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(version 5.1)

QUAL2K

simulating river and

stream water quality

July 2008

Publication No. 08-03-xxx

printed on recycled paper

This report is available on the Department of Ecology home page on the World Wide Web

at http://www.ecy.wa.gov/biblio/04030??.html

For a printed copy of this report, contact:

Department of Ecology Publications Distributions Office

Address: PO Box 47600, Olympia WA 98504-7600

E-mail: ecypub@ecy.wa.gov

Phone: (360) 407-7472

Refer to Publication Number 04-03-010

Any use of product or firm names in this publication is for descriptive purposes only and

does not imply endorsement by the author or the Department of Ecology.

The Department of Ecology is an equal-opportunity agency and does not discriminate on

the basis of race, creed, color, disability, age, religion, national origin, sex, marital

status, disabled veterans status, Vietnam-era veterans status, or sexual orientation.

If you have special accommodation needs or require this document in alternative format,

please contact Joan LeTourneau at 360-407-6764 (voice) or 711 or 1-800-833-6388

(TTY).

QUAL2K

QUAL2Kw

theory and documentation

(version 5.1)

A modeling framework for simulating

river and stream water quality

by

Greg Pelletier and Steve Chapra2

1

Olympia, Washington 98504-7710

1

2

Professor and Louis Berger Chair in Computing and Engineering, Tufts University, Medford, MA.

July 2008

printed on recycled paper

QUAL2K

INTRODUCTION

QUAL2Kw (or Q2K) is a river and stream water quality model that is intended to

represent a modernized version of the QUAL2E (or Q2E) model (Brown and Barnwell

1987). QUAL2Kw is adapted from the QUAL2K model that was originally developed by

Dr. Steven C. Chapra of Tufts University (Chapra and Pelletier, 2003). Q2K is similar to

Q2E in the following respects:

Steady state hydraulics. Non-uniform, steady flow is simulated.

Diel heat budget. The heat budget and temperature are simulated as a function of

meteorology on a diel time scale.

Diel water-quality kinetics. All water quality variables are simulated on a diel

time scale.

Heat and mass inputs. Point and non-point loads and abstractions are simulated.

The QUAL2Kw framework includes the following new elements:

Windows environment. It is programmed in the Windows macro language: Visual

Basic for Applications (VBA). Excel is used as the graphical user interface.

Model segmentation. Q2E segments the system into river reaches comprised of

equally spaced elements. In contrast, Q2K uses unequally-spaced reaches. In addition,

multiple loadings and abstractions can be input to any reach.

Carbonaceous BOD speciation. Q2K uses two forms of carbonaceous BOD to

represent organic carbon. These forms are a slowly oxidizing form (slow CBOD) and

a rapidly oxidizing form (fast CBOD).

Anoxia. Q2K accommodates anoxia by reducing oxidation reactions to zero at

low oxygen levels. In addition, denitrification is modeled as a first-order reaction that

becomes pronounced at low oxygen concentrations.

Sediment-water interactions. Sediment-water fluxes of dissolved oxygen and

nutrients are simulated internally rather than being prescribed. That is, oxygen (SOD)

and nutrient fluxes are simulated as a function of settling particulate organic matter,

reactions within the sediments, and the concentrations of soluble forms in the

overlying waters.

Bottom algae. The model explicitly simulates attached bottom algae. These algae

have variable stoichiometry.

Light extinction. Light extinction is calculated as a function of algae, detritus and

inorganic solids.

pH. Both alkalinity and total inorganic carbon are simulated. The rivers pH is

then simulated based on these two quantities.

Pathogens. A generic pathogen is simulated. Pathogen removal is determined as a

function of temperature, light, and settling.

Hyporheic metabolism. Hyporheic exchange and sediment pore water quality are

simulated, including optional simulation of the metabolism of heterotrophic bacteria

in the hyporheic zone.

Automatic calibration. A genetic algorithm is included to determine the optimum

values for the kinetic rate parameters to maximize the goodness of fit of the model

compared with measured data.

The QUAL2K framework does not include the following elements that are included

in Q2E:

Branching. Q2K presently simulates the main stem of a river. It does not model

branches.

Q2K does not presently include an uncertainty component.

QUAL2K

GETTING STARTED

Installation is required for many water-quality models. This is not the case for

QUAL2Kw because the model is packaged as an Excel Workbook. The program is

written in Excels macro language: Visual Basic for Applications or VBA. An optional

Fortran executable version of the model is also available to run. The Excel Workbooks

worksheets and charts are used to enter data and display results. Consequently, you

merely have to open the Workbook to begin modeling. The following are the

recommended step-by-step instructions on how to obtain your first model run.

Step 1: Unzip the model files to any folder on the hard drive on your PC. When you

extract the zip archive to a drive or folder on your hard drive, a new subfolder in that

drive or folder will be created with the files for QUAL2Kw. For example, if you

unzipped to your C:\ drive, then a subfolder named C:\qual2kw will be created if it does

not exist, and the QUAL2Kw files will be in a subfolder of the qual2kw folder. The

qual2kw5.xls and qual2kw5.exe files may be copied to any working folder on any drive

of your computer. Both files must be present together in the same working folder for the

Fortran executable to run. Copies of .xls file may be given any name. The qual2kw5.exe

may not be re-named if you want to run the Fortran executable version from the .xls file.

Step 2: Open Excel and make sure that your macro security level is set to medium or low

(Figure 1). This can be done using the menu commands: Tools Macro Security.

Make certain that either the Medium or Low radio button is selected.

Figure 1 The Excel Macro Security Level dialogue box. In order to run Q2K, the Medium

level of security should be selected.

Step 3: Open qual2kw5.xls. When you do this, the Macro Security Dialogue Box will be

displayed if you selected medium security in step 3 (Figure 2).

Figure 2 The Excel Macro security dialogue box. In order to run Q2K, the Enable Macros

button must be selected.

QUAL2K

Step 4: Click on either the Run VBA or Run Fortran button (Figure 3). QUAL2K

will begin to execute. Both of these yield identical results except that the Fortran

version runs much faster because it is a compiled executable program. You can follow

the progress of the execution on the status bar that is shown in the bottom left corner

of the worksheet (Figure 4). If the Fortran version is run then a DOS window will

open to show the progress during the integration.

Figure 4 The QUAL2K Status Bar is positioned at the lower left corner of the worksheet. It

allows you to follow the progress of a model run.

If the program runs properly, the Travel Time plot will be displayed. If it does not

work properly, three possibilities exist:

First, you may be using an old version of Microsoft Office. Although Excel is

downwardly compatible for some earlier versions, Q2K will not work with very old

versions.

Second, your computer may not have enough RAM to run the model. The amount of

RAM needed depends on the model application (e.g. number of reaches, calculation time

step, etc.). A minimum RAM of 256 Mb for Windows 98, or 512 Mb with Windows XP is

recommended for small applications, and more is probably needed for larger applications.

Third, you may have made a mistake in implementing the preceding steps. A common

mistake is to make a copy the .xls file in a working folder and forget to also copy the

qual2kw5.exe file to the same working folder (the Fortran executable will not run unless

it is the same working folder as the .xls file)

Occasionally the model may crash. In some cases the crash may result in a Microsoft

Visual Basic error message as shown in Figure 5. If this occurs, click on the End button.

This will terminate the run and bring you back to the Excel Workbook where you can

check for bad input values. If you are proficient in VBA then you may click on the

Debug button to attempt to find out where the program crashed and diagnose the

problem.

10

Step 5: On the QUAL2K Worksheet click on the Open Old File button. Browse to get to

the working directory. You should see that a new file has been created with the name that

was specified in B9. Click on the Cancel button to return to Q2K.

Note that every time that Q2K is run, a data file will be created with the file name

specified in cell B9 on the QUAL2K Worksheet (Figure 3). The program automatically

affixes the extension .q2k to the file name. Since this will overwrite the file, make certain

to change the file name when you perform a new application. A .q2k file may be opened

by clicking on the Open File button on the QUAL2K Worksheet. This feature allows

you the option to save the inputs for many different simulations without having to save

the .xls for every model run.

QUAL2K

11

The model presently simulates the main stem of a river as depicted in Figure 6.

Tributaries are not modeled explicitly, but can be represented as point sources.

Headwater boundary

1

Point source

Point abstraction

Point abstraction

3

4

5

6

Point source

Non-point

source

Non-point

abstraction

7

Point source

Downstream boundary

Flow Balance

A steady-state flow balance is implemented for each model reach (Figure 7)

Qi Qi 1 Qin ,i Qab ,i

(1)

where Qi = outflow from reach i into the downstream reach i + 1 [m3/d], Qi1 = inflow

from the upstream reach i 1 [m3/d], Qin,i is the total inflow into the reach from point and

nonpoint sources [m3/d], and Qab,i is the total outflow from the reach due to point and

nonpoint abstractions [m3/d].

Qin,i

i1

Qi1

Qab,i

Qi

i+1

12

Qin,i

psi

npsi

j 1

j 1

Q ps,i, j Qnps,i, j

(2)

where Qps,i,j is the jth point source inflow to reach i [m3/d], psi = the total number of point

sources to reach i, Qnps,i,j is the jth non-point source inflow to reach i [m3/d], and npsi =

the total number of non-point source inflows to reach i.

The total outflow from abstractions is computed as

Qab,i

pai

j 1

Q pa,i , j

npai

Qnpa,i, j

(3)

j 1

where Qpa,i,j is the jth point abstraction outflow from reach i [m3/d], pai = the total number

of point abstractions from reach i, Qnpa,i,j is the jth non-point abstraction outflow from

reach i [m3/d], and npai = the total number of non-point abstraction flows from reach i.

The non-point sources and abstractions are modeled as line sources. As in Figure 8,

the non-point source or abstraction is demarcated by its starting and ending kilometer

points. Its flow is distributed to or from each reach in a length-weighted fashion.

Qnpt

25%Qnpt 25%Qnpt

start

50%Qnpt

end

Hydraulic Characteristics

QUAL2K

13

Once the outflow for each reach is computed, the depth and velocity are calculated in one

of three ways: weirs, rating curves, and Manning equations. The program decides among

these options in the following manner:

If the weir height is zero and a roughness coefficient is entered (n), the Manning

equation option is implemented.

If neither of the previous conditions are met, Q2K uses rating curves.

Weirs

Figure 9 shows how weirs are represented in Q2K. The symbols are defined as: Hi = the

depth of the reach upstream of the weir [m], Hi+1 = the depth of the reach downstream of

the weir [m], elev2i = the elevation above sea level of the tail end of the upstream reach

[m], elev1i+1 = the elevation above sea level of the head end of the downstream reach [m],

Hw = the height of the weir above elev2i [m], Hd = the drop between the elevation above

sea level of the surface of reach i and reach i+1 [m], Hh = the head above the weir [m], Bi

= the width of reach i [m].

(a) Side

(b) Cross-section

Bi

Hi

Hd

Hw

Hh

Hi

Hw

Hi+1

elev2i

elev1i+1

elev2i

elev1i+1

For a sharp-crested weir where Hh/Hw < 0.4, flow is related to head by (Finnemore

and Franzini 2002)

Qi 1.83Bi H h3 / 2

(4)

where Qi is the outflow from the segment upstream of the weir in m3/s, and Bi and Hh are

in m. Equation (4) can be solved for

Qi

1.83Bi

H h

2/3

(5)

14

Hi Hw Hh

(6)

H d elev 2 i H i elev1i 1 H i 1

(7)

Ac ,i Bi H i

Ui

(8)

Qi

Ac ,i

(9)

Rating Curves

Power equations can be used to relate mean velocity and depth to flow,

U aQ b

(10)

H Q

(11)

where a, b, and are empirical coefficients that are determined from velocity-discharge

and stage-discharge rating curves, respectively. The values of velocity and depth can then

be employed to determine the cross-sectional area and width by

Ac

Q

U

(12)

Ac

H

(13)

The exponents b and typically take on values listed in Table 1. Note that the sum of

b and must be less than or equal to 1. If their sum equals 1, the channel is rectangular.

Table 1 Typical values for the exponents of rating curves used to determine velocity and

depth from flow (Barnwell et al. 1989).

Equation

QUAL2K

Exponent

Typical

15

Range

U aQ b

value

0.43

H Q

0.45

0.40.6

0.30.5

Manning Equation

Each reach is idealized as a trapezoidal channel (Figure 10). Under conditions of steady

flow, the Manning equation can be used to express the relationship between flow and

depth as

S 01 / 2 Ac5 / 3

n P2/3

(14)

where Q = flow [m3/s]3, S0 = bottom slope [m/m], n = the Manning roughness coefficient,

Ac = the cross-sectional area [m2], and P = the wetted perimeter [m].

S0

1

H

ss2

ss1

B0

Q, U

Ac B0 0.5( s s1 s s 2 ) H H

(15)

where B0 = bottom width [m], ss1 and ss2 = the two side slopes as shown in Figure 10

[m/m], and H = reach depth [m].

The wetted perimeter is computed as

P B0 H s s21 1 H s s22 1

(16)

Notice that time is measured in seconds in this and other formulas used to characterize hydraulics. This is

how the computations are implemented within Q2K. However, once the hydraulic characteristics are

determined they are converted to day units to be compatible with other computations.

16

After substituting Eqs. (15) and (16), Eq. (14) can be solved iteratively for depth

(Chapra and Canale 2002),

(Qn) 3 / 5 B0 H k 1 s s21 1 H k 1 s s22 1

Hk

S 3 / 10 B0 0.5( s s1 s s 2 ) H k 1

2/5

(17)

employed. The method is terminated when the estimated error falls below a specified

value of 0.001%. The estimated error is calculated as

a

H k 1 H k

100%

H k 1

(18)

The cross-sectional area can be determined with Eq. (15) and the velocity can then be

determined from the continuity equation,

U

Q

Ac

(19)

B

Ac

H

(20)

Table 2 The Manning roughness coefficient for various open channel surfaces (from Chow

et al. 1988).

MATERIAL

Man-made channels

Concrete

Gravel bottom with sides:

concrete

mortared stone

riprap

Natural stream channels

Clean, straight

Clean, winding and some weeds

Weeds and pools, winding

Mountain streams with boulders

Heavy brush, timber

n

0.012

0.020

0.023

0.033

0.025-0.04

0.03-0.05

0.05

0.04-0.10

0.05-0.20

Mannings n typically varies with flow and depth (Gordon et al. 1992). As the depth

decreases at low flow, the relative roughness increases. Typical published values of

Mannings n, which range from about 0.015 for smooth channels to about 0.15 for rough

natural channels, are representative of conditions when the flow is at the bankfull

QUAL2K

17

capacity (Rosgen, 1996). Critical conditions of depth for evaluating water quality are

generally much less than bankfull depth, and the relative roughness may be much higher.

