~ between
The ionization of aluminum sulfate in water produces sulfate anion s (SO/ - ) ~ particles
and aluminum cations (A1 3 +). The sulfate ions may remain in this form or combine
with o th er ca tion s. However. the A1 3 + cations react immediately with water to
form a var ie ty of 3quometallic ion s and hydrogen.

AI.l + + H 20 ----'--+ AIOH 2 + + H ' (4-13a)

A1 3
+ + 2H 2 0 Al(OH 2 )! + :!W (4-13&)
7A I J
' + 17 H 2 0 AJ 7 (OH)! " ~ ' -/- 171-1 ' (4- 13c) Figure 4-14 Ionic compression: (a)
reduction of thickness in diffused layer;
(b) (b) reduction of net force .

AI" -/- 3 H 2 0 ---~ Al(OH), -/- 3 11 (4-IJn)


The aquometallic ions thu s fo rm ed become part of the ionic cloud surround- Inili a l odsorpll o n 01 Ihe optimum polym e r dosage
ing the colloid and, because they have a great affinity for surfaces, are ad sorbed

o nto the surface of the colloid whe re they neutra lize the surface c harge. Once .the
surface charge has been neutralized , the ionic cloud di ssipates and the electrostatic
potential disappears so that contact occurs fre e ly. Overdosing with coagulants ~ Polymer
Pori icl e

Destabi li zed
pa rt iele
can result in rest a bilizing the suspens ion. If enough a quomet a llic ions are form ed

and adsorbed: the charges on the ' particles beco me reversed and the ionic clo ud s F loc forination
reform , with nega tive ions bein g the cbunter io ns. This phen omenon will be dis-

Flo ccul a tion
cussed more fully in a later section.
(pe rik inetic or
orthokin e ti c)
Sweep coagulation According to Eq. (4-13n), th e la st produ ct fo rmed in the
Destabili zed pa rti cles
hydrolysis of alum is aluminum hydroxide , AI(OHh. The AI(OHh form s in
amorphous, gelatinous flocs th a t a re heavier than water and se ttle by gravity. Secondary adsor pll on of po ly mer

Colloids may become entrapped in a floc as it is formed , or th ey may beco me Restab ili zed padicle
enmeshed b y its "stick y" surface as th e floes sett le. The process by which colloid s
are swept from su spension in thi s manner is known as sweep coagulation.
Destabiliz ed particl e

No contact wit h vacant site s

on ano lher particle
Interparticle bridging Large m o lec ul es may be formed when aluminum or fe rri c Ini tial adsor pti on excess

- ~
sa lts dissociate in water. Equati o n (4-13c) is an exa mple , although larger o nes poly mer dosage
are probably formed also. Synthetic polymers a lso may be used in stead of, or
in addition to, metallic salts. These polymers ma y be linear or branched a nd are
highly surface re a ctive. Thu s, seve ral colloids m ay become a tt ac hed to o ne
polymer and seve ral of the polymer-co lloid groups may becom e en meshed (Fi g.
4-15), resulting in a se ttleable m ass.
5 it 7
Excess polymers
Part ide
Ruplurc of !loc
Stabl e particle
(no vacant sit es)

~ -96~
In addition to the adsorption forces, charges o n the pol ymer ma y assist in ' I
the coagulation process. Metallic polymers form ed by the addition o f aluminum
.. .- ..... ............or.ferr.icsalts are positively cha rged , while synthetic polymers ma y carry positive Intense or
. . ..

or negative charges or may be neutral. Judicious choice of appropriate charges pro longed fragments
Floc part ide agi tatio n
may do much to enhance the effectiveness of coagulation.
Secondary adsorp tio n oj pol y mer

Jar Tests for Optimum Coagulant Dosage
Coagulation is no t yet an exact sc ience. a lthou g h rece nt advances have been m ade
in understanding the mechanics o f the process . Therefore. selection and optinlum Ftoc fra gmen t -' cY
Restabilized !loc
dosages of coagulant s are determin ed experimentally by the jar tes t instead o f
quantitatively b y fo rmula. The j ar test must be performed on eac h wa ter th a t is 'Figure 4-15 Irll crparticle bridging with polymers. (Alier O' M elia [4'-41].)
to be coagulated and must be repea ted with each significa nt cha n ge in the q ua lit y

of a given. water.
The jar test is p erfo using a se ries of g lass co ntainers that ho ld at leas t Aft er chemical addi t io n. th e \vater IS mixed rap idl y for about j min to ensure
I L and are of uniFo rm size and s ha pe. Normall y. s ix jars are used w ith a stirrin g co mplete di spersion of the c hemicals. then mix ed slow ly for. 15 to 20 min to aid
device (Fig. 4-16) th a t simultaneollsly mixes th e co nt ents o f each jar with a uni- in tlie formati on of flocs. The water is nex. t a ll owed to se ttl e for app ro ximately
fo rm power input. Each of the s ix. jars is filled to the I-L mark wit h water whose 30 min , or' un til clar ifica ti on 'h a s occ urred P o rtions o f th e se ttl ed wa ter are then
turbidity, pH, and a lk a linit y ha ve been predetermined. One jar is used as a co ntro l, removed a nd tes ted to d eter min e th e re maini ng turbidity. Test res ults are used
while the rem a inin g fi ve are do sed wi th different amou nt s of coagulan t(s) a t to calc ul a te th e type and quantity of coagu la n t to be u sed in th e wate r-trea tm en t
different pH va lu es until the minimum valu es o f residual turbidit y are obta ined. plan t.