Waterfalls

In Section , the drop of water over a weir was computed. This value is needed in order to

compute the enhanced reaeration that occurs in such cases. In addition to weirs, such

drops can also occur at waterfalls (Figure 11).

Hi

Hd

elev2i

Hi+1

elev1i+1

Figure 11 Waterfall.

QUAL2K computes such drops for cases where the elevation above sea level drops

abruptly at the boundary between two reaches. For both the rating curve and the Manning

equation options, the model uses Eq. (7) for this purpose. It should be noted that the drop

is only calculated when the elevation above sea level at the downstream end of a reach is

greater than at the beginning of the next downstream reach; that is, elev2i > elev1i+1.

Travel Time

The residence time of each reach is computed as

k

Vk

Qk

(21)

where k = the residence time of the kth reach [d], Vk = the volume of the kth reach [m3] =

Ac,kxk, and xk = the length of the kth reach [m]. These times are then accumulated to

determine the travel time from the headwater to the downstream end of reach i,

i

t t ,i k

k 1

(22)

18

Longitudinal Dispersion

Two options are used to determine the longitudinal dispersion for a boundary between

two reaches. First, the user can simply enter estimated values on the Reach

Worksheet. If the user does not enter values, a formula is employed to internally

compute dispersion based on the channels hydraulics (Fischer et al. 1979),

E p ,i 0.011

U i2 Bi2

(23)

H iU i*

where Ep,i = the longitudinal dispersion between reaches i and i + 1 [m2/s], Ui = velocity

[m/s], Bi = width [m], Hi = mean depth [m], and Ui* = shear velocity [m/s], which is

related to more fundamental characteristics by

U i*

(24)

gH i S i

[dimensionless].

After computing or prescribing Ep,i, the numerical dispersion is computed as

E n ,i

U i xi

2

(25)

The model dispersion Ei (i.e., the value used in the model calculations) is then computed

as follows:

If En,i > Ep,i, the model dispersion is set to zero.

For the latter case, the resulting dispersion will be greater than the physical dispersion.

Thus, dispersive mixing will be higher than reality. It should be noted that for most

steady-state rivers, the impact of this overestimation on concentration gradients will be

negligible. If the discrepancy is significant, the only alternative is to make reach lengths

smaller so that the numerical dispersion becomes smaller than the physical dispersion.

QUAL2K

19

TEMPERATURE MODEL

As in Figure 12, the heat balance takes into account heat transfers from adjacent reaches,

loads, abstractions, the atmosphere, and the sediments. A heat balance can be written for

reach i as

Qab,i

dTi Qi 1

Q

E'

E'

Ti 1 i Ti

Ti i 1 Ti 1 Ti i Ti 1 Ti

dt

Vi

Vi

Vi

Vi

Vi

J h ,i

m3

w C pwVi 10 6 cm 3 w C pw H i

W h ,i

J s ,i

m

100 cm w C pw H i

100 cm

(26)

where Ti = temperature in reach i [oC], t = time [d], Ei = the bulk dispersion coefficient

between reaches i and i + 1 [m3/d], Wh,i = the net heat load from point and non-point

sources into reach i [cal/d], w = the density of water [g/cm3], Cpw = the specific heat of

water [cal/(g oC)], Jh,i = the air-water heat flux [cal/(cm2 d)], and Js,i = the sediment-water

heat flux [cal/(cm2 d)].

heat load

inflow

dispersion

atmospheric

transfer

heat abstraction

outflow

dispersion

sediment-water

transfer

sediment

E i'

E i Ac ,i

xi xi 1 / 2

(27)

Note that two types of boundary condition are used at the rivers downstream terminus:

(1) a zero dispersion condition (natural boundary condition) and (2) a prescribed

20

these options is made on the Headwater Worksheet.

The net heat load from sources is computed as

psi

j 1

Wh ,i C p

Q ps ,i , j T psi , j

npsi

j 1

Qnps,i, j Tnpsi, j

(28)

where Tps,i,j is the jth point source temperature for reach i [oC], and Tnps,i,j is the jth nonpoint source temperature for reach i [oC].

As depicted in Figure 13, surface heat exchange is modeled as a combination of five

processes:

J h I (0) J an J br J c J e

(29)

where I(0) = net solar shortwave radiation at the water surface, Jan = net atmospheric

longwave radiation, Jbr = longwave back radiation from the water, Jc = conduction, and

Je = evaporation. All fluxes are expressed as cal/cm2/d.

non-radiation terms

radiation terms

air-water

interface

solar

shortwave

radiation

atmospheric

longwave

radiation

water

longwave

radiation

conduction

and

convection

evaporation

and

condensation

water-dependent terms

Solar Radiation

The model computes the amount of solar radiation entering the water at a particular

latitude (Lat) and longitude (Llm) on the earths surface. This quantity is a function of the

QUAL2K

21

transmission, cloud cover, reflection, and shade,

I ( 0)

I0

at

ac

(1 R s )

reflection

radiation attenuation attenuation

(30)

(1 S f )

shading

where I(0) = solar radiation at the water surface [cal/cm2/d], I0 = extraterrestrial radiation

(i.e., at the top of the earths atmosphere) [cal/cm2/d], at = atmospheric attenuation, ac =

cloud attenuation, Rs = albedo (fraction reflected), and Sf = effective shade (fraction

blocked by vegetation and topography).

Extraterrestrial radiation. The extraterrestrial radiation is computed as (TVA 1972)

I0

W0

r2

sin

(31)

where W0 = the solar constant [1367 W/m2 or 2823 cal/cm2/d], r = normalized radius of

the earths orbit (i.e., the ratio of actual earth-sun distance to mean earth-sun distance),

and = the suns altitude [radians], which can be computed as

sin sin sin Lat cos cos Lat cos

(32)

where = solar declination [radians], Lat = local latitude [radians], and = the local hour

angle of the sun [radians].

The normalized radius can be estimated as

2

(186 Dy )

365

r 1 0.017 cos

(33)

The solar declination can be estimated as

22

23.45

cos

(172 Dy )

180

365

(34)

trueSolarTime

180

4

180

(35)

where:

trueSolarTime localTime eqtime 4 Llm 60 timezone

(36)

where trueSolarTime is the solar time determined from the actual position of the sun in

the sky [minutes], localTime is the local time in minutes (local standard time), Llm is the

local longitude (positive decimal degrees for the western hemisphere), and timezone is

the local time zone in hours relative to Greenwich Mean Time (e.g. 8 hours for Pacific

Standard Time; the local time zone is selected on the QUAL2K Worksheet). The value

of eqtime represents the difference between true solar time and mean solar time in

minutes of time.

QUAL2K calculates the suns altitude and eqtime, as well as the times of sunrise and

sunset using the Meeus (1999) algorithms as implemented by NOAAs Surface Radiation

Research Branch (www.srrb.noaa.gov/highlights/sunrise/azel.html). The NOAA method

for solar position that is used in QUAL2K also includes a correction for the effect of

atmospheric refraction.

The photoperiod f [hours] is computed as

f t ss t sr

(37)

where tss = time of sunset [hours] and tsr = time of sunrise [hours].

Atmospheric attenuation. Various methods have been published to estimate the fraction

of the atmospheric attenuation from a clear sky (at). Two alternative methods are

available in QUAL2K to estimate at:

Bras (1990)

QUAL2K

23

Note that the solar radiation model is selected on the Light and Heat Worksheet of

QUAL2K.

The Bras (1990) method computes at as:

at e

n fac a1m

(38)

where nfac is an atmospheric turbidity factor that varies from approximately 2 for clear

skies to 4 or 5 for smoggy urban areas. The molecular scattering coefficient (a1) is

calculated as

a1 0.128 0.054 log10 m

(39)

m

1

sin 0.15( d 3.885) 1.253

(40)

The Ryan and Stolzenbach (1972) model computes at from ground surface elevation

and solar altitude as:

at atc

288

5.256

(41)

0.8), and elev is the ground surface elevation in meters.

Direct measurements of solar radiation are available at some locations. For example,

NOAAs Integrated Surface Irradiance Study (ISIS) has data from various stations across

the United States (http://www.atdd.noaa.gov/isis.htm). The selection of either the Bras or

Ryan-Stolzenbach solar radiation model and the appropriate atmospheric turbidity factor

or atmospheric transmission coefficient for a particular application should ideally be

guided by a comparison of predicted solar radiation with measured values at a reference

location.

Cloud Attenuation. Attenuation of solar radiation due to cloud cover is computed with

24

a c 1 0.65C L2

(42)

Reflectivity. Reflectivity is calculated as

Rs A d

(43)

Table 3 Coefficients used to calculate reflectivity based on cloud cover.

Cloudiness

CL

Coefficients

Clear

0

A

1.18

B

0.77

Scattered

0.1-0.5

A

B

2.20

0.97

Broken

0.5-0.9

A

0.95

B

0.75

Overcast

1.0

A

B

0.35

0.45

Shade. Shade is an input variable for the QUAL2K model. Shade is defined as the

fraction of potential solar radiation that is blocked by topography and vegetation. An

Excel/VBA program named Shade.xls is available from the Washington Department of

Ecology to estimate shade from topography and riparian vegetation (Ecology 2003).

Input values of integrated hourly estimates of shade for each reach are put into the Shade

Worksheet of QUAL2K.

The downward flux of longwave radiation from the atmosphere is one of the largest

terms in the surface heat balance. This flux can be calculated using the StefanBoltzmann law

J an Tair 273

sky

1 R L

SKOPi

(44)

temperature [oC], sky = effective emissivity of the atmosphere [dimensionless], and RL =

longwave reflection coefficient [dimensionless]. Emissivity is the ratio of the longwave

radiation from an object compared with the radiation from a perfect emitter at the same

temperature. The reflection coefficient is generally small and in typically assumed to

equal 0.03. The term SKOPi is the sky opening fraction (Rutherford et al, 1997).

QUAL2K

25

The atmospheric longwave radiation model is selected on the Light and Heat

Worksheet of QUAL2K. Three alternative methods are available for use in QUAL2K to

represent the effective emissivity (sky):

Brutsaert (1982). The Brutsaert equation is physically-based instead of empirically

derived and has been shown to yield satisfactory results over a wide range of atmospheric

conditions of air temperature and humidity at intermediate latitudes for conditions above

freezing (Brutsaert, 1982).

1.333224eair

clear k brut

Ta

1/ 7

where eair is the air vapor pressure [mm Hg], and Ta is the air temperature in K. The

factor of 1.333224 converts the vapor pressure from mm Hg to millibars. Brutsaert

(1982) recommended a default value of 1.24 for kbrut based on typical values for various

physical constants. Several articles have since been published with various recommended

values for kbrut considering the uncertainty and calibration to observations of downwelling

longwave radiation. Crawford and Duchon (1999) suggested a range for kbrut from 1.28 in

January to 1.16 in July with sinusoidal seasonal variaton. Sridhar and Elliot (2002)

recommended an average value for kbrut of 1.31 based on calibration to observed

longwave radiation data in Oklahoma, with values ranging from 1.30 to 1.32 between

four sites. Culf and Gash (1993) also recommended a value of 1.31 instead of 1.24 during

dry seasons in Niger, and a reduced value during wet seasons. QUAL2Kw allows the user

to specify the input value of kbrut and suggests a default value of 1.24.

The air vapor pressure [in mm Hg] is computed as (Raudkivi 1979):

17.27 Td

e air 4.596e

237.3 Td

(45)

Brunt (1932). Brunts equation is an empirical model that has been commonly used in

water-quality models (Thomann and Mueller 1987),

clear Aa Ab eair

where Aa and Ab are empirical coefficients. Values of Aa have been reported to range from

about 0.5 to 0.7 and values of Ab have been reported to range from about 0.031 to 0.076

mmHg0.5 for a wide range of atmospheric conditions. QUAL2K uses a default mid-range

value of Aa = 0.6 with Ab = 0.031 mmHg-0.5 if the Brunt method is selected on the Light

and Heat Worksheet.

26

Koberg (1964). Koberg (1964) reported that the Aa in Brunts formula depends on both

air temperature and the ratio of the incident solar radiation to the clear-sky radiation (Rsc).

As in Figure 14, he presented a series of curves indicating that Aa increases with Tair and

decreases with Rsc with Ab held constant at 0.0263 millibars0.5 (about 0.031 mmHg0.5).

The following polynomial is used in Q2K to provide a continuous approximation of

Kobergs curves.

2

Aa a k Tair

bk Tair c k

where

3

2

a k 0.00076437 R sc

0.00121134 R sc

0.00073087 R sc 0.0001106

3

2

bk 0.12796842 R sc

0.2204455 R sc

0.13397992 R sc 0.02586655

3

2

c k 3.25272249 R sc

5.65909609 R sc

3.43402413R sc 1.43052757

The fit of this polynomial to points sampled from Kobergs curves are depicted in Figure

14. Note that an upper limit of 0.735 is prescribed for Aa.

Brunts equation for longwave radiation

0.8

0.50

0.65

0.75

0.80

0.85

0.7

0.6

0.90

0.95

0.5

1.00

0.4

0.3

-4

12

16

20

24

28

32

Figure 14 The points are sampled from Kobergs family of curves for determining the

value of the Aa constant in Brunts equation for atmospheric longwave radiation

(Koberg, 1964). The lines are the functional representation used in Q2K.

increased water vapor content. High cirrus clouds may have a negligible effect on

atmospheric emissivity, but lower stratus and cumulus clouds may have a significant

QUAL2K

27

effect. The Koberg method accounts for the effect of clouds on the emissivity of

longwave radiation in the determination of the Aa coefficient.

Idso (1981). Two equations were proposed by Idso (1981) as summarized by Hatfield et

al. (1983):

Idso 1:

clear 0.179(1.333224eair )1 / 7 exp(350 / Ta )

Idso 2:

clear 0.70 5.95 X 10 5 (1.333224eair ) exp(1500 / Ta )

Idso and Jackson (1969). The following equation was proposed by Idso and Jackson

(1969) (Ta is air temperature in degrees K):

clear 1 0.261exp(0.000777(Ta 273.15) 2 )

Swinbank (1963). The following equation was proposed by Swinbank (1963):

clear 0.0000092Ta 2

All methods except for Koberg (1964) determine emissivity of a clear sky and do not

account for the effect of clouds. Therefore, the effective atmospheric emissivity for

cloudy skies (sky) is estimated from the clear sky emissivity for all methods except for

Koberg (1964) by using a nonlinear function of the fractional cloud cover (CL) of the

form (TVA, 1972):

sky clear (1 0.17C L2 )

(46)

The selection of the longwave model for a particular application should ideally be

guided by a comparison of predicted results with measured values at a reference location.

However, direct measurements are rarely collected. The Brutsaert method is

recommended to represent a wide range of atmospheric conditions.