At higher co lloida l concen trations (Fig. 4-17b), destabilization by adsorption

and charge neutra lizati o n OCC llrs early (zone 2), but continued addition of the
coagulant results in c harge reversal and restabilization (zone 3). Still greater
colloidal concentrations (Fig. 4-17c) resu lt in more chances of collisions, and thus
better coagulation over a wider range of concen tra ti on. Continued addition of
coagulants result s first in restabilization and eventually in hydro xide f1bc formation
and sweep coagu la ti on (zo ne 4). .
Extremely large co lloidal concentrati o ns (Fig. 4-I7d) theo retically provide
eno ugh co lloids to result in coagulation by adsorption and charge neutra lizati o n
(zone 2), a lthough it is probab le that polymer bridging and sweep coagu lation
also occur. Restab ilizat ion of highly turbid waters is seldom a problem.
Information from many curves similar to th ose in Fi g. 4-17 can be summarized
Figure 4-16 J ar test apparatus. as show n in Fig. 4-18. Two very useful observations can be made from this figure.
First. coagulation by adsorp ti on an d charge neutralizati on (zone 2) is impractical
Jar tests also serve to illu stra te the me'c banics of coagulation. Ge nera lized unless coagu lant dosage can be ve ry carefully con trolled . As illustrated by the
coagula ti on region for t he colloid concentra tions S 2, a very sli gh t overdose results
curves for residual turbidit y as a fury:tionof coagu lant dosages and initia l turbidit y
in restabilization . Second , highly turbid wa ters may require a lesser a mount o f
appear Il1 FIg. 4-17 . Co ll o Id concen tra tIOn? S are measured in terms of surfac e
coagulan t for good coagu la ti o n th a n waters wi th slig ht turbidit y. For this reason
area per liter a nd increase from SI to S4' A-t low coll oidal concen t ra ti ons (Fig.
it is sometimes adva nt ageo us to odd turbidit y to re lati vely clear water. For example,
4-170), insufficient numbers of colloids are present to form settleable masses
if water with an initial turbidity correspond ing to SI were made more turbid ,
(zo ne I), even if the surface charges la re neutralized. In such a case. co agu lat io n is
no t initiated until enough coagulant has been added to precipitate as a metallic
hydroxide . At low collo idal concentrations. the preqominant mechanism is-sweep
co agu lation. I ' '!

Coll o id co nc. = S.

Zone I
(d ) c:
Co ll oid conc. ~ Optimum
'8 coagu lan I
~ (losage to
Zone I ~ produce
~ "sweep noc"
; ; ~---. . ;. .:;.:, ~--=--------~,..., Zone 1
e>: 0plimum
Zo ne 3 coagula nl dusage I
I in s[oichiomerric I
( b) I destabiliza tion :
Benl oni te I
Co lloid co ne . =St I
addi ti on I I

Zone I s; S4
(a) Co ll oid concen t ration , e x pressed
as co ncen lration of surface (S)
Dosage of coagulant

Figure 4-17 Results of ja r tests at increasing turbidities . (Af ter O'Jleliu [4 . 4 1).) Figure 4-18 Coagulant dosage as a funcliu n of lurbidil Y. (A/ ter 0' Melia [44 I l)