28

The back radiation from the water surface is represented by the Stefan-Boltzmann law,

J br T 273

SKOPi

(47)

where = emissivity of water (= 0.97) and T = the water temperature [oC]. The term

SKOPi is the sky opening fraction (Rutherford et al, 1997).

Conduction is the transfer of heat from molecule to molecule when matter of different

temperatures are brought into contact. Convection is heat transfer that occurs due to mass

movement of fluids. Both can occur at the air-water interface and can be described by,

J c c1 f U w Ts Tair

(48)

where c1 = Bowen's coefficient (= 0.47 mmHg/oC). The term, f(Uw), defines the

dependence of the transfer on wind velocity over the water surface where Uw is the wind

speed measured a fixed distance above the water surface.

Many relationships exist to define the wind dependence. Bras (1990), Edinger et al.

(1974), and Shanahan (1984) provide reviews of various methods. Some researchers have

proposed that conduction/convection and evaporation are negligible in the absence of

wind (e.g. Marciano and Harbeck, 1952), which is consistent with the assumption that

only molecular processes contribute to the transfer of mass and heat without wind

(Edinger et al. 1974). Others have shown that significant conduction/convection and

evaporation can occur in the absence of wind (e.g. Brady Graves and Geyer 1969,

Harbeck 1962, Ryan and Harleman 1971, Helfrich et al. 1982, and Adams et al. 1987).

This latter opinion has gained favor (Edinger et al. 1974), especially for waterbodies that

exhibit water temperatures that are greater than the air temperature.

Brady, Graves, and Geyer (1969) pointed out that if the water surface temperature is

warmer than the air temperature, then the air adjacent to the water surface would tend to

become both warmer and more moist than that above it, thereby (due to both of these

factors) becoming less dense. The resulting vertical convective air currents might be

expected to achieve much higher rates of heat and mass transfer from the water surface

[even in the absence of wind] than would be possible by molecular diffusion alone

(Edinger et al. 1974). Water temperatures in natural waterbodies are frequently greater

than the air temperature, especially at night.

QUAL2K

29

Edinger et al. (1974) recommend that the relationship that was proposed by Brady,

Graves and Geyer (1969) based on data from cooling ponds, could be representative of

most environmental conditions. Shanahan (1984) recommends that the Lake Hefner

equation (Marciano and Harbeck, 1952) is appropriate for natural waters in which the

water temperature is less than the air temperature. Shanahan also recommends that the

Ryan and Harleman (1971) equation as recalibrated by Helfrich et al. (1982) is best suited

for waterbodies that experience water temperatures that are greater than the air

temperature. Adams et al. (1987) revisited the Ryan and Harleman and Helfrich et al.

models and proposed another recalibration using additional data for waterbodies that

exhibit water temperatures that are greater than the air temperature.

Three options are available on the Light and Heat Worksheet in QUAL2K to

calculate f(Uw):

Brady, Graves, and Geyer (1969)

f (U w ) 19.0 0.95U w2

Adams et al. (1987)

Adams et al. (1987) updated the work of Ryan and Harleman (1971) and Helfrich et al.

(1982) to derive an empirical model of the wind speed function for heated waters that

accounts for the enhancement of convection currents when the virtual temperature

difference between the water and air (v in degrees F) is greater than zero. Two wind

functions reported by Adams et al., also known as the East Mesa method, are

implemented in QUAL2K (wind speed in these equations is at a height of 2m).

convection currents caused by virtual temperature differences between water and

air, and the Harbeck (1962) equation is used to represent the contribution to

conduction/convection and evaporation that is not due to convection currents

caused by high virtual water temperature.

0.05

2

f (U w ) 0.271 ( 22.4 v1 / 3 ) 2 ( 24.2 Aacres

,iU w, mph )

where Uw,mph is wind speed in mph and Aacres,i is surface area of reach i in acres.

The constant 0.271 converts the original units of BTU ft2 day1 mmHg1 to cal

cm2 day1 mmHg1.

differences with the Marciano and Harbeck (1952) equation for the contribution to

conduction/convection and evaporation that is not due to the high virtual water

temperature

30

Virtual temperature is defined as the temperature of dry air that has the same density

as air under the in situ conditions of humidity. The virtual temperature difference between

the water and air ( v in F) accounts for the buoyancy of the moist air above a heated

water surface. The virtual temperature difference is estimated from water temperature

(Tw,f in F), air temperature (Tair,f in F), vapor pressure of water and air (es and eair in

mmHg), and the atmospheric pressure (patm is estimated as standard atmospheric pressure

of 760 mmHg in QUAL2K):

Tw, f 460

Tair , f 460

v

460

460

1 0.378e s / p atm

1 0.378e air / p atm

(49)

estimating conduction/convection and evaporation. QUAL2K internally adjusts the wind

speed to the correct height for the wind function that is selected on the Light and Heat

Worksheet. The input values for wind speed on the Wind Speed Worksheet in

QUAL2K are assumed to be representative of conditions at a height of 7 meters above

the water surface. To convert wind speed measurements (Uw,z in m/s) taken at any height

(zw in meters) to the equivalent conditions at a height of z = 7 m for input to the Wind

Speed Worksheet of QUAL2K, the exponential wind law equation may be used (TVA,

1972):

z

z

w

0.15

U w U wz

(50)

For example, if wind speed data were collected from a height of 2 m, then the wind

speed at 7 m for input to the Wind Speed Worksheet of QUAL2K would be estimated

by multiplying the measured wind speed by a factor of 1.2.

The heat loss due to evaporation can be represented by Daltons law,

J e f (U w )(e s e air )

(51)

QUAL2K

31

where es = the saturation vapor pressure at the water surface [mmHg], and eair = the air

vapor pressure [mmHg]. The saturation vapor pressure is computed as

17.27T

(52)

A heat balance for bottom sediment underlying a water reach i can be written as

dT2 ,i

dt

J s ,i J hyp ,i

s C ps H 2,i

(53)

where T2,i = the temperature of the bottom sediment below reach i [oC], Js,i = the

sediment-water conduction heat flux [cal/(cm2 d)], Jhyp,i is the heat flux between the water

and sediment due to hyporheic flow exchange, s = the density of the sediments [g/cm3],

Cps = the specific heat of the sediments [cal/(g oC)], and H2,i = the effective thickness of

the sediment layer [cm]. The quantity s C ps may be estimated as s /s, where s is

the thermal conductivity [cal/(s cm C)] and s is the thermal diffusivity [cm2/s]. The

values of H2,i, s , and s are inputs to the Reach sheet of QUAL2Kw.

The conduction heat flux from the sediments to the water can be computed as

J s ,i

86400 s

T2,i T1,i

H 2 ,i / 2

(54)

where the thermal conductivity s = s s C ps and the constant of 86400 converts units

of cal/cm2/s to cal/cm2/d.

The thermal properties of some natural sediments along with its components are

summarized in Table 4. Note that soft, gelatinous sediments found in the deposition zones

of lakes are very porous and approach the values for water. Some very slow, impounded

rivers may approach such a state. However, rivers tend to have coarser sediments with

significant fractions of sands, gravels and stones. Upland streams can have bottoms that

are dominated by boulders and rock substrates.

Inspection of the component properties of Table 4 suggests that the presence of solid

material in stream sediments leads to a higher coefficient of thermal diffusivity than that

32

for water or porous lake sediments. In Q2K, we suggest a default value of 0.0064 cm2/s

for this quantity.

QUAL2K

33

Table 4 Thermal properties for natural sediments and the materials that comprise natural

sediments.

In addition, specific heat tends to decrease with density. Thus, the product of these

two quantities tends to be more constant than the multiplicands. Nevertheless, it appears

that the presence of solid material in stream sediments leads to a lower product than that

for water or gelatinous lake sediments. In Q2K, we suggest a default value of 1.6 W/(m

C) for the thermal conductivity.

A sediment thickness of 10 cm is recommended in the absence of significant

hyporheic exchange in order to capture the effect of the sediments on the diel heat budget

for the water (Appendix C). If hyporheic flow exchange is significant, then the effective

thickness of the hyporheic zone of rapid transient storage may typically range from about

20 to 300% of the stream depth (Harvey and Wagner, 2000; Gooseff et al., 2003), with

higher relative values in smaller streams. The residence time of materials in the transient

scale hyporheic zone is typically on the order of 0.01 to 10 days (Poole and Berman,

2001).

34

The transient storage zone is the location of exchange of main channel flow with

subsurface hyporheic flow and surface water dead zones. The hyporheic zone is the layer

of saturated sediment that is adjacent to and underneath the stream. The hyporheic zone

is hydraulically connected to the stream, and stream flow continually exchanges in and

out of the hyporheic zone. The hydraulic characteristics such as size and exchange rates

between the water column and the transient storage or hyporheic zone can be estimated

by fitting an advection-dispersion-transient storage zone model similar to that of Bencala

and Walters (1983). An efficient method for estimating the parameters of the hyporheic

zone volume and exchange rate is provided by Hart (1995).

Significant amounts of flow exchange can occur depending on geomorphic controls.

Kasahara and Wondzell (2003) report flow exchange ranging from about 0.6-5% of the

total surface flow per 100 meter in fifth-order streams, up to 76 to >100% of the total

surface flow per 100 meter in second-order streams. Fernald et al. (2001) reported >72%

of the surface flow of the eighth-order Willamette River exchanged with the transient

storage and hyporheic zones with a thickness on the order of 20-30% of the stream depth

and residence times of 0.2-30 hour over a 26 km reach. In general, smaller streams

usually have higher proportions of surface flow in and out of the hyporheic zone

compared with larger streams.

The heat flux from hyporheic exchange of water between the stream and the

hyporheic sediment zone is computed as

J hyp ,i

'

Ehyp

,i C p

Asf ,i

2 ,i

100 cm

T1,i

(55)

'

where E hyp ,i is the bulk hyporheic exchange flow in reach i [m3/day], and Asf,i is the

surface area of the hyporheic zone in reach i (m2). The hyporheic exchange flow is an

input to the Reach sheet of Q2K, and the surface area is computed from reach length and

channel width also based on inputs to the Reach sheet.

QUAL2K

35

CONSTITUENT MODEL

Constituents and General Mass Balance

The model constituents are listed in Table 5. The constituents in the water column are

indicated by either the subscript 1 or no subscript, and in the hyporheic pore water zone

are indicated by the subscript 2 except for attached bottom algae in the water column

(ab INb, IPb) and heterotrophic bacteria in the hyporheic sediment zone (ah).

Table 5 Model state variables

Variable

Conductivity

Inorganic suspended solids

Dissolved oxygen

Slow-reacting CBOD

Fast-reacting CBOD

Organic nitrogen

Ammonia nitrogen

Nitrate nitrogen

Organic phosphorus

Inorganic phosphorus

Phytoplankton

Detritus

Pathogen

Generic constituent

Alkalinity

Total inorganic carbon

Bottom algae (ab in the surface water layer), biofilm

of attached heterotrophic bacteria (ah in the

hyporheic sediment zone for the Level 2 option)

Bottom algae nitrogen

Bottom algae phosphorus

Symbol

Units*

s1, s2

mi,1, mi,2

o1, o2

cs,1, cs,2

cf,1, cf,2

no,1, no,2

na,1, na,2

nn,1, nn,2

po,1, po,2

pi,1, pi,2

ap,1, ap,2

mo,1, mo,2

x1, x2

gen1, gen2

Alk1, Alk2

cT,1, cT,2

ab,ah

mhos

mgD/L

mgO2/L

mg O2/L

mg O2/L

gN/L

gN/L

gN/L

gP/L

gP/L

gA/L

mgD/L

cfu/100 mL

user defined

mgCaCO3/L

mole/L

gD/m2

INb

IPb

mgN/m2

mgP/m2

* mg/L g/m3

optional in Q2K. Three options are provided:

hyporheic pore water, and water quality kinetics in the hyporheic pore water will

not be simulated.

Level 1: simulation of zero-order or first-order oxidation of fast-reacting CBOD

with attenuation from CBOD and dissolved oxygen in the hyporheic sediment

zone.

Level 2: simulation of heterotrophic bacteria biofilm growth (zero-order or firstorder), respiration, and death with attenuation of growth from CBOD, dissolved

oxygen, ammonia, nitrate, and inorganic phosphorus in the hyporheic pore water

zone.

For all but the bottom algae variables, a general mass balance for a constituent in the

water column of a reach is written as (Figure 15)

'

E hyp

Qab ,i

dci Qi 1

Qi

Ei'1

Ei'

Wi

ci 1 ci

ci

ci 1 ci ci1 ci S i ,i c2,i ci

dt

Vi

Vi

Vi

Vi

Vi

Vi

Vi

(56)

where Wi = the external loading of the constituent to reach i [g/d or mg/d], and Si =

sources and sinks of the constituent due to reactions and mass transfer mechanisms

[g/m3/d or mg/m3/d]. Exchange of mass between the surface water and the hyporheic

'

sediment zone is represented by the bulk hyporheic exchange flow in reach i [ E hyp ,i in

m3/day] and the difference in concentration in the surface water (ci) and in the hyporheic

sediment zone (c2,i).

mass load

atmospheric

transfer

inflow

mass abstraction

outflow

dispersion

bottom algae

dispersion

sediments

For all but the heterotrophic bacteria biofilm, the general mass balance for a

constituent concentration in the hyporheic sediment zone of a reach (c2,i) is written as

dc 2,i

dt

S 2 ,i

'

E hyp

,i

V 2 ,i

c 2 ,i

(57)

where S2,i = sources and sinks of the constituent in the hyporheic zone due to

reactions, V2,i = s ,i Ast ,i H 2,i / 100 = volume of pore water in the hyporheic sediment

zone [m3], s ,i is the porosity of the hyporheic sediment zone [dimension less number

between 0 and 1], Ast,i = the surface area of the reach [m2], and H2,i = the thickness of the

38

hyporheic zone [cm]. Porosity is defined as the fraction of the total volume of sediment

that is in the liquid phase and is interconnected (Chapra, 1997).

The external load is computed as

psi

npsi

j 1

j 1

(58)

where cps,i,j is the jth point source concentration for reach i [mg/L or g/L], and cnps,i,j is the

jth non-point source concentration for reach i [mg/L or g/L].

For bottom algae, the transport and loading terms are omitted,

dab , i

dt

Sb,i

(59)

dIN b

S bN ,i

dt

(60)

dIPb

S bP ,i

dt

(61)

where Sb,i = sources and sinks of bottom algae biomass due to reactions [gD/m2/d], SbN,i =

sources and sinks of bottom algae nitrogen due to reactions [mgN/m2/d], and SbP,i =

sources and sinks of bottom algae phosphorus due to reactions [mgP/m2/d].

For heterotrophic bacteria in the hyporheic sediment zone (Level 2 option), the

transport and loading terms are omitted,

dah ,i

S ah ,i

dt

(62)

where Sah,i = sources and sinks of heterotrophic bacteria in the hyporheic sediment zone

due to reactions [gD/m2/d].

Settled inorganic suspended solids, phytoplankton, and detritus are assumed to be

deposited from the water column layer to the sediment diagenesis zone and do not enter

the hyporheic pore water. The rationale for this assumption is that hyporheic exchange

typically does not occur in depositional areas of fine sediment. The sediment diagenesis

sub-model accounts for anaerobic metabolism of settled material in the sediment. The

hyporheic sub-model accounts for aerobic metabolism of heterotrophic bacteria in the

hyporheic zone. Suspended materials are transported to the hyporheic pore water for the

Level 1 and Level 2 simulation options of hyporheic metabolism.

QUAL2K

39

The sources and sinks for the state variables are depicted in Figure 16 (note that the

internal levels of nitrogen and phosphorus in the bottom algae are not depicted). The

mathematical representation of these processes are presented in the following sections.

re

rda

ds

mo

rod

cs

ox

cT

cf

se

no

na

se

sod

cf

X

s

cT

rna

cT

ox

s

nn

mi

dn

Alk

se

cT

rpa

s

po

IN

pi

s

se

IP

u

e

o

cT

Figure 16 Model kinetics and mass transfer processes. The state variables are defined in

Table 5. Kinetic processes are dissolution (ds), hydrolysis (h), oxidation (ox),

nitrification (n), denitrification (dn), photosynthesis (p), respiration (r), excretion

(e), death (d), respiration/excretion (rx). Mass transfer processes are reaeration

(re), settling (s), sediment oxygen demand (SOD), sediment exchange (se), and

sediment inorganic carbon flux (cf).

Reaction Fundamentals

Biochemical Reactions

The following chemical equations are used to represent the major biochemical

reactions that take place in the model (Stumm and Morgan 1996):

Plant Photosynthesis and Respiration:

Ammonium as substrate:

2

106CO 2 16 NH

108H 2 O

4 HPO 4

P

C106 H 263 O110 N 16 P1 107O 2 14 H

(63)

40

Nitrate as substrate:

106CO 2 16 NO 3

HPO 2

122H 2 O + 18H +

4

P

C106 H 263 O110 N16 P1 138O 2

(64)

Nitrification:

NH 4 2O 2 NO 3 H 2 O 2H

(65)

Denitrification:

5CH 2 O 4NO 3 4H 5CO 2 2N 2 7H 2 O

(66)

Note that a number of additional reactions are used in the model such as those involved

with simulating pH and unionized ammonia. These will be outlined when these topics

are discussed later in this document.

The model requires that the stoichiometry of organic matter (i.e., phytoplankton and

detritus) be specified by the user. The following representation is suggested as a first

approximation (Redfield et al. 1963, Chapra 1997),

100 gD : 40 gC : 7200 mgN :1000 mgP :1000 mgA

(67)

where gX = mass of element X [g] and mgY = mass of element Y [mg]. The terms D, C,

N, P, and A refer to dry weight, carbon, nitrogen, phosphorus, and chlorophyll a,

respectively. It should be noted that chlorophyll a is the most variable of these quantities

with a range of approximately 500-2000 mgA (Laws and Chalup 1990, Chapra 1997).

These values are then combined to determine stoichiometric ratios as in

rxy

gX

gY

(68)

For example, the amount of detritus (in dry weight) that is released due to the death of 1

mgA of phytoplankton can be computed as

rda

100 gD

gD

0.1

1000 mgA

mgA

QUAL2K

41

The model requires that the rates of oxygen generation and consumption be prescribed. If

ammonia is the substrate, the following ratio (based on Eq. 60) can be used to determine

the grams of oxygen generated for each gram of plant matter that is produced through

photosynthesis.

roca

gO 2

2.69

106 moleC(12 gC/moleC)

gC

(69)

If nitrate is the substrate, the following ratio (based on Eq. 61) applies

rocn

gO 2

3.47

106 moleC(12 gC/moleC)

gC

(70)

Note that Eq. (60) is also used for the stoichiometry of the amount of oxygen

consumed for plant respiration.

For nitrification, the following ratio is based on Eq. (62)

ron

gO 2

4.57

1 moleN(14 gN/moleN)

gN

(71)

As represented by Eq. (63), CBOD is utilized during denitrification,

rondn 2.67

gO 2 5 moleC 12 gC/moleC

gO 2

1 gN

0.00286

gC 4 moleN 14 gN/moleN 1000 mgN

mgN

(72)

The temperature effect for all first-order reactions used in the model is represented by

k (T ) k ( 20) T 20

(73)

where k(T) = the reaction rate [/d] at temperature T [oC] and = the temperature

coefficient for the reaction.

Composite Variables

In addition to the model's state variables, Q2K also displays several composite variables

that are computed as follows:

Total Organic Carbon (mgC/L):

42

TOC

cs c f

roc

rca a p rcd mo

(74)

TN no na nn rna a p

(75)

TP po pi rpa a p

(76)

TKN no na rna a p

(77)

TSS rda a p m o mi

(78)

CBODu c s c f roc rca a p roc rcd mo

(79)

For all but slow and fast CBOD (cf and cs), there exists a relatively straightforward

relationship between the model state variables and standard water-quality measurements.

These are outlined next. Then we discuss issues related to the more difficult problem of

measuring CBOD.

The following are measurements that are needed for comparison of non-BOD variables

with model output:

TEMP = temperature (oC)

TKN = total kjeldahl nitrogen (gN/L) or TN = total nitrogen (gN/L)

NH4 = ammonium nitrogen (gN/L)

NO2 = nitrite nitrogen (gN/L)

NO3 = nitrate nitrogen (gN/L)

CHLA = chlorophyll a (gA/L)

TP = total phosphorus (gP/L)

QUAL2K

43

TSS = total suspended solids (mgD/L)

VSS = volatile suspended solids (mgD/L)

TOC = total organic carbon (mgC/L)

DOC = dissolved organic carbon (mgC/L)

DO = dissolved oxygen (mgO2/L)

PH = pH

ALK = alkalinity (mgCaCO3/L)

COND = specific conductance (mhos)

The model state variables can then be related to these measurements as follows:

s = COND

mi = TSS VSS or TSS rdc (TOC DOC)

o = DO

no = TKN NH4 rna CHLA

or

na = NH4

nn = NO2 + NO3

po = TP SRP rpa CHLA

pi = SRP

ap = CHLA

mo = VSS rda CHLA or rdc (TOC DOC) rda CHLA

pH = PH

Alk = ALK

Carbonaceous BOD

The interpretation of BOD measurements in natural waters is complicated by three

primary factors:

Filtered versus unfiltered. If the sample is unfiltered, the BOD will reflect

oxidation of both dissolved and particulate organic carbon. Since Q2K

distinguishes between dissolved (cs and cf) and particulate (mo and ap) organics, an

unfiltered measurement alone does not provide an adequate basis for

distinguishing these individual forms. In addition, one component of the

44

particulate BOD, phytoplankton (ap) can further complicate the test through

photosynthetic oxygen generation.

nitrification also contributes to oxygen depletion (NBOD). Thus, if the sample (a)

contains reduced nitrogen and (b) nitrification is not inhibited, the measurement

includes both types of BOD.

Because Q2K uses ultimate CBOD, 5-day BODs must be converted to ultimate

BODs in a sensible fashion.

accounts for the above factors and results in measurements that are compatible with Q2K.

Filtration. The sample should be filtered prior to incubation in order to separate

dissolved from particulate organic carbon.

Nitrification inhibition. Nitrification can be suppressed by adding a chemical inhibiting

agent such as TCMP (2-chloro-6-(trichloro methyl) pyridine. The measurement then truly

reflects CBOD. In the event that inhibition is not possible, the measured value can be

corrected for nitrogen by subtracting the oxygen equivalents of the reduced nitrogen (=

ron TKN) in the sample. However, as with all such difference-based adjustments, this

correction may exhibit substantial error.

Incubation time. The model is based on ultimate CBOD, so two approaches are

possible: (1) use a sufficiently long period so that the ultimate value is measured, or (2)

use a 5-day measurement and extrapolate the result to the ultimate. The latter method is

often computed with the formula

CBODFNU

CBODFN5

1 e k1 5

(80)

the 5-day dissolved carbonaceous BOD [mgO2/L], and k1 = the CBOD decomposition

rate in the bottle [/d].

It should be noted that, besides practical considerations of time and expense, there

may be other benefits from using the 5-day measurement with extrapolation, rather that

performing the longer-term CBOD. Although extrapolation does introduce some error,

the 5-day value has the advantage that it would tend to minimize possible nitrification

effects which, even when inhibited, can begin to be exerted on longer time frames.

The nomenclature FNU stands for Filtration, Nitrification inhibition and Ultimate

QUAL2K

45

If all the above provisions are implemented, the result should correspond to the model

variables by

cf + cs = CBODFNU

Slow versus Fast CBOD. The final question relates to discrimination between fast and

slow CBODU. Although we believe that there is currently no single, simple,

economically-feasible answer to this problem, we think that the following 2 strategies

represent the best current alternatives.

Option 1: Represent all the dissolved, oxidizable organic carbon with a single pool (fast

CBOD). It will still be necessary to specify rate parameters for slow CBOD because the

process of dissolution of particulate organic carbon in detritus contributes to slow CBOD.

If no slow CBOD inputs are entered for headwater, point sources, or nonpoint sources,

then slow CBOD will most likely exert a very minor influence on dissolved oxygen and it

is effectively dropped from the model. For this case,

cf = CBODFNU

cs = 0

Option 2: Use an ultimate CBOD measurement for the fast fraction and compute slow

CBOD by difference with a DOC measurement. For this case,

cf = CBODFNU

cs = rocDOC CBODFNU

Option 2 works very nicely for systems where two distinct types of CBOD are

present. For example, sewage effluent and autochthonous carbon from the aquatic food

chain might be considered as fast CBOD. In contrast, industrial wastewaters such as pulp

and paper mill effluent or allochthonous DOC from the watershed might be considered

more recalcitrant and hence could be lumped into the slow CBOD fraction. In such case,

the hydrolysis rate converting the slow into the fast fraction could be set to zero to make

the two forms independent, and the cs and cf could each be represented by CBODFNU

data from their respective sources (e.g. for some sources such as municipal wastewaters

the CBODFNU could contribute to cf, and for others such as pulp mill effluents with more

refractory organic carbon their CBODFNU could contribute to cs).

For options 1 and 2, the CBODFNU can either be (a) measured directly using a long

incubation time or (b) computed by extrapolation with Eq. 75. In both situations, a time

frame of several weeks to a month (i.e., a 20- to 30-day CBOD) is probably a valid period

in order to oxidize most of the readily degradable organic carbon. We base this

assumption on the fact that bottle rates for sewage-derived organic carbon are on the

order of 0.05 to 0.3/d (Chapra 1997). As in Figure 17, such rates suggest that much of the

readily oxidizable CBOD will be exerted in about 20 to 30 days.

46

Figure 17 Progression of CBOD test for various levels of the bottle decomposition rate.

CBOD tests at 30oC rather than at the commonly employed temperature of 20oC. The

choice of 20oC originated from the fact that the average daily temperature of most

receiving waters and wastewater treatment plants in the temperate zone in summer is

approximately 20oC.

If the CBOD measurement is intended to be used for regulation or to assess treatment

plant performance, it makes sense to standardize the test at a particular temperature. And

for such purposes, 20oC is as reasonable a choice as any. However, if the intent is to

measure an ultimate CBOD, anything that speeds up the process while not jeopardizing

the measurement's integrity would seem beneficial.

The saprophytic bacteria that break down nonliving organic carbon in natural waters

and sewage thrive best at temperatures from 20C to 40C. Thus, a temperature of 30oC is

not high enough that the bacterial assemblage would shift to thermophilic organisms that

are atypical of natural waters and sewage. The benefit should be higher oxidation rates

which would result in shorter analysis times for CBOD measurements. Assuming that a

Q10 2 is a valid approximation for bacterial decomposition, a 20-day BOD at 30oC

should be equivalent to a 30-day BOD at 20oC.

In some cases where available data are very limited and only 5-day BOD (BOD5)

data are available to represent organic carbon, it may be reasonable to use a simplification

of option 1 by assuming that BOD5 is approximately equivalent to of CBODFN5. If the

BOD decay rate constant is assumed to be a typical value of about -0.23 day-1 (Brown

and Barnwell, 1985), then the fast CBOD could be approximated as about 1.46 X BOD5.

A better simple alternative could be to estimate the carbonaceous fraction of the total

BOD5 (CBOD5) from literature summaries or available data and then estimate the fast

CBOD as 1.46 X CBOD5.

Constituent Reactions

QUAL2K

47

The mathematical relationships that describe the individual reactions and concentrations

of the model state variables (Table 5) are presented in the following paragraphs.

By definition, conservative substances are not subject to reactions:

(81)

Ss = 0

Phytoplankton (ap)

Phytoplankton increase due to photosynthesis. They are lost via respiration, death, and

settling

S ap PhytoPhoto PhytoResp PhytoDeath PhytoSettl

(82)

Photosynthesis

Phytoplankton photosynthesis is computed as

PhytoPhoto p a p

(83)

and light,

p k gp (T ) Np Lp

(84)

phytoplankton nutrient attenuation factor [dimensionless number between 0 and 1], and

Lp = the phytoplankton light attenuation coefficient [dimensionless number between 0

and 1].

Nutrient Limitation. Michaelis-Menten equations are used to represent growth

limitation for inorganic nitrogen, phosphorus and inorganic carbon. The minimum value

is then used to compute the nutrient attenuation factor,

na nn

pi

[ H 2 CO *3 ] [ HCO 3 ]

,

,

k sNp n a n n k sPp p i k sCp [ H 2 CO *3 ] [ HCO 3 ]

Np min

(85)

constant [gP/L], ksCp = inorganic carbon half-saturation constant [mole/L], [H2CO3*] =

48

concentration [mole/L].

Light Limitation. It is assumed that light attenuation through the water follows the BeerLambert law,

PAR ( z ) PAR (0)e ke z

(86)

water surface [ly/d]5, and ke = the light extinction coefficient [m1]. The PAR at the

water surface is assumed to be a fixed fraction of the solar radiation:

PAR(0) = 0.47 I(0)

The extinction coefficient is related to model variables by

k e k eb i mi o mo p a p pn a 2p / 3 mac ab / H i

(87)

where keb = the background coefficient accounting for extinction due to water and

color [/m], i, o, p, pn,, and mac are constants accounting for the impacts of

inorganic suspended solids [L/mgD/m], particulate organic matter [L/mgD/m], and

chlorophyll [L/gA/m and (L/gA)2/3/m], and macrophytes [m3/gD/m], respectively.