say ro S3 or beyond , savings In coagulants could be realized. Bentonite clay is do sage. Addition of so me turbidit y may decrease the amount of coag ul a nt
generally used for this purpose. needed.
Group 4: Lo\\' liIrniditr-low alkalinilY. Again. the small number of colloids make
coag ul a tion difTicult. <lndlow alkalinity prevents eflective AI(OHh formation.
Additio nal turbidity can be added to convert thi s wate r to that of group I. or
Alkalinity-Coagulation Relationships
additional alka linit y ca n beadded to convert it Lo a G roup 3 type. It may be
As noted in Eq. (4-13), the coagulation of metallic salts releases hydroge n ion s advantageou s to add both turbidit y and alkalinity.
as well as coagulant species. These hydroge n ions neutralize alkalinity. H ydrogen
resulting from the addition of I mg/ L of alum will neutrali ze 0.5 mg/ L of a lkalinit y. It s hould be recognized that the above cases are generali zat ions. Optimum
If the'initial alkalinity of a water is low. further reduction will destro y it s buffer- trea tm e nt of an y wate r c an o nl y be determined by ca reful analysis us in g th e jar
ing capacity and the pH will drop rapidly. Since optimum pH values must be
test o r o ther pilot -plant procedures.
maintained for best coagulation and since alkalinity must be prese nt for hyd roxide The laborat o ry coag ulation jar test is model ed after the coagulation process
floc formation, low alkalinity wate rs must be artificially buffered. This is usuall y used in most water- treatme nt plants. In both cases. the coagulant is first added to
accomplished by the addition of lime [Ca(OH)2J or soda ash (Na 2 CO). the water, and the water is then vio lentl y agitated to ensure uniform mixing. This
operation is termed rapid lIIixilly. Th e water is then gently stirred to k eep all the
so lids in suspension and to promote co llisions between destabilized particles and
Coagulation Practice between p artic les and floc s. This ope rati o n is ca ll edjlocclilat ion. Finally . the water
Aluminum sulfate. the most commonly used coagulant in water purifica tion , is is passed through a se ttling basin wherc the fl occ ulated solids are removed by
most eflective between pH ranges of 5.0 and 7.5. Ferric chloride. effective down to type-2 se ttlin g. These operatio ns a re illu strated in Fig. 4-19. and detailed descrip-
pH 4.5. and ferrous sulfate. effective on ly' above pH 9.5. are sometimes used. [4- 54J tions ar,' given in the following scc ti o ns.
Although less expensive than alum . these coagulants can cause color problems if
the precipitate is not removed completely. It is sometimes advantageous to use
Rapid mixing Thorough mixing is essentia l if uniform coagulation is to occur.
synthetic polymers in addition to alum. These pol ymers bind small fl ocs togethcr
Conseq uently. careful attention must be paid to the design of rapid-mix units.
to make larger masses for faster settling. Design param cter s for rapid-mix unit s are mixing time I and ve locit y gradient G.
Alum dosage may range from 5 mg/ L to 50 mg/ L. depending upon the turbidity
The velocity gradient is a measure of th e relative veloc it y of tw o particles of fluid
and nature of the water. At low turbidity and high dosage, AI(OH) , is almost
..... ,uJd .. the.distance .. bctwee n.... As .an examp le, two water particles m oving I m /s
certain to form so that thepredominant tubidity~removal' meclTanis~y is 'sweep-"
rela tivc to cach othcr ai a dista nce 0.1 111 apart would have a ve loci ty grad ient of:
coagulation . At high turbidity and lower dosages. adsorption and charge neu tra l-
ization will be the predominant mechanis m. although interparticle bonding prob-
1.0 m/s
ably plays a significant role. Ionic layer compression woilld not be significant at I () S I
0. 1 m
these concentrations. With regard to coagulation. surface waters can be gro uped
into the four general categories described below. [4-41 J A more useful concept of velocity gradi e nt s. however. is given in term s o f power
di ssipation per vo lum e. [4- 12J
Group 1: High turbidity-low alkalinity. With relatively sma ll dosages of coag ulant.
water of this type should be easily coagulated by adsorption and charge
neutrali zation . Depression of pH m akes this method more elfecti ve. since the Ci (4-14)
aquometallic ions are more effeclive at lower pH values. Howeve r. care should
be used to prevent excessively low pH.
Group 2: ,High turbidity-high alkalinity. The pH will be relatively unaffected by \\'jlerc (i. = vclocity g.radient. s . I
coagulant addition. Because of the higli alkalinity, adsorption and charge P '= polYcr iilput. W (N . m /s)
neutralization will be less effective than in waters of low alkalinity. Higher I' = \o luill c ,)f"lllixing basin. Ill .'
/1 = \'isc0s it y, N s/ m
coagulant dosage should be used to e ns ure sweep coagulation.
Group 3: LOll" fIIrbiliily-hiyh allwlinity. The small number of colloid s mak e coag u-
lation difficult. even if the particle charge has been neutralized. The principal Ibp iLi mi'\ln g ca n he aC C<l lllpllShed III IlUlllc rou s ways. Illcluding Injection o f
coagulation mechanism is sweep coag ulati o n with moderate coagu lant Coag ul<lllt s at th e s uc ti <>n side u f pumps. ups tr ea m rl"Olll hydr a ulic Jumps. or in

Fl oct'ulalor C lar lfi~ r


.. '
2J . ,
impeller ~ .'.

, .- D

:..:~ .

(a) (b)

Figure 4-20 Typical rapid-mixing tanks: (a) back-mix impeller and (b) flat-blade impeller.

impellers (Fig. 4-20a). A more effective unit might be a square tank with baffles
and flat blade impellers as shown in Fig. 4-20b. [4-4J
In-line blenders are designed for complete mixing in less than 1 s. Values of C
Ge:.H Chain for in-line blenders, calculated from flow rate and power input or head loss, range
motor (a)
from 3000 to 50000 s - I [4-32J Several configurations of in-line blenders are

available ; two models are shown in Fig. 4-21.
..... Haodrail
Turntable Tor of tank Flocculation The flocculation process relies on turbulence to promote collisions.
Velocity gradients are also a convenient way of measuring this turbulence. Time
is an important factor, and the design parameter for flocculation is Gt, a dimen-
sionless number. Values of Ct from 104 to 10 5 are commonly used, with t ranging
from 10 to 30 min. [4-28J Large G values with'short times tend to produce small,
den'se floes, while low C 'values and long times produce larger, lighter floes. Since
Sludge discharge pipe
large, dense floes are more easily removed in the settling basin, it may be advan-
tageous to vary the G values over the length of the flocculation basin. The small,
Figure 4-19 Rapid mixing and flocculatio n followed by a sq uare settling ba sin: (a) plan and (b) sec- gense floes produced at high G values subsequently combine into larger floes at"
tional elevati o n (cuurtesy 0/ Dorr-Olin:T , In c.). the lower G values. Reduction in G values by a factor of 2 from the influent end
to the effluent end of the ftocculator has been shown to be effective. [4-33J
flow-throu g h basins where head loss around baffles provides power input. Most Traditional flocculator design is illustrated in Fig. 4-22. These units consist
modcrn designs. howevcL use either mixing tanks with back-mix impellers or of long-rectangular basis equipped with mechanically operated paddles to provide
in -lin e flash mixers .. In-line fla sh mixers Illay ha ve mechanically dri ven impellers power input. The paddles are usually constructed of redwood or aluminum slats
or may rel y o n head loss created by static constrictions in the pipe. and may operate either transverse or parallel to the longitudinal axis of the basin.
Rapid -mixing tanks operate best at C va lu es from 700 to 1000, wi th detention . More recent design tends toward units which combine rapid mixing, floccula-
times of ap prox imately 2 min . [4-10,4- 36J Numerolls config urati ons of ta nks and tIon, and settling in one tank. Such a unit is shown in Fig. 4-23. The principles
impel lers are used, with the most popular units being square tank s with back-mix of mixing and floccu lation in this unit are the same as those for the long-rectangular