Suggested values for these coefficients are listed in Table 6.

Table 6 Suggested values for light extinction coefficients

Symbol

Value

i

o

p

pn

mac

mac

mac

mac

0.052

0.174

0.0088

0.054

0.01

0.006

0.013 to 0.019

0.024

Reference

Di Toro (1978)

Di Toro (1978)

Riley (1956)

Riley (1956)

Ikusima, 1970 (Myriophyllum spicatum)

Titus and Adams, 1979 (Myriophyllum spicatum)

Titus and Adams, 1979 (Vallisneria americana)

Van der Bijl et al., 1989 (Potamogeton pectinatus)

photosynthesis (Figure 18):

ly/d = langley per day. A langley is equal to a calorie per square centimeter. Note that a ly/d is related to

the E/m2/d by the following approximation: 1 E/m2/s 0.45 Langley/day (LIC-OR, Lincoln, NE).

QUAL2K

49

Smith

Steele

Half-saturation

0.5

0

0

100

200

300

400

500

Figure 18 The three models used for phytoplankton and bottom algae photosynthetic light

dependence. The plot shows growth attenuation versus PAR intensity [ly/d].

FLp

I ( z)

K Lp I ( z )

(88)

where FLp = phytoplankton growth attenuation due to light and KLp = the

phytoplankton light parameter. In the case of the half-saturation model, the light

parameter is a half-saturation coefficient [ly/d]. This function can be combined with

the Beer-Lambert law and integrated over water depth, H [m], to yield the

phytoplankton light attenuation coefficient

Lp

K Lp I (0)

1

ln

k e H K Lp I (0)e ke H

(89)

FLp

I ( z)

2

K Lp

(90)

I ( z) 2

where KLp = the Smith parameter for phytoplankton [ly/d]; that is, the PAR at which

growth is 70.7% of the maximum. This function can be combined with the Beer-Lambert

law and integrated over water depth to yield

Lp

I (0) / K Lp 1 I (0) / K Lp 2

ln

k e H I (0) / K e ke H 1 I (0) / K e ke H

Lp

Lp

(91)

50

FLp

I (z)

e

K Lp

I (z)

K Lp

(92)

where KLp = the PAR at which phytoplankton growth is optimal [ly/d]. This function can

be combined with the Beer-Lambert law and integrated over water depth to yield

Lp

I ( 0)

I (0) e ke H

2.718282

K Lp

K Lp

e

e

ke H

(93)

Losses

Respiration. Phytoplankton respiration is represented as a first-order rate that is

attenuated at low oxygen concentration,

PhytoResp Foxp k rp (T ) a p

(94)

attenuation due to low oxygen [dimensionless]. Oxygen attenuation is modeled by Eqs.

(111) to (113) with the oxygen dependency represented by the parameter Ksop.

Death. Phytoplankton death is represented as a first-order rate,

PhytoDeath k dp (T ) a p

(95)

Settling. Phytoplankton settling is represented as

PhytoSettl

va

ap

H

(96)

Bottom algae increase due to photosynthesis. They are lost via respiration and death.

S b BotAlgPhoto BotAlgResp BotAlgDeath

(97)

Photosynthesis

QUAL2K

51

simplification. The first is based on a temperature-corrected zero-order rate attenuated by

nutrient and light limitation (Rutherford et al. 1999),

BotAlgPhoto C gb (T ) Nb Lb

(98)

(m2 d)], Nb = bottom algae nutrient attenuation factor [dimensionless number between 0

and 1], and Lb = the bottom algae light attenuation coefficient [dimensionless number

between 0 and 1].

The second uses a first-order model,

BotAlgPhoto C gb (T ) Nb Lb Sb a b

(99)

photosynthesis rate [d1], and Sb = bottom algae space limitation attenuation factor.

Temperature Effect. As for the first-order rates, an Arrhenius model is employed to

quantify the effect of temperature on bottom algae photosynthesis,

C gb (T ) C gb ( 20) T 20

(100)

modeled in a different way than for the phytoplankton. Rather than being dependent on

external nutrient concentration, the photosynthesis rate is dependent on intracellular

nutrients using a formulation originally developed by Droop (1974),

Nb

q0 N

q0P

[ H 2 CO *3 ] [HCO 3 ]

min 1

,1

,

qN

q P k sCb [H 2 CO *3 ] [ HCO 3 ]

(101)

where qN and qP = the cell quotas of nitrogen [mgN gD1] and phosphorus [mgP gD1],

respectively, q0N and q0P = the minimum cell quotas of nitrogen [mgN gD1] and

phosphorus [mgP gD1], respectively, and , ksCb = inorganic carbon half-saturation

constant for the bottom algae [mole/L]. The minimum cell quotas are the levels of

intracellular nutrient at which growth ceases.

The cell quotas represent the ratios of the intracellular nutrient to the bottom plants

dry weight,

qN

IN b

ab

(102)

52

qP

IPb

ab

(103)

phosphorus concentration [mgP/m2].

The change in intracellular nitrogen and phosphorus in bottom algal cells is calculated

from

S bN BotAlgUptakeN q N BotAlgDeath q N k excb (T )ab

(104)

(105)

where BotAlgUptakeN and BotAlgUptakeP = uptake rates for nitrogen and phosphorus in

bottom algae (mgN/m2/d and mgP/m2/d), kexcb(T) = the temperature-dependent bottom

algae excretion rate [/d], and BotAlgDeath is the death term for bottom algae (gD/m2/d)

as defined in the Losses subsection below. The N and P uptake rates depend on both

external and intracellular nutrients as in (Rhee 1973),

BotAlgUptakeN mN

K qN

na nn

ab

k sNb n a n n K qN (q N q 0 N )

(106)

BotAlgUptakeP mP

K qP

pi

ab

k sPb p i K qP ( q P q 0 P )

(107)

where mN and mP = the maximum uptake rates for nitrogen [mgN/gD/d] and phosphorus

[mgP/gD/d], respectively, ksNb and ksPb = half-saturation constants for external nitrogen

[gN/L] and phosphorus [gP/L], respectively and KqN and KqP = half-saturation

constants for intracellular nitrogen [mgN gD1] and phosphorus [mgP gD1], respectively.

Light Limitation. If bottom plants represent macrophytes, then light limitation is

determined by the PAR in the integrated water column similar to the method for

phytoplankton. Bottom plants are assumed to represent macrophytes if any N or P uptake

is specified to occur from the sediments. If bottom plants represent periphyton or bottom

algae instead of macrophytes, then light limitation at any time is determined by the

amount of PAR reaching the bottom of the water column. The quantity of bottom light is

computed with the Beer-Lambert law (recall Eq. 76) evaluated at the bottom of the river,

I ( H ) I (0)e ke H

(108)

As with the phytoplankton, three models (Eqs. 78, 80 and 82) are used to characterize the

impact of light on bottom algae photosynthesis. Substituting Eq. (98) into these

models yields the following formulas for the bottom algae light attenuation

coefficient,

QUAL2K

53

Lb

I (0)e ke H

K Lb I (0)e ke H

(109)

Lp

I (0)e ke H

2

K Lb

I (0)e ke H

(110)

Lb

I (0)e ke H 1

e

K Lb

I ( 0) e ke H

K Lb

(111)

where KLb = the appropriate bottom algae light parameter for each light model.

Space Limitation. If a first-order growth model is used, a term must be included to

impose a space limitation on the bottom algae. A logistic model is used for this purpose

as in

Sb 1

ab

a b ,max

Losses

Respiration. Bottom algae respiration is represented as a first-order rate that is

attenuated at low oxygen concentration,

BotAlgResp Foxb [k rb ,1 (T ) ab k rb , 2 BotAlgPhoto]

(112)

where krb,1(T) = temperature-dependent bottom algae basal respiration rate [/d], krb,2 =

bottom algae photo-respiration respiration rate constant [dimensionless], and Foxb =

attenuation due to low oxygen [dimensionless]. Laws and Chalup (1990) suggest a

typical basal respiration rate (krb,1) of about 0.042 d-1 and a photo-respiration rate constant

(krb,2) of about 0.389, which corresponds to about 39% of the actual growth rate (Chapra,

1997). Oxygen attenuation is modeled by Eqs. (111) to (113) with the oxygen

dependency represented by the parameter Ksob.

54

BotAlgDeath k db (T )ab

(113)

Detritus (mo)

Detritus or particulate organic matter (POM) increases due to plant death. It is lost via

dissolution and settling

S mo rda PhytoDeath BotAlgDeath DetrDiss DetrSettl

(114)

where

DetrDiss k dt (T ) mo

(115)

DetrSettl

v dt

mo

H

(116)

Slowly reacting CBOD increases due to detritus dissolution. It is lost via hydrolysis.

S cs rod DetrDiss SlowCHydr SlowCOxid

(117)

where

SlowCHydr k hc (T )c s

(118)

(119)

where khc(T) = the temperature-dependent slow CBOD hydrolysis rate [/d], kdcs(T) = the

temperature-dependent fast CBOD oxidation rate [/d] and Foxcf = attenuation due to low

oxygen [dimensionless].

QUAL2K

55

Fast reacting CBOD is gained via the hydrolysis of slowly-reacting CBOD. It is lost via

oxidation and denitrification.

S cf SlowCHydr FastCOxid rondn Denitr J CH4,d

Ast ,i

Vi

(120)

where

FastCOxid Foxcf k dc (T )c f

(121)

where kdc(T) = the temperature-dependent fast CBOD oxidation rate [/d] and Foxcf =

attenuation due to low oxygen [dimensionless]. The parameter rondn is the ratio of oxygen

equivalents lost per nitrate nitrogen that is denitrified (Eq. 69). The term Denitr is the rate

of denitrification [gN/L/d] defined in a later section. The term JCH4,d is the sediment flux

of dissolved methane in oxygen equivalents (gO2/m2/d) as described in a later section.

Three formulations are used to represent the oxygen attenuation:

Half-Saturation:

Foxrp

(122)

K socf o

where Ksocf = half-saturation constant for the effect of oxygen on fast CBOD oxidation

[mgO2/L].

Exponential:

Foxrp (1 e

K socf o

(123)

where Ksocf = exponential coefficient for the effect of oxygen on fast CBOD oxidation

[L/mgO2].

Second-Order Half Saturation:

Foxrp

o2

K socf o 2

(124)

where Ksocf = half-saturation constant for second-order effect of oxygen on fast CBOD

oxidation [mgO22/L2].

Organic nitrogen increases due to plant death. It is lost via hydrolysis and settling.

56

(125)

ONHydr k hn (T ) n o

(126)

ONSettl

v on

no

H

(127)

Ammonia nitrogen increases due to organic nitrogen hydrolysis and phytoplankton

respiration. It is lost via nitrification and plant photosynthesis:

S na ONHydr rna PhytoResp NH4Nitrif rna Pap PhytoPhoto

[J NH4 Pab BotAlgUptakeN ( NUpWCfrac)]

Ast ,i

(128)

Vi

NH4Nitrif Foxna k n (T ) n a

(129)

where kn(T) = the temperature-dependent nitrification rate for ammonia nitrogen [/d] and

Foxna = attenuation due to low oxygen [dimensionless]. Oxygen attenuation is modeled by

Eqs. (111) to (113) with the oxygen dependency represented by the parameter Ksona.

The coefficients Pap and Pab are the preferences for ammonium as a nitrogen source

for phytoplankton and bottom algae, respectively,

Pap

Pab

(k hnxp

n a k hnxp

na nn

(130)

(k hnxb

na nn

n a k hnxb

(131)

where khnxp = preference coefficient of phytoplankton for ammonium [mgN/m3] and khnxb =

preference coefficient of bottom algae for ammonium [mgN/m3].

QUAL2K

57

The fraction of N uptake from the water column by bottom plants is described by

NUpWCfrac. For periphyton, the value of NUpWCfrac is 1 since 100% of their nutrient

uptake occurs from the water column. For macrophytes the value of NUpWCfrac may be

less than 1.

The term JNH4 is the sediment flux of ammonia as described in a later section.

Unionized Ammonia

The model simulates total ammonia. In water, the total ammonia consists of two forms:

ammonium ion, NH4+, and unionized ammonia, NH3. At normal pH (6 to 8), most of the

total ammonia will be in the ionic form. However at high pH, unionized ammonia

predominates. The amount of unionized ammonia can be computed as

nau Fu na

(132)

where nau = the concentration of unionized ammonia [gN/L], and Fu = the fraction of the

total ammonia that is in unionized form,

Fu

1

1 10

pH

(133)

Ka

where Ka = the equilibrium coefficient for the ammonia dissociation reaction, which is

related to temperature by

pK a 0.09018

2729.92

Ta

(134)

Nitrate nitrogen increases due to nitrification of ammonia. It is lost via denitrification and

plant photosynthesis:

S ni NH4Nitrif Denitr rna (1 Pap ) PhytoPhoto

[J NO3 (1 Pab ) BotAlgUptakeN(NUpWCfrac)]

Ast ,i

(135)

Vi

Denitr (1 Foxdn )k dn (T ) n n

(136)

58

where kdn(T) = the temperature-dependent denitrification rate of nitrate nitrogen [/d] and

Foxdn = effect of low oxygen on denitrification [dimensionless] as modeled by Eqs. (111)

to (113) with the oxygen dependency represented by the parameter Ksodn.

The fraction of N uptake from the water column by bottom plants is described by

NUpWCfrac. For periphyton, the value of NUpWCfrac is 1 since 100% of their nutrient

uptake occurs from the water column. For macrophytes the value of NUpWCfrac may be

less than 1.

The term JNO3 is the sediment flux of nitrate (mgN/m2/d) as described in a later section.

Organic phosphorus increases due to plant death. It is lost via hydrolysis and settling.

S po rpa PhytoDeath q P BotAlgDeath OPHydr OPSettl

(137)

OPHydr k hp (T ) p o

(138)

Organic phosphorus settling is determined as

OPSettl

v op

H

(139)

po

Inorganic phosphorus increases due to organic phosphorus hydrolysis and phytoplankton

respiration. It is lost via plant photosynthesis. In addition, a settling loss is included for

cases in which inorganic phosphorus is lost due to sorption onto settleable particulate

matter such as iron oxyhydroxides:

S pi DOPHydr rpa PhytoResp rpa PhytoPhoto IPSettl

[J PO4 BotAlgUptakeP( PUpWCfrac) ]

Ast ,i

(140)

Vi

where

QUAL2K

59

IPSettl

v ip

H

(141)

pi

The fraction of P uptake from the water column by bottom plants is described by

PUpWCfrac. For periphyton, the value of PUpWCfrac is 1 since 100% of their nutrient

uptake occurs from the water column. For macrophytes the value of PUpWCfrac may be

less than 1.

The term JPO4 is the sediment flux of inorganic P (mgP/m2/d) as defined in a later section.

Inorganic suspended solids are lost via settling,

Smi = InorgSettl

where

InorgSettl

vi

mi

H

(142)

Dissolved oxygen increases due to plant photosynthesis. It is lost via fast and slow

CBOD oxidation, nitrification and plant respiration, and oxidation of non-carbonaceous

non-nitrogenous chemical oxygen demand (COD). Depending on whether the water is

undersaturated or oversaturated it is gained or lost via reaeration,

S o roa (PhytoPhoto - PhytoResp) ro d (BotAlgPhoto - BotAlgResp)

Ast ,i

Vi

Ast ,i

Vi

(143)

where

OxReaer k a (T ) o s (T , elev) o

(144)

60

where ka(T) = the temperature-dependent oxygen reaeration coefficient [/d], os(T, elev) =

the saturation concentration of oxygen [mgO2/L] at temperature, T, and elevation above

sea level, elev. The term CODoxid is the COD oxidation (mgO2/L/d) as defined in the

section below on the generic constituent. SOD is the sediment oxygen demand [gO2/m2/d]

as described in a later section.

Oxygen Saturation

The following equation is used to represent the dependence of oxygen saturation on

temperature (APHA 1992)

ln o s (T , 0) 139.34411

1.575701 10 5 6.642308 10 7

Ta

Ta2

1.243800 10

Ta3

10

11

8.621949 10

(145)

Ta4

[mgO2/L] and Ta = absolute temperature [K] where Ta = T +273.15.

The effect of elevation is accounted for by

o s (T , elev) e ln os (T , 0 ) (1 0.0001148elev)

(146)

Reaeration Formulas

The reaeration coefficient (at 20 oC) can be prescribed on the Reach Worksheet. If

reaeration is not prescribed (that is, it is blank or zero for a particular reach), it is computed

as a function of the rivers hydraulics and (optionally) wind velocity,

k a ( 20) k ah ( 20)

K Lw ( 20)

H

(147)

where kah(20) = the reaeration rate at 20 oC computed based on the rivers hydraulic

characteristics [d1], KL(20) = the reaeration mass-transfer coefficient based on wind

velocity [m/d], and H = mean depth [m].

Hydraulic-based Formulas:

OConnor-Dobbins (OConnor and Dobbins 1958):

k ah ( 20) 3.93

QUAL2K

U 0.5

H 1.5

(148)

61

where U = mean water velocity [m/s] and H = mean water depth [m].

Churchill (Churchill et al. 1962):

k ah ( 20) 5.026

U

H 1.67

(149)

k ah ( 20) 5.32

U 0.67

H 1.85

(150)

Low flow, Q = 0.0283 to 0.4247 cms (1 to 15 cfs):

k ah (20) 31,183 US

(151)

k ah ( 20) 15,308 US

(152)

Thackston-Dawson (Thackston and Dawson 2001):

k ah ( 20) 2.16(1 9 F 0.25 )

U*

H

(153)

where U* = shear velocity [m/s], and F = the Froude number [dimensionless]. The shear

velocity and the Froude number are defined as

U*

gR h S

(154)

and

F

U

gH d

(155)

slope [m/m], and Hd = the hydraulic depth [m]. The hydraulic depth is defined as

Hd

Ac

Bt

(156)

62

USGS (Pool-riffle) (Melching and Flores 1999):

Low flow, Q < 0.556 cms (< 19.64 cfs):

k ah (20) 517(US ) 0.524 Q 0.242

(157)

k ah (20) 596(US ) 0.528 Q 0.136

(158)

USGS (Channel-control) (Melching and Flores 1999):

Low flow, Q < 0.556 cms (< 19.64 cfs):

k ah (20) 88(US ) 0.313 H 0.353

(159)

k ah ( 20) 142(US ) 0.333 H 0.66 Bt0.243

(160)

Reaeration can also be internally calculated based on the following scheme patterned

after a plot developed by Covar (1976) (Figure 19):

If H < 0.61 m, use the Owens-Gibbs formula

If H > 0.61 m and H > 3.45U2.5, use the OConnor-Dobbins formula

Otherwise, use the Churchill formula

This is referred to as option Internal on the Rates Worksheet of Q2K. Note that if no

option is specified, the Internal option is the default.

QUAL2K

63

10

OConnor

Dobbins

0.05

0.1

Churchill

Depth (m)

0.2

0.5

1

2

5

10

20

50

100

0.1

0.1

Owens

Gibbs

Velocity (mps)

Figure 19 Reaeration rate (/d) versus depth and velocity (Covar 1976).

Wind-based Formulas:

Three options are available to incorporate wind effects into the reaeration rate: (1) it can

be omitted, (2) the Banks-Herrera formula and (3) the Wanninkhof formula.

Banks-Herrera formula (Banks 1975, Banks and Herrera 1977):

K lw 0.728U w0.,510 0.317U w,10 0.0372U w2 ,10

(161)

where Uw,10 = wind speed measured 10 meters above the water surface [m s1]

Wanninkhof formula (Wanninkhof 1991):

1.64

K lw 0.0986U w

,10

(162)

Note that the model uses Eq. (50) to correct the wind velocity entered on the

Meteorology Worksheet (7 meters above the surface) so that it is scaled to the 10-m

height.

Effect of Control Structures: Oxygen

Oxygen transfer in streams is influenced by the presence of control structures such as

weirs, dams, locks, and waterfalls (Figure 20). Butts and Evans (1983) have reviewed

efforts to characterize this transfer and have suggested the following formula,

rd 1 0.38a d bd H d (1 0.11H d )(1 0.046T )

(163)

64

where rd = the ratio of the deficit above and below the dam, Hd = the difference in water

elevation [m] as calculated with Eq. (7), T = water temperature (C) and ad and bd are

coefficients that correct for water-quality and dam-type.

Values of ad and bd are summarized in Table 7. At present, Q2K uses the following

values for these coefficients: ad = 1.25 and bd = 0.9.

Qi1 oi1

Qi1 oi1

Hd

i1

Table 7 Coefficient values used to predict the effect of dams on stream reaeration.

Polluted state

Gross

Moderate

Slight

Clean

(b) Dam-type coefficient

Dam type

Flat broad-crested regular step

Flat broad-crested irregular step

Flat broad-crested vertical face

Flat broad-crested straight-slope

face

Flat broad-crested curved face

Round broad-crested curved face

Sharp-crested straight-slope face

Sharp-crested vertical face

Sluice gates

ad

0.65

1.0

1.6

1.8

bd

0.70

0.80

0.60

0.75

0.45

0.75

1.00

0.80

0.05

The oxygen mass balance for the reach below the structure is written as

QUAL2K

65

Qab,i

Wo ,i

doi Qi 1

Q

E'

o'i 1 i oi

oi i oi 1 oi

S o ,i

dt

Vi

Vi

Vi

Vi

Vi

(164)

where oi1 = the oxygen concentration entering the reach [mgO2/L], where

o'i 1 o s ,i 1

o s ,i 1 oi 1

(165)

rd

Pathogen (x)

Pathogens are subject to death and settling,

S x PathDeath PathSettl

(166)

Death

Pathogen death is due to natural die-off and light (Chapra 1997). The death of pathogens

in the absence of light is modeled as a first-order temperature-dependent decay and the

death rate due to light is based on the Beer-Lambert law,

PathDeath k dx (T ) x path

I (0) / 24

1 e ke H x

ke H

(167)

where kdx(T) = temperature-dependent pathogen die-off rate [/d] and path is a constant for

the light-induced mortality (day-1 per ly/hour). Thomann and Mueller (1987) suggest that

path is a approximately unity.

Settling

Pathogen settling is represented as

PathSettl

vx

x

H

(168)

A generic constituent is available for optional use. The user has the option of either

assuming that the generic constituent has no interaction with other state variables, or it

can be treated as a non-carbonaceous non-nitrogenous chemical oxygen demand (COD).

The generic constituent is also subject to first-order decay and settling,

66

v gen

H

(169)

gen

where kgen(T) = temperature-dependent decay rate [/d] and vgen = settling velocity [m/d].

If the generic constituent is used as COD, then the COD oxidation rate (mgO2/L/d) is

determined by

CODoxid k gen (T ) gen

(170)

pH

The following equilibrium, mass balance and electroneutrality equations define a

freshwater dominated by inorganic carbon (Stumm and Morgan 1996),

K1

K2

[ HCO 3 ][H ]

(171)

[ H 2 CO *3 ]

[CO 32 ][H ]

(172)

[HCO 3 ]

K w [H ][OH ]

(173)

cT [ H 2 CO *3 ] [HCO 3 ] [CO 32 ]

(174)

(175)

where K1, K2 and Kw are acidity constants, Alk = alkalinity [eq L1], H2CO3* = the sum of

dissolved carbon dioxide and carbonic acid, HCO3 = bicarbonate ion, CO32 = carbonate

ion, H+ = hydronium ion, OH = hydroxyl ion, and cT = total inorganic carbon

concentration [mole L1]. The brackets [ ] designate molar concentrations.

Note that the alkalinity is expressed in units of eq/L for the internal calculations. For

input and output, it is expressed as mgCaCO3/L. The two units are related by

Alk ( mgCaCO 3 /L) 50,000 Alk (eq/L)

(176)

QUAL2K

67

pK w =

4787.3

7.1321 log10 (Ta ) 0.010365Ta 22.80

Ta

(177)

126.8339 log Ta 1,684,915 / Ta2

(178)

38.92561 log Ta 563,713.9 / Ta2

(179)

The nonlinear system of five simultaneous equations (158 through 162) can be solved

numerically for the five unknowns: [H2CO3*], [HCO3], [CO32], [OH], and {H+}. An

efficient solution method can be derived by combining Eqs. (158), (159) and (161) to

define the quantities (Stumm and Morgan 1996)

0

[H ] 2

(180)

[H ] 2 K1[H ] + K1 K 2

K1[H ]

(181)

[H ] 2 K1[H ] + K1 K 2

K1 K 2

(182)

[H ] K1[H ] + K1 K 2

bicarbonate, and carbonate, respectively. Equations (160), (162), (168) and (169) can then

be combined to yield,

Alk = ( 1 2 2 )cT

Kw

[H ]

[H ]

(183)

f ([H ]) = ( 1 2 2 )cT

Kw

[H ]

[H ] Alk

(184)

68

pH log10 [ H ]

(185)

The root of Eq. (155) is determined with a numerical method. The user can choose

either the Newton-Raphson or the bisection method (Chapra and Canale 2002) as

specified on the QUAL2K sheet. The Newton-Raphson is faster and is the default

method. However, it can sometimes diverge. In such cases, because it is more stable, the

bisection method would be preferable.

Total inorganic carbon concentration increases due to fast carbon oxidation and plant

respiration. It is lost via plant photosynthesis. Depending on whether the water is

undersaturated or oversaturated with CO2, it is gained or lost via reaeration,

S cT rcco FastCOxid rcca (PhytoResp PhytoPhoto)

rccd (BotAlgResp BotAlgPhoto)

Ast ,i

Vi

CO2Reaer

(186)

where

CO2Reaer k ac (T ) [CO 2 ] s 0 cT

(187)

where kac(T) = the temperature-dependent carbon dioxide reaeration coefficient [/d], and

[CO2]s = the saturation concentration of carbon dioxide [mole/L].

The stoichiometric coefficients are derived from Eq. (60)6

gC

moleC

m3

12 gC 1000 L

mgA

(188)

gC

moleC

m3

12 gC 1000 L

gD

(189)

gC

gO 2

(190)

rcca rca

rccd rcd

rcco

1

roc

moleC

m3

12 gC 1000 L

6

The conversion, m3 = 1000 L is included because all mass balances express volume in m3, whereas total

inorganic carbon is expressed as mole/L.

QUAL2K

69

[CO 2 ]s K H p CO2

(191)

where KH = Henry's constant [mole (L atm)1] and pCO2 = the partial pressure of carbon

dioxide in the atmosphere [atm]. Note that the partial pressure is input on the Rates

Worksheet in units of ppm. The program internally converts ppm to atm using the

conversion: 106 atm/ppm.

The value of KH can be computed as a function of temperature by (Edmond and

Gieskes 1970)

pK H =

2385.73

0.0152642Ta 14.0184

Ta

(192)

The partial pressure of CO2 in the atmosphere has been increasing, largely due to the

combustion of fossil fuels (Figure 21). Values in 2003 are approximately 103.43 atm (=

372 ppm).

Observatory, Hawaii. (http://www.cmdl.noaa.gov/ccg/figures/co2mm_mlo.jpg).

70

The CO2 reaeration coefficient can be computed from the oxygen reaeration rate by

32

44

k ac ( 20)

0.25

(193)

As was the case for dissolved oxygen, carbon dioxide gas transfer in streams can be

influenced by the presence of control structures. Q2K assumes that carbon dioxide

behaves similarly to dissolved oxygen (recall Sec. ). Thus, the inorganic carbon mass

balance for the reach immediately downstream of the structure is written as

Qab,i

WcT ,i

Qi 1

Qi

Ei'

c'T ,i 1

cT ,i

cT ,i

cT ,i 1 cT ,i

S cT ,i

dt

Vi

Vi

Vi

Vi

Vi

dcT ,i

(194)

where c'T,i1 = the concentration of inorganic carbon entering the reach [mgO2/L], where

c'T ,i 1 ( 1 2 )cT ,i 1 CO2, s ,i 1

CO2 , s ,i 1 0 cT ,i 1

(195)

rd

Alkalinity (Alk)

The present model accounts for changes in alkalinity due to plant photosynthesis and

respiration, nitrogen and phosphorus hydrolysis, nitrification, and denitrification.

S alk ralkaa Pap ralkan (1 Pap ) PhytoPhoto ralkaa PhytoResp

ralkbn ONHydr ralkbp OPHydr ralkn NH4Nitr ralkden Denitr

[ralkbn (1 Pap )BotAlgUptakeN ralkbn Pap BotAlgUptakeN ralkbp BotAlgUptakeP]

Ast ,i

Vi

(196)

where the rs are ratios that translate the processes into the corresponding amount of

alkalinity. The stoichiometric coefficients are derived from Eqs. (60) through (63) as in

Phytoplankton Photosynthesis (Ammonia as Substrate) and Respiration:

gC

14 eqH

moleC

m3

mgA

ralkaa rca

(197)

QUAL2K

71

gC

18 eqH

moleC

m3

mgA

ralkan rca

(198)

ralkbn

16 eqH

moleN

gN

m3

16 moleN 14 gN

1000 mgN 1000 L

(199)

ralkbp

2 eqH

moleP

gP

m3

1 moleP

31 gP

1000 mgP 1000 L

(200)

Nitrification:

ralkn

2 eqH

1 gN

moleN

1 m3

1 moleN

14 gN

1000 mgN 1000 L

(201)

Denitrification:

ralkden

4 eqH

1 gN

moleN

1 m3

1 moleN

14 gN

1000 mgN 1000 L

(202)

(Level 1)

The Level 1 option in Q2K for constituents in the hyporheic pore water includes

simulation of zero-order or first-order oxidation of fast-reacting dissolved CBOD with

attenuation from temperature, CBOD, and dissolved oxygen. The Level 1 option does not

include simulation of the biofilm of heterotrophic bacteria as a state variable. Instead, the

net growth of the biofilm is estimated from the input of either a zero-order or first-order

oxidation rate of fast-reacting CBOD that is attenuated by temperature, dissolved oxygen,

and fast-reacting CBOD concentrations.