Figure 4-21 In-line blenders: (a) powe r-driven (courtesy of Walker Process Corp.); (b) sialic mixer
pipe section (courtesy of Kom ax Systems, In c.); (c) static mi xe r in2.5 x 2.5-m-squarc channel secl io n
This mixer processes 530.000 m 3 /d a t Ih e Val Visla waler-Irealment pJa~1 in Ph oenix, Arizona. NOle
chemical reed lines in front o r vanes (courtesy of Komax Systems, Inc.)

basin. although the method of operation is some~hat different. While these unit s
are limited in the quantity of flow th at they can handle. l11ulti ple units ca n he
provided in parallel to meet any demand .
. . 'The G value for mechanicall y dri ven flocculators is calculated as follows.
First. the power input is determined by
P (4- 15)
Figun' 4-22 Flnccuialnr unil'. (a) paJdk arr:tngemcnl III long "Ink (pho to cOl/rtesy of Emirex Illc., a
where P = power input. W (N . l11 /s) Iinnor" Cllmp/my): (h) mulllStage 11111" (pito to m:"lt '.'.1' or WlIlkl'r Profess Corp.) : (c) lurbine-type
unIt:-, (pho/(J ('UIIr!('.\'Y oj /:,,,,-irex. /11(' . (J RI .\ non A q'0 111/70'11 ').
D = drag. force on paddles. N
t:p = \'e locity of paddles. mis
./. ' '1
I 1~ 5

I i

The drag force on the paddle is given by

C (4-16)
c: 0.
.E t
where CD = dimensionless coefficient of drag, 1.8 for flat blades
Ir Ap = area of paddle blades, m 2
p = density of m 3
"0 I
c t Equation (4-15) now becomes
:::'"0 r~
: ~
..... 0 1

..!: I
!; r Subst ituting into Eq. (4-14)
C) ~ c
A 3
'"coc '"c " [ G= _ D_ p_.-!!.
) 1{ 2

( 2V,u

0 'c-
The area of the paddle A p refers to the combined area of the slats that are
'" u
"0 '"
C ., ., ~ perpendicular to the cylinder of rotation. This area should not exceed 40 percent

., .~ of the total area encompassed by the paddle. The veloci ty of the paddle tip up is the
... 1. veloc it y relative to the water and is about 75 percent of the actual paddle speed.
'"c "U

Paddle velocity should be less than I mis, and a minimum distance of 0.3 m
C u"c shou ld be maintained between paddle tips and all o ther structures in the f1occulator
.2 f .
... .......
'''> 'c ' . . Tei 'pteveiifTocal":rr"t:as' of'ex'ce-ssive'vetoc1ty" gradients: ..... . .... .
.2 f~
~ e'" It should be noted th at in transferri ng water from the flocculator basin to the
settling basin, extreme care must be exercised to avoid turbulence that can break
0 "E
up the floc. T his is usua :ly not a problem in units in which mixing, fl occu lation,
and settling are comb ined. In the long- rectangula r units, the settling basin is



iI often constructed adjacent to the floccu)ator, with the common wall omitted.
Necessary baffles are designed for low G va lues.
,.'" -5 Design of fl occu lation units is illustrated in the following example.
'1< ~

<= ~

~ Example 4-6: Designing a flocculator A water-treatment plant is being designed to pro-
0'" u'"
, cess 50,000 m' /d of water. Jar testing and pilot-plant ana lysis indicate tha t an alum
u dosage of 40 mg/ L with flocculation at a GI va lu e of 4.0 x 10' produces op tim al results
;:'" at t he expected waler temperatures of 15C. Determ ine:
i" I. The mon th ly alum requ irement.
~ 2. The fl occulati o n ba sin dimens ions if three cross flow horizontal paddles are to be used.
c c:
,j. The flocculator should be a maximum of 12 m wide and 5 m deep in order to co nn ect
:J ~
appropriat e ly with the sett ling basin .
E "
a<: ~
w (Z 3. The power requirement.
146 4. The paddle conligur:ltioll.

I. Monthly alum requirements:
----, ---., ---,
40 mg/L = 0.04 kg/m 3
r--- r--- r---
and I I I I I
0.04 kg ' m 3
_ _ x 50000 - x 30 d/mo = 60,000 kg/mo
IL ___ ___ J
L ___ ___ .JI IL ___ ___ J I

m3 . ' d 0
r--- - - - , r - - - r--- ---..,
2. Basin dimensions: E I I I I I I
a. Assume an average. G value of 30 s - 1 '"
0 I
IL ___
___ JI IL ___
___ ...JI
GI = 4.0 x 10'
4.0 X \0 4 I min
L ___


r--- ---"I r---

___ ...J

---,I ,---
---., I
1= 30 ~ I I I I I
I I I, I I
1 = 22.22 min
IL ___ I I I
___ J .IL ___ ___ .J L ___ ___ JI

b. Volume of the tank is 1""'" ... E PI<ln

V = QI = 50,000 m 3/d x 22.22 rrT)'!fl x I d/ 1440 min ""

= 771.5 m 3 3. Power requirements:

c. The tank will contain three cross-flow paddles. so its length will be divided into a. Assume G value tapered as follows.
three compartments. For equal distribution of velocity gradients, the end area of First compartment. G = 40 s - 1
each compartment should be square, i.e., depth equals t length. Assuming maximum
Second compartment, G = 30 s - 1
depth of 5 m, length is
Third compartment, G = 20 s - I
3x5=15m I
b. Calculate power requirements for compartments 1,2, and 3:
and width is
P = G' V/I
.... ";'; ~iO.3 m' V =: 771.5 m 3 /3 = 257.2 m 3
At 15 C
d. The configuration of the tanks and paddles should be as follows: J1 = 1.139 x 10- P N '5/m'
P, = 40 2 / S 2 x 2572m 3 x 1.139 x 1O - 3 N.s/m 2
E = 468.7 N . m)s x 10 " 3 kW,f N mls = 0.47 kW

, I

P2 = 30 2 x 2572 x 1.139 X 10- 3 x 10- 3 = 0.26 kW'

i C>() iEB k9;)

3 3
P, = 20' x 257.2 x 1.139 x 10 - x 10 - = 0.12kW
E 4. Paddle configuration
u. Assume paddle design as shown below.

~l~/: --/

. 6t ~/. ~--T-
~j H ~

. ,
~ '0:4;;;""
1r-rrr77""TTT:~ ~~ 4.2 m
0.8 m 0.8 m V//////////// _~____ ~_
J 5m (.


Third compartment:
Each paddle wheel has four b oa rds 2.5 m long and w wide- three paddle wheels per
compa rtment.
b. Calc ulate IV from power input and paddle velocity.
l' = (120 N. m /s x _1_~)'{3
p 3777 N s'
p = - - --
2 = (0.03 m) /s) ' !) = 0.32 mrs J
. . I ,
At 15C L' p actual = 0.32 m/s x - = 0.42 m/s -'
. 0.75
'p = 999.1 kg/ m J
(<) = 1.91 rev/min
Assume "p = 0.67 m/s x 0.75 = 0.5 m/s and CD = I.lI.

Ap = length of boards x IV x number of boards

.\ paddles at 4 boards per paddle = 12 boards
Hardness as a water-quali ty parameter was discussed in Sec. 2- 10. The reduction
12 x 2.5 x IV = JOw = Ap
of hardness. or sojiening, is a process commonly practiced in water treatment.
P, = 468.7 Nm/s = (1.8 x 30w m x 999.1 kg/m) x N s'/kgm x 05) m)/ s) / 2 Softening may be done by the water utility at the treatment plant or by the con-
sumer at the point of use, depending on the economics of the situation and the public
937.4 m = 1.8 x 30 x 999.1 X 0.5)w
desire for soft water. Generally, softening of moderately hard water (50 to 150
937.4 m = 674~w mg/ L hardness) is best left to the consumer, while harder water should be softened
IV = 0.14 m
at the water-t reatment plant. Soften ing processes commonly used are chemical
precipitation and ion exchange, either of which may be employed at the utility-
c. Calculate rotational speed of paddles. owned treatment plant. Home-use softeners are almost exclusively ion-exchange
Fir sl compartment: units.
v = nD -
P rev
x (lJ Chemical Precipitation ----)

The different species of hanJness have different solubility limits, as shown in Table
= 1l4.2 -
x (;.) 4-2. The least soluble forms are calcium carbonate and magnesi'lim hYdroxlde.......... .
Chemical precipitation is accomplished by converting calcium hardness to calcium
rev 60 s carbonate and magnesium hardness to magnesium hydroxide. This can be ac-
0.67 m/s x - - - - x - -. = J05 rev/ min = w
4.21l m min complished by the lime - soda ash process or by the caustic soda process.

Second compartment: Lime- soda ash All forms of carbonate hardness as "well as magnesium noncar-
bonate hardness can be converted to the precipitating species by the addition of
) N . m/ s
p = 0.26 kW x 10 - - - lime (CaO). In the following equations, the symbol s is used to indicate that a
solid precipitate forms and that it is sufficiently dense to settle by gravity.
Ca2+ + 2(HC01r + CaO + H20 -----+ 2CaC0 3 $ + 2H 2 0 (4-17)
Mg 2+ + 2(HCO,)- + CaO + H20 ~ CaCO)$ + Mg2+ + CO/-
= 1.8 (30 x 0 14)m ' x 999. 1 kg /mJ x N s,lg ' m x 1' ~12
260 N . m!s = -37}7 N 5' j m x rF

up =
( 260 N . m/s x '3 77 17-mN'~ s:-'_) 1: J

= (007 m ' /s.1 )") = 0.41 m is

AClual speed = u,,/075 = 0.55 mi s
(() = 2.5 rev/ min

Table 4-2 Equilibrium of solid and dissolved species of 200

common ions

Mineral F o rmula
Soillbility, ..
mg/L CaCO) at oec
rf 100

Calcium bica r bonate Ca(HCO,h 1,620

r,. - 160
Calcium carbonate CaCO, 15 t "-
. Calcium
chlo ri de
sulfa te
CaCl, 336,000 ! ,2