The mathematical relationships that describe the individual reactions and concentrations

of the model state variables (Table 5) for Level 1 simulation of water quality constituents

in the hyporheic pore water are presented in the following paragraphs.

By definition, conservative substances are not subject to reactions. Therefore the net gain

or loss in the hyporheic sediment zone (Ss,2) is calculated as

72

(203)

Ss,2 = 0

Phytoplankton (ap)

Phytoplankton are lost via respiration and death. The net gain or loss in the hyporheic

sediment zone (Sap,2) is calculated as

S ap , 2 PhytoResp2 PhytoDeath 2

(204)

Losses

Respiration. Phytoplankton respiration is represented as a first-order rate that is

attenuated at low oxygen concentration. Phytoplankton respiration in the hyporheic

sediment zone is calculated as

PhytoResp2 Foxrp , 2 k rp (T ) a p , 2

(205)

where krp(T) = temperature-dependent phytoplankton respiration rate [/d] (Ti,2 is used for

temperature adjustment of all rates in the hyporheic sediment zone of a reach) and Foxrp,2

= attenuation in the hyporheic zone due to low oxygen. Three formulations are used to

represent the oxygen attenuation (o2 is used to determine oxygen attenuation in the

hyporheic pore water zone).

Death. Phytoplankton death is represented as a first-order rate. Death in the hyporheic

sediment zone is calculated as

PhytoDeath 2 k dp (T ) a p , 2

(206)

The Level 1 option of Q2K does not include simulation of the biofilm of heterotrophic

bacteria (aerobic bacteria) as a state variable. Instead, the net growth of attached

heterotrophic bacteria is estimated from the input of either a zero-order or first-order

oxidation rate of fast-reacting CBOD that is attenuated by temperature, dissolved oxygen,

and fast-reacting CBOD concentrations. The Rates sheet of Q2K allows the user to select

either a zero-order or first-order oxidation rate model, and specify the appropriate zeroorder or first-order oxidation rates. If a zero-order oxidation rate is selected on the Rates

sheet, then the following equation represents the net growth rate of heterotrophic

bacteria:

HeteroGrow C gh (T ) Nh rdo

QUAL2K

(207)

73

attached heterotrophic bacteria [as gO2m-2d-1)], and Nh = the attenuation factor due to the

concentration of fast-reacting CBOD and dissolved oxygen [dimensionless number

between 0 and 1], and rdo is the stoichiometric ratio between dry weight of organic

material in bacteria and oxygen [g dry weight/gO2] as discussed in the water column

section on Stoichiometry of Organic Matter.

If a first-order oxidation rate is specified on the Rates sheet, then the following equation

is used to represent the net growth rate of heterotrophic bacteria:

HeteroGrow k gh (T ) Nh c f , 2 rdo

V2 , i

Ast ,i

(208)

where kgh(T) = the maximum oxidation rate of fast-reacting CBOD at temperature T due

to the net growth of attached heterotrophic bacteria [d-1], and Nh = the attenuation factor

due to the concentration of fast-reacting CBOD and dissolved oxygen [dimensionless

number between 0 and 1], cf,2 is the concentration of fast-reacting CBOD in the hyporheic

pore water [gO2/m3], rdo is the stoichiometric ratio between dry weight and oxygen

equivalents [g dry weight/gO2], V2,i is the volume of hyporheic pore water in reach i [m3],

and Ast,i is the surface area of reach i [m2].

Temperature Effect. As for the first-order reactions described in the water column

section on Temperature Effects on Reactions, an Arrhenius model is employed to quantify

the effect of temperature if a zero-order oxidation model is selected:

C gh (T ) C h ( 20) T 20

(209)

Nutrient and Substrate Limitation. Michaelis-Menten equations are used to represent the

attenuation of oxidation due to fast-reacting CBOD. Three formulations are used to

represent the oxygen attenuation (o2 is used to determine oxygen attenuation in the

hyporheic zone). The minimum value is then used to compute the nutrient attenuation

coefficient,

Nh min

c f ,2

k c

f ,2

sCh

, Foxrh

(210)

where ksNh = nitrogen half-saturation constant [gN/L] and ksPh = phosphorus halfsaturation constant [gP/L], k sCh = fast-reacting dissolved CBOD half-saturation

constant (mgO2/L), and Foxrh = the oxygen attenuation factor [dimensionless number

between 0 and 1].

Detritus (mo)

74

lost from the hyporheic pore water via dissolution. The net gain or loss from the

hyporheic sediment zone (Smo,2) is calculated as

S mo , 2 rda PhytoDeath 2 DetrDiss 2

(211)

where

DetrDiss 2 k dc (T ) mo , 2

(212)

Slow-reacting CBOD increases due to detritus dissolution. It is lost via hydrolysis. The

net gain or loss in the hyporheic sediment zone (Scs,2) is calculated as

S cs , 2 rcd DetrDiss 2 SlowCHydr2 SlowCOxid 2

(213)

where

SlowCHydr2 k hc (T )cs , 2

(214)

(215)

where khc(T) = the temperature-dependent slow CBOD hydrolysis rate [/d], kdcs(T) = the

temperature-dependent fast CBOD oxidation rate [/d] and Foxcf = attenuation due to low

oxygen [dimensionless].

Fast-reacting CBOD is gained via the hydrolysis of slowly-reacting CBOD. It is lost via

oxidation by suspended bacteria, oxidation from the net growth of the biofilm of

heterotrophic bacteria, and denitrification. The net gain or loss from the hyporheic

sediment zone (Scf,2) is calculated as

S cf , 2 SlowCHydr2 FastCOxid 2 rod HeteroGrow

Ast ,i

V2 ,i

rondn Denitr2

(216)

FastCOxid 2 Foxcf , 2 kcf (T )c f , 2

(217)

where kcf(T) = the temperature-dependent fast carbon oxidation rate [/d] and Foxcf =

attenuation due to low oxygen [dimensionless]. Oxygen attenuation (Foxcf) is represented

with the oxygen dependency represented by the parameter Ksocf with o2 in the hyporheic

QUAL2K

75

zone. The parameter rondn is the ratio of oxygen equivalents of carbon lost per nitrate

nitrogen that is denitrified. The term Denitr is the rate of denitrification [gN/L/d]. It

will be defined in the water column section on Nitrate Nitrogen.

Organic nitrogen increases due to detritus dissolution. It is lost via hydrolysis. The net

gain or loss from the hyporheic sediment zone (Sno,2) is calculated as

S no , 2 rnd DetrDiss 2 ONHydr2

(218)

ONHydr2 k hn (T )no , 2

(219)

Ammonia nitrogen increases due to organic nitrogen hydrolysis and respiration of

phytoplankton. It is lost via nitrification. The net gain or loss from the hyporheic

sediment zone (Sna,2) is calculated as

S na , 2 ONHydr2 rna PhytoResp 2 NH4Nitrif 2

(220)

NH4Nitrif 2 Foxna , 2 k na (T ) na , 2

(221)

where kna(T) = the temperature-dependent nitrification rate for ammonia nitrogen [/d] and

Foxna = attenuation due to low oxygen [dimensionless]. Oxygen attenuation is modeled

with the oxygen dependency represented by the parameter Ksona.

Nitrate nitrogen increases due to nitrification of ammonia. It is lost via denitrification.

The net gain or loss from the hyporheic sediment zone (Snn,2) is calculated as

S nn , 2 NH4Nitrif 2 Denitr2

(222)

Denitr2

c f ,2

0 .1 c f , 2

(1 Foxdn , 2 )k dn (T )nn , 2

(223)

76

where kdn(T) = the temperature-dependent denitrification rate of nitrate nitrogen [/d] and

Foxdn = effect of low oxygen on denitrification [dimensionless] as modeled with the

oxygen dependency represented by the parameter Ksodn.

Organic phosphorus increases due to dissolution of detritus. It is lost via hydrolysis. The

net gain or loss for the hyporheic sediment zone (Spo,2) is calculated as

S po , 2 rpd DetrDiss 2 OPHydr2

(224)

where

OPHydr2 k hp (T ) po , 2

(225)

Inorganic phosphorus in the hyporheic sediment zone increases due to organic

phosphorus hydrolysis and respiration of phytoplankton. The net gain in the hyporheic

sediment zone (Spi,2) is calculated as

S pi , 2 OPHydr2 rpa PhytoResp 2

(226)

Dissolved oxygen is lost via oxidation of fast and slow CBOD by suspended bacteria, and

the net effect of growth and respiration of heterotrophic bacteria. It is also lost due to

nitrification, phytoplankton respiration, and oxidation of non-carbonaceous nonnitrogenous chemical oxygen demand (COD). The loss of dissolved oxygen from the

hyporheic sediment zone (So,2) is calculated as

S o , 2 SlowCOxid 2 FastCOxid 2 rod HeteroGrow

Ast ,i

V2,i

(227)

The term CODoxid2 is the COD oxidation (mgO2/L/d) as defined in the section below on

the generic constituent.

Pathogen (x)

QUAL2K

77

Pathogens are subject to death in the hyporheic sediment zone. The loss in the hyporheic

zone (Sx,2) is computed as

S x , 2 PathDeath 2

(228)

Pathogen death is due to natural die-off. The death of pathogens in the absence of light is

modeled as a first-order temperature-dependent decay,

PathDeath 2 k dx (T ) x2

(229)

A generic constituent is available for optional use. The user has the option of either

assuming that the generic constituent has no interaction with other state variables, or it

can be treated as a non-carbonaceous non-nitrogenous chemical oxygen demand (COD).

The generic constituent is also subject to first-order decay and settling in the hyporheic

zone,

S gen , 2 k gen (T ) gen2

(230)

If the generic constituent is used as COD, then the COD oxidation rate (mgO2/L/d) is

determined by

CODoxid 2 k gen (T ) gen

(231)

pH

The equilibrium, mass balance, and electroneutrality equations described in the water

column section on pH are used to determine the pH in the hyporheic pore water.

Total inorganic carbon concentration (cT) increases due to fast carbon oxidation from

suspended bacteria and the net growth of heterotrophic bacteria. It is also gained due to

the respiration of phytoplankton. The net gain in the hyporheic sediment zone (ScT,2) is

calculated as

78

rccd HeteroGrow

Ast ,i

V 2 ,i

(232)

rcca PhytoResp 2

The stoichiometric coefficients are derived in the water column section on Total

Inorganic Carbon.

Alkalinity (Alk)

Changes in alkalinity in the hyporheic zone are due to phytoplankton respiration,

nitrification, and denitrification. The net gain or loss for the hyporheic sediment zone

(Salk,2) is calculated as

S alk , 2 ralkaa PhytoResp 2 ralkn NH4Nitr2 ralkdn Denitr2

(233)

where the rs are ratios that translate the processes into the corresponding amount of

alkalinity. The stoichiometric coefficients are derived the water column section on in

Alkalinity.

(Level 2)

The metabolism of microbial assemblages in the hyporheic zones of streams and rivers

can influence the concentrations of nutrients, carbon, and dissolved oxygen of the

overlying water column. Naegeli and Uehlinger (1997) reported hyporheic respiration

rates that ranged from 3.9 to 5.9 g O2 m-2 d-1 and contributed 76-96% of the whole

ecosystem respiration in a sixth-order gravel bed river in Switzerland. Grimm and Fisher

(1984) found that respiration in hyporheic sediments accounted for at least half of the

whole ecosystem respiration in a fourth-order Arizona stream. Mulholland et al. (1997)

showed that ecosystem respiration rates and nutrient uptake rates are strongly correlated

with the rate of water exchange between the surface water and the hyporheic transient

storage zone.

The organic matter in the hyporheic zones can be attributed to three main pools: plant

tissue, biofilm, and sediment fauna (Spacil and Rulik, 1997). Biofilms of heterotrophic

bacteria typically make up most of the biomass of the hyporheic community (Leichtfried,

1988, 1991). The growth of heterotrophic biofilms involves the consumption of organic

carbon, uptake of nutrients and dissolved oxygen, and excretion of inorganic carbon.

Endogenous respiration of heterotrophic organisms involves uptake of dissolved oxygen

and excretion of nutrients. Death of heterotrophic organisms contributes to the detritus

(POM) in the ecosystem.

The Level 2 option in Q2K includes simulation of heterotrophic bacteria biofilm growth

(zero-order or first-order), respiration, and death, with attenuation of growth from

QUAL2K

79

temperature, DOC, dissolved oxygen, ammonia, nitrate, and inorganic phosphorus. The

Level 2 option simulates the biofilm concentration of heterotrophic bacteria in the

hyporheic zone as a state variable.

The mathematical relationships that describe the individual reactions and concentrations

of the model state variables (Table 5) for Level 2 simulation of water quality constituents

in the hyporheic pore water are presented in the following paragraphs.

By definition, conservative substances are not subject to reactions. Therefore the net gain

or loss in the hyporheic sediment zone (Ss,2) is calculated as

Ss,2 = 0

(234)

Phytoplankton (ap)

Phytoplankton are lost via respiration and death. The net gain or loss in the hyporheic

sediment zone (Sap,2) is calculated as

S ap , 2 PhytoResp2 PhytoDeath 2

(235)

Losses

Respiration. Phytoplankton respiration is represented as a first-order rate that is

attenuated at low oxygen concentration. Phytoplankton respiration in the hyporheic

sediment zone is calculated as

PhytoResp2 Foxrp , 2 k rp (T ) a p , 2

(236)

where krp(T) = temperature-dependent phytoplankton respiration rate [/d] (Ti,2 is used for

temperature adjustment of all rates in the hyporheic sediment zone of a reach) and Foxrp,2

= attenuation in the hyporheic zone due to low oxygen. Three formulations are used to

represent the oxygen attenuation (o2 is used to determine oxygen attenuation in the

hyporheic zone).

Death. Phytoplankton death is represented as a first-order rate. Death in the hyporheic

sediment zone is calculated as

PhytoDeath 2 k dp (T ) a p , 2

(237)

80

The Level 2 option of Q2K includes simulation of the biofilm of heterotrophic (aerobic)

bacteria as a state variable. Heterotrophic bacteria in the hyporheic sediment zone grow

due to the uptake of fast-reacting dissolved organic carbon. This functional group of

bacteria utilizes oxygen in their growth and respiration and represents a diverse crosssection of microorganisms. They are lost via respiration and death.