CaSO. 1.290
Calcium hydroxide Ca (OHl, 2,390 E. 140

M agnes ium bicarbonate Mg(H CO J ), 37, 100 <


Magnesium carbo nate MgCO , 101 I co

E 120
hydrox ide
MgC l,
Mg(OH ),
362, 000
i ~
Concentralion 01 calcium
io n in t:'qui li briul1l wilh
ca lcium l'arhonah'
SodwlILbica rbon ate NaHCO J 38.700 '" ~
Sodiu m ca rbona te Na ,CO) 61.400 "i::;
Sodium ch lo ride NaCI 225,000 :; xo
Sodium hydroxide NaOH 370,000 '-
Sodium sulfate Na ,SO. 33,600

Source: Adapted from Loe wenth a l and Marais. [4 38J "..,


Iv 4()
As seen in Eq. (4-20). removal o f magnesium no ncarb o nate ha rdness results in
the formation of ca lcium noncarbonate hardness. Thi s calcium no nca rbon a te \ t i -.O llcentlatlonol magnesium
hardness. as well as any initially present in the water, can be removed by the ad 20 ~. io n in cqlulibrruill wIth
dition of soda ash (Na 2 CO): .
....... ma g JlC' slllll1 hydrox](je
f'.,.. ...,/
..... -. ~ ... . ... I j J
l) 10 II 0
\3 14
pH ,crlU e"

Figure 4.24 E4uilibrium concent ration of ca lciu m and magnesi~m io ns a s a function o f pH (From
I'o,,ell [4.43].)

The sodium in Eq. (4-21) is so luble a nd . unless excessive a m o unt s are added . is Although thi s reaclion does !l o t redu ce hardn ess. it d oes co ns um e lime. Rem ova l
permiss ib le in p o table water. o f super sal urated CO 2 by ae ratio n is o ft en pracliced to reduce lun e reljUlrements.
The precipi ta t ion of CaCO J and Mg(OH }z is pH-depend ent. as is illustrat ed If CO 2 exceeds 10 m g/ L it ma y be eco n o mi ca ll y advanlageous to remove tt prIor
in F ig. 4-24. The optimum pH fo r CaCO) precipita tion by line addition is from lo soft ening.
9 t o 9.5, wh ile effective precipitati o n o f Mg(OH) 2 under water-treatment p lant Caustic soda. All forms of hardn ess can also be conve rt ed t o th e precipit aling
';.... -
condit ions requires a pH of ab o ut J 1.0. Since mo st n a tural waters have a pH species by the addil ion of caus li c soda (N aOH ).
cons iderab ly below t hese va lues. it is often necessar y to a rti fi c iall y r:lise the pH .
Th is ca n be accomp li s hed by the additi o n o f an excess am o unt o f lime :
CO 2 + 2Na O l1 ----> 2Na- + ('0,/ - + H20 (4 24)
Ca: ' + 2( HCO,) ' + 2N aOH
(422) CaC0 3 $ + 2Na + + ('0/ - + ~ H;O (425)

The addition of about 1.25 mequi\ !L of lime is sufli c ient to raise the pH to 11.0. i\ lg'; + 2( HC O ,) + 4 NaO H
If di sso lved ca rb o n di ox ide is present in water it wi ll a lso react wi th lime. M g.( OI1) 2$ + -iNa ' + 2(0 / - + 2 H20 (426)

- '\

Example 4-7: Single-stage softening A water with the ionic characteristics shown in the
The soda ash formed [Egs. (4-24), (4-25), and (4-26)] will react with calcium non-
bar diagram below is to be softened to the minimum calcium hardness by the lime-soda
carbonate hardness as previou sly shown in Eg. (4-21). As in the lime - soda ash
ash process. Magnesium removal is not deemed necessary.
process, it is necessary to raise pH to 11.0 to precipitate magnesium hydroxide.
An excess of 1.25 meguiv/ L of sodium hydroxide is added for this purpose. I. Calculate the chemical requirements and solids produced in milliequivalents per liter.
2. Draw a bar diagram for the finished water.
NaOH (4-28)
3. For a flow of 25,000 m'/d, calculate the daily chemical requirement and the mass of
solids produced: Assume that the lime used is 90 percent pure and the soda ash is
Stabilization Complete removal of hardness cannot be accomplished by chemical 85 percent pure.
precipitation. Under conditiolls normally prevailing in water-treatment plants,
up to 40 mgjL CaCO) and 10 mg/ L Mg(OHh usually remain in the softened water. to 50 60 80
Precipitation of the supersaturated solution of CaCO } will continue slowly. mequiv/ L
however. resulting in deposits in water lines and storage facilities. It is therefore
necessary to "stabilize " the water by converting the supersaturated CaCO) back CO~
Ca 2 +
I Mg 2 +
I Na+

to the soluble form. Ca,2+ + 2(HCO-. Stabilization can be accomplished by

the addition of anyone of several acids. Using sulfuric acid as an example:
mequiv/ L

I SO~-

2CaCO} + H 2 S0 4 2Ca 2 ' + 2(HC01 f -I- SO/ (4-29)

Mg(OH)2 + Hz SO (4-:l0) SOLUTION

The most common practice. however. is to make the cOllyersion with carbon The following treatment scheme will be used.
CaCO) + CO 2 + H 2 0 Ca 2 + -I- 2(HCO}) - (4-31 ) Lime
Mg(OH)2 + 2CO l Mg 2' + 2 (HCO) (4- 32) Soda ash

This process is .generally called recarbollalioll. Flocculator basin
If the pH has been raised to facilitate the precipitation of magnesium. it will Recarbonation
.... Rapi~ . . . . . . . . . .. ... .
be necessary to neutralize. theexcess..bydroxy.l..ions. PLjQ[. 10. stabilization. This mix
necessitates a two-stage treatment process. Typical reactions are:
l. Calculate chemical requirements using appropriate formulas.
With sulfuric acid
I.OC0 2 + I.OCaO - - l.OCaCO,!
Ca 2 + +'20H~ + H 2 S0 4 Ca2+ -I- SO/ - + '21:-1 2 0 (4-33)
2.5(Ca2+ + 2HCO,) + 2.5CaO - - 5.0CaCO,! + S.OH 2 0
2Na+ + .20H - + H 2 S0 4 2Na + + SO/- -I- 2H 2 () (4-34 )
1.5(Ca2+ + SO/ - ) + 1.5Na 2CO, - - I.SCaCO,! + 1.5(2Na+ + S042-)
With carbon dioxide
Second-stage recarbonation will be required to stabilize the water. Assuming a CaC0 1
Cal f -I- 20H- -I- 2C0 2 CaC03~ + H 2 0 (4-35)
concentration of 40 mg/L in the effluent from the settling basin, 25 mg/L should be
2Na ~ -I- 20H 2 + CO 2 - ---> 2Na + -I- CO/- + H 2 0 (4- 36) converted to reach the equilibrium of 15 mg/L of CaCO,.
05CaCO, + 0.SC0 2 + 0.5H2Sl - - 0.5Ca(HC0 3 h
The pH must be lowered to approximately 9.5 before signiticant stabilization
occurs. Total chemical requirements are:
Lime = 1.0 + 2.5 = 3.5 mequiv/L
Chemical requirement The CJuantity of chemicals to soften wat e r can be calculated Soda ash = 1.5 = 1.5 mequiv/L
using the appropriate formulas from Eqs. (4-17) through (4-36 ). These calcula-
CO 2 = 0.5 mequiv/L
tions arc illustrated in Examples 4-7 and 4-8.

SOLUTION The following Irealment scheme will be used.

So lids produced are

CaC0 3 = 1.0 + 5.0 + 1.5 - 0.8 = 6.7 mequ iv/ L

Lim c . sod" ash
2. T he ba r diagram for the finis hed water is

o 08 18 53 3

Ca 2>

l HCO;
I SO~-

Rapid mix
2. Flocculation
3. Set tling
0.3 0.8 5.3 4. Fir st-stage
3. The equi va lent mass of lime and soda ash is reca rbonation

. 40 + 16 .
Lune = -2-- = 28 mg/ meq ulv
I. Calculate che mical quantities using appropriate formulas.

2m) + 12 + 3(16)
.. 0.6CaCO ) 1
Soda ash = - ..- - - - - - - . - - = 53 mgj mequJ\ 0.6CO , + 0.6CaO
34(Ca' > + 2HCO) - ) + 14CaO 6.8 CaCO ) 1+ 6.8 HP
12 + 2( 16) .
Carbon d iox ide = ---
~ -- = 22 mg! meq ll iv
1. 5(Mg H + 2HCO, - ) + JOCaO
1. 5 Mg(O H ), t+ 3.0CaCO, t
The da ily c hemica l req uirements are: 1.5(Mg H + SO.' - ) + 1. 5CaO + 1.5H , 0
I kg 6
~) (1 /0.9) 28 m g!m equiv x 3.5 meq ll iv/ L x 25 x 10 Ljd x - 6 - = 2722 kg/ d
. 10 mg
1.5( Ca' + S04 + 1.5Na,CO,
. ___ ________ ____ . __ (I / 0 .gS)-53- m g/rnequi V")(" 15-meqoiv/ t- x 23 -x I06T/d-x Tkg/ (Oi;-i;;g--~ -iiiR k-gjd-

22 mg/mequ iv x 0.5 meq uiv/ L x 25 x 10 6 Li d x J kg/ 10 6 m g = 275 kg/ d Excess lime = 1.25 mequivj L

T he m ass of d ry so li ds p rod uced per day is For first-stage recarbo Jl ation_ use CO, to neutralize excess lime.

50 mg/ mequiv x 6.7 meqlliv! L x 25 x lOb Lid x I kgllO" mg = 8375 kg;d 125(Ca' + + 201r) + 125CO , -- 125CaCOd + 1.25H zO

E x ampl e 4-8: T wo-s tage soft ening A water with the ionic characteristics shown below Ass umin g 40 mg/ L CaCO J and IQ mg /L Mg(OH) , remain ing in so lution af~er second-
is to be softened to th e mi n im um possible hardness by the limc - soda-ash - excess-lime stage se ttling_
process. Calcu la te the required chemica l quanti ties in milliequivalent s per liter. Draw a 0.2 Mg(OH) , + OACO,
bar d iagram of the fin ished water.
0.5CaCO) + 0.5eO, + 0. 5 1-1 , 0

06 40 70 80 Total c hemi cal quantities are

Ca 2> Mg1 N,,>
I I Lim e = 0.6 + 3.4 + 10 + 1. 5 + 1.25 = 'US

soi- .Soda ash = 1. 5


I- co, = 1. 25 + 0.4 + OJ = 2.1 5

2. Bar diagram of final water: Mg, = magnesium concentration in the raw water, mg/L
Mgt = magnesium concentration remaining in the fraction of the water
08 10 35
.. receiving first-stage treatment. [As previously stated, practical
C, a 2+
I Mg2+ Na' limits are 10 mg/ L Mg(OH)2 (as CaC0 3 )]
A typical split-treatment system for removing magnesium is shown in Fig.
C05-\ HCO:; SO~- 4-25. The quantity of softe:1ing chemicals saved by this system is illustrated in the
following example.
0.3 3.5 e Soda ash

Softening operations Softening operations consist of several steps and may be
carried out in one or two stages. The operations include mixing of the chemicals
with ' the water, flocculation to aid in precipitate growth, settling of precipitate,
and stabilization. The solids-contact system shown in Fig. 4-23 is often use'd for
softening operations. These systems operate in much the same manner as the
systems for coagulating and ' removing turbidity discussed in Sec. 4-6. Design
criteria, however , are slightly different and are summarized in Table 4-3.
Bypassed flow Qx
Table 4-3 Typical design criteria for softening systems

Selliin g Solids'- Figure 4-25 rIow diagram for softening by split trcatment.
Parameter Mixer Flocculator basin contact ba sin
Example 4-9: Softening by split treatmcnt Use split treatment to soften the water with
Detention time* 5 min 30- 50 min 2- 4 h 1- 4 h ionic strength given in Example 4-S. Assume that a final hardness of less than 100 mg/L
Velocity gradient, s - 1 700 10- 100 NA t is acceptable, provided the magnesium IS less than 45 mg/L. Calculate the chemical
Flow-th rough velocity. I'tis NA o 15- 0.45 0.15- 0.45 NA requirements and draw a bar diagram of the finished water.
Overtlow rate, gal / min / ft' NA NA 0.85 - 1. 7 1 427t
This should be confirmed by pilot-plant analysis for each water. The treatment scheme shown in Fig. 4-25 wi'li b~-useif. -., ., . - - - . ............. ., . ., .. ... .. _. - .... .
. 't Velocit y gradient in mixer and Aocculator compone nt sho uld be approximatel y
the sa me as in flow-through units. J. Calculate the bypass fraction:
t At slurry blanket-clarifier watcr interface. Q = Mg f - Mg,
SOllrce: Adapted from Recommended Standards . [4-44J
x Mg, - Mg,
0.9 - 0.2
Water with high magnesium hardness is often softened by a process called
split treatment. This process bypasses the first-stage softening unit with a part of the = 3.0 - 0.2
incoming water. Excess lime is added to facilitate the removal ofinagnesium in the = 0.25
first stage and, instead of being neutralized thereafter. is used to precipitate the 2. Calculate the quantity of chemicals added to first stage:
calcium hardness in the bypassed water in the second stage. Since no magnesium
06CO, + 0.6CaO
is removed in the bypassed water, the initial magnesium hardness and the allow-
able magnesium hardness in the finished water govern the quantity that Olay be 3.4(Ca'+ + 2HC0 3 - ) + 3.4CaO - - - - - t .SCaCOd + 6.SH,O
bypa ssed: (1.0 - o 25)(1.5)(Mg 2 + + 2HC0 3 - ) + (10 - 0.25)3.0CaO
. -----to I.13Mg(OH),! + 2.25CaC0 3 i
Qx = Mg f - Mgt (4-37)
Mg, - Mgt (1.0 - 0.25)(1.5)(Mg 2+ + SO/ - ) + (1.0 - O.25)1.5CaO
-----t 1.13 Mg(OH), + 1.l3(Ca2+ + SO/ - )
where Qx = fract ion of the total flow bypassed
Mg r = Magnesium concentration in the finished water , 40 50 mg/ L 1.I 3(Ca 2 + + SO/ - ) + 113(Na,C0 3 )
(as CaC0 3 ) usually acceptable -----t I.I3CaCO}! + 1.13(2Na+ _I- S04' - )


Check to make sure extra lime is enough to provide 1.25 mequiv/L: Gas

(0.6 + 3.4)0.25 Air

- -0-.7-5-'--- = 1.33

1.33 > 1.25, so acceptable

.~ ..... -. : .:", --;, ..:.~:- " ".: ::: ~"". '.;.::
For second-stage recarbonation:
O,5CaC0 3 + O,5CO l + 0.5H 2 0
0:75 x 0.2Mg(OHh + 0.30C0 2
Total quantity of chemicals:

Lime = 0.6 + J4 + (1.0 - 0.25)(30 + 1.5)

05(Ca 2+ + 2 HC0 3 -J
015(Mg2+ + 2HC0 3 -

= 7.38 mequiv/ L
I ','


.. ,'

.~ ~ :
' .~.

Soda ash = 1.13 mequiv/ L

CO 2 = 0.30 + 0.5 = 0.80 mequiv/ L
I :(7

')" :
. .

. . ' . ':'.~ .
3. Calculate ionic strength of finished water: .'0

. ,. '.


Ca2+ = 0.8
.. ','
'.: :
Mg2+ = 0.75 A 0.2 (first stage) + 0.25 x 3.0 (in bypass) = 0.9 # "'I'

- ;~.~I' . ' . ; .!-. :::.'" :,~ .. ')

Na+ = 1.0 + 1.13 = 2.13
CO/- = 0.3 .. ~.' :'::::.: :.~'.
:: :.
HCC?3 - = 0.5(conversion "fCaCO,) t- O.15(conversion of Mg(OH),)
+ 0.25 x 1.5 (associated with by passed Mg) = 1.03