S ah HeteroGrow HeteroResp HeteroDeath

(238)

Growth

The representation of the growth of the heterotrophic bacteria is an adaptation of a model

developed by Rutherford et al. (1999). Growth is based on a temperature-corrected, zeroorder or first-order rate attenuated by nutrient and substrate concentrations. The Rates

sheet of QUAL2Kw allows the user to select either a zero-order or first-order growth rate

model, and the appropriate maximum growth rates are entered on the Reach sheet. If a

zero-order growth model is selected on the Rates sheet, then the following equations

represent the growth rate:

HeteroGrow C gh (T ) Nh rdo

(239)

heterotrophic bacteria [in terms of the equivalent amount of oxygen oxidized gO2m-2 d-1)],

and Nh = the heterotrophic bacteria nutrient/substrate attenuation factor [dimensionless

number between 0 and 1].

If a first-order growth rate is specified on the Rates sheet, then the following equation is

used to represent growth:

HeteroGrow k gh (T ) Nh Sh a h

(240)

where khb(T) = the maximum growth rate of the biofilm of heterotrophic bacteria at

temperature T [d-1], and Nh = the heterotrophic bacteria nutrient/substrate attenuation

factor [dimensionless number between 0 and 1], and Sh = biofilm space limitation

attenuation factor.

Temperature Effect. As for the first-order reactions described in the water column

section on Temperature Effects on Reactions, an Arrhenius model is employed to quantify

the effect of temperature if a zero-order growth model is selected:

C gh (T ) C h ( 20) T 20

(241)

growth limitation due to inorganic nitrogen and phosphorus, fast-reacting CBOD, and

oxygen attenuation. Three formulations are used to represent the oxygen attenuation (o2

QUAL2K

81

is used to determine oxygen attenuation in the hyporheic zone). The minimum value is

then used to compute the nutrient attenuation coefficient,

c f ,2

na , 2 nn , 2

pi , 2

,

,

, Foxrh

k n n

a ,2

n , 2 k sPh pi , 2 k sCh c f , 2

sNh

Nh min

(242)

where ksNh = nitrogen half-saturation constant [gN/L] and ksPh = phosphorus halfsaturation constant [gP/L], k sCh = fast-reacting CBOD half-saturation constant

(mgO2/L), and Foxrh = the oxygen attenuation factor [dimensionless number between 0 and

1].

Space Limitation. If a first-order growth model is used, a term must be included to

impose a space limitation on the biomass of heterotrophic biofilm. A logistic model is

used for this purpose as in

Sh 1

ah

ah ,max

Losses

Respiration. Endogenous respiration of heterotrophic bacteria is represented as a firstorder rate that is attenuated at low oxygen concentration,

HeteroResp Foxrh k rh (T ) ah

(243)

where krh(T) = temperature-dependent heterotrophic bacteria respiration rate [/d] and Foxrh

= attenuation due to low oxygen [dimensionless].

Death. Heterotrophic bacteria death is represented as a first-order rate,

HeteroDeath k dh (T )ah

(244)

Detritus (mo)

Detritus or particulate organic matter (POM) increases due to plant or bacteria death. It is

lost from the hyporheic pore water via dissolution. The net gain or loss from the

hyporheic sediment zone (Smo,2) is calculated as

82

Ast ,i

V2 , i

DetrDiss 2

(245)

where

DetrDiss 2 k dc (T ) mo , 2

(246)

Slow-reacting carbon increases due to detritus dissolution. It is lost via hydrolysis. The

net gain or loss in the hyporheic sediment zone (Scs,2) is calculated as

S cs , 2 rcd DetrDiss 2 SlowCHydr2 SlowCOxid 2

(247)

where

SlowCHydr2 k hc (T )cs , 2

(248)

(249)

where khc(T) = the temperature-dependent slow CBOD hydrolysis rate [/d], kdcs(T) = the

temperature-dependent fast CBOD oxidation rate [/d] and Foxcf = attenuation due to low

oxygen [dimensionless].

Fast-reacting carbon is gained via the hydrolysis of slowly-reacting carbon. It is lost via

oxidation by suspended bacteria, oxidation from the growth of the biofilm of

heterotrophic bacteria, and denitrification. The net gain or loss from the hyporheic

sediment zone (Scf,2) is calculated as

S cf , 2 SlowCHydr2 FastCOxid 2 rod HeteroGrow

Ast ,i

V2 ,i

rondn Denitr2

(250)

represented as

FastCOxid 2 Foxrh k cf (T )c f , 2

(251)

where kcf(T) = the temperature-dependent fast carbon oxidation rate [/d] and Foxrh =

attenuation due to low oxygen [dimensionless]. The parameter rondn is the ratio of oxygen

equivalents of carbon lost per nitrate nitrogen that is denitrified. The term Denitr is the

rate of denitrification [gN/L/d]. It will be defined Nitrate Nitrogen.

QUAL2K

83

Organic nitrogen increases due to detritus dissolution. It is lost via hydrolysis. The net

gain or loss from the hyporheic sediment zone (Sno,2) is calculated as

S no , 2 rnd DetrDiss 2 ONHydr2

(252)

ONHydr2 k hn (T )n o , 2

(253)

Ammonia nitrogen increases due to organic nitrogen hydrolysis and respiration of

phytoplankton and heterotrophic bacteria. It is lost via nitrification and growth of

heterotrophic bacteria. The net gain or loss from the hyporheic sediment zone (Sna,2) is

calculated as

S na , 2 ONHydr2 rna PhytoResp 2 NH4Nitrif 2

rnd [ HeteroResp Pah HeteroGrow]

Ast ,i

(254)

V 2 ,i

NH4Nitrif 2 Foxna , 2 k na (T ) na , 2

(255)

where kna(T) = the temperature-dependent nitrification rate for ammonia nitrogen [/d] and

Foxna = attenuation due to low oxygen [dimensionless]. Oxygen attenuation is modeled

with the oxygen dependency represented by the parameter Ksona.

The coefficient Pah is the preferences for ammonium as a nitrogen source for

heterotrophic bacteria:

Pah

(k hnxh

na , 2 nn , 2

na , 2 k hnxh

(256)

84

and the growth of heterotrophic bacteria. The net gain or loss from the hyporheic

sediment zone (Snn,2) is calculated as

S nn , 2 NH4Nitrif 2 Denitr2 rnd (1 Pah ) HeteroGrow

Ast ,i

(257)

V2,i

Denitr2

c f ,2

0 .1 c f , 2

(1 Foxdn , 2 )k dn (T )nn , 2

(258)

where kdn(T) = the temperature-dependent denitrification rate of nitrate nitrogen [/d] and

Foxdn = effect of low oxygen on denitrification [dimensionless] as modeled by Eqs. (82) to

(84) with the oxygen dependency represented by the parameter Ksodn.

Dissolved organic phosphorus increases due to dissolution of detritus. It is lost via

hydrolysis. The net gain or loss for the hyporheic sediment zone (Spo,2) is calculated as

S po , 2 rpd DetrDiss 2 OPHydr2

(259)

where

OPHydr2 k hp (T ) po , 2

(260)

Inorganic phosphorus in the hyporheic sediment zone increases due to dissolved organic

phosphorus hydrolysis and respiration of phytoplankton and heterotrophic bacteria. It is

lost via growth of heterotrophic bacteria. The net gain or loss in the hyporheic sediment

zone (Spi,2) is calculated as

S pi , 2 OPHydr2 rpa PhytoResp 2 rpd [HeteroResp HeteroGrow]

Ast ,i

V2 ,i

(261)

Dissolved oxygen is lost via oxidation of fast and slow CBOD by suspended bacteria, and

growth and respiration of heterotrophic bacteria. It is also lost due to nitrification,

phytoplankton respiration, and oxidation of non-carbonaceous non-nitrogenous chemical

QUAL2K

85

oxygen demand (COD). The loss of dissolved oxygen from the hyporheic sediment zone

(So,2) is calculated as

S o , 2 SlowCOxid 2 FastCOxid 2 [ro d HeteroGrow rod HeteroResp]

Ast ,i

V 2 ,i

(262)

The term CODoxid2 is the COD oxidation (mgO2/L/d) as defined in the section below on

the generic constituent.

Pathogen (x)

Pathogens are subject to death in the hyporheic sediment zone. The loss in the hyporheic

zone (Sx,2) is computed as

S x , 2 PathDeath 2

(263)

Pathogen death is due to natural die-off. The death of pathogens in the absence of light is

modeled as a first-order temperature-dependent decay,

PathDeath 2 k dx (T ) x2

(264)

A generic constituent is available for optional use. The user has the option of either

assuming that the generic constituent has no interaction with other state variables, or it

can be treated as a non-carbonaceous non-nitrogenous chemical oxygen demand (COD).

The generic constituent is also subject to first-order decay and settling in the hyporheic

zone,

S gen , 2 k gen (T ) gen2

(265)

If the generic constituent is used as COD, then the COD oxidation rate (mgO2/L/d) is

determined by

CODoxid 2 k gen (T ) gen

(266)

86

pH

The equilibrium, mass balance, and electroneutrality equations described in the water

column section on pH are used to determine the pH in the hyporheic pore water.

Total inorganic carbon concentration (cT) increases due to fast carbon oxidation from

suspended bacteria and the growth and respiration of heterotrophic bacteria. It is also

gained due to the respiration of phytoplankton. The net gain in the hyporheic sediment

zone (ScT,2) is calculated as

S cT , 2 rccoSlowCOxid 2 rcco FastCOxid 2

rccd [HeteroGrow HeteroResp]

Ast ,i

V 2 ,i

(267)

rcca PhytoResp 2

The stoichiometric coefficients are derived in the water column section on Total

Inorganic Carbon.

Alkalinity (Alk)

Changes in alkalinity in the hyporheic zone are due to phytoplankton respiration,

heterotrophic bacteria growth and respiration, nitrification, and denitrification. The net

gain or loss for the hyporheic sediment zone (Salk,2) is calculated as

S alk , 2 ralkaa PhytoResp 2

[ ralkda Pah ralkdn (1 Pah ) HeteroGrow ralkda HeteroResp]

Ast ,i

V2 ,i

(268)

where the rs are ratios that translate the processes into the corresponding amount of

alkalinity. The stoichiometric coefficients are derived from in the water column section

on Alkalinity.

QUAL2K

87

Automatic calibration

Q2K uses a genetic algorithm to determine the optimum values for the kinetic rate

parameters for the model state variables in Table 5. Pelletier et al. (2006) describe the

genetic algorithm in Q2K.

Genetic algorithms are a class of search techniques that can be used to construct

numerical optimization techniques. The genetic algorithm used in Q2K is the public

domain subroutine PIKAIA (Charbonneau and Knapp, 1995). The genetic algorithm finds

the set of selected kinetic rate parameters that maximize the goodness of fit of the model

results compared with measured data. Detailed documentation of the PIKAIA algorithm

is available in Charbonneau and Knapp (1995) and the PIKAIA Web site at the following

link:

http://www.hao.ucar.edu/public/research/si/pikaia/pikaia.html

The genetic algorithm carries out its maximization task on a user-selected number of

model runs to define a population. This population size remains constant throughout the

evolutionary process. Rather than evolving the population until some preset tolerance

criterion is satisfied, the genetic algorithm carries the evolution forward over a userspecified number of generations.

Sediment nutrient fluxes and sediment oxygen demand (SOD) are based on a model

developed by Di Toro (Di Toro et al. 1991, Di Toro and Fitzpatrick. 1993, Di Toro 2001).

The present version also benefited from James Martins (Mississippi State University,

personal communication) efforts to incorporate the Di Toro approach into EPAs WASP

modeling framework.

A schematic of the model is depicted in Figure 22. As can be seen, the approach

allows oxygen and nutrient sediment-water fluxes to be computed based on the

downward flux of particulate organic matter from the overlying water. The sediments are

divided into 2 layers: a thin ( 1 mm) surface aerobic layer underlain by a thicker (10 cm)

lower anaerobic layer. Organic carbon, nitrogen and phosphorus are delivered to the

anaerobic sediments via the settling of particulate organic matter (i.e., phytoplankton and

detritus). There they are transformed by mineralization reactions into dissolved methane,

ammonium and inorganic phosphorus. These constituents are then transported to the

aerobic layer where some of the methane and ammonium are oxidized. The flux of

oxygen from the water required for these oxidations is the sediment oxygen demand. The

following sections provide details on how the model computes this SOD along with the

sediment-water fluxes of carbon, nitrogen and phosphorus that are also generated in the

process.

88

cf o

AEROBIC

WATER

Jpom

CH4

CO2

nn

pi

NH4p

NH4d

NO3

N2

NH4p

NH4d

NO3

N2

PO4p

PO4d

PO4p

PO4d

CH4(gas)

POC

ANAEROBIC

na

PON

POP

DIAGENESIS

METHANE

AMMONIUM

NITRATE

PHOSPHATE

Diagenesis

As summarized in Figure 23, the first step in the computation involves determining

how much of the downward flux of particulate organic matter (POM) is converted into

soluble reactive forms in the anaerobic sediments. This process is referred to as

diagenesis. First the total downward flux is computed as the sum of the fluxes of

phytoplankton and detritus settling from the water column

J POM rda v a a p v dt m o

(269)

where JPOM = the downward flux of POM [gD m2 d1], rda = the ratio of dry weight to

chlorophyll a [gD/mgA], va = phytoplankton settling velocity [m/d], ap = phytoplankton

concentration [mgA/m3], vdt = detritus settling velocity [m/d], and mo = detritus

concentration [gD/m3].

QUAL2K

89

vaap

vdtmo

fG1

rda

JPOC

fG3

roc

JPOM

fG2

rcd

fG1

rnd

JPON

fG2

fG3

rpd

fG1

JPOP

fG2

fG3

JPOC, G1

POC2,G1

JPOC, G2

POC2,G2

JPOC, G3

POC2,G3

JPON, G1

PON2,G1

JPON, G2

PON2,G2

JPON, G3

PON2,G3

JPOP, G1

POP2,G1

JPOP, G2

POP2,G2

JPOP, G3

POP2,G3

JC, G1

JC, G2

JC

JN, G1

JN, G2

JN

JP, G1

JP, G2

JP

detritus) are transformed into fluxes of dissolved carbon (JC) , nitrogen (JN) and

phosphorus (JP) in the anaerobic sediments.

Stoichiometric ratios are then used to divide the POM flux into carbon, nitrogen and

phosphorus. Note that for convenience, we will express the particulate organic carbon

(POC) as oxygen equivalents using the stoichiometric coefficient roc. Each of the nutrient

fluxes is further broken down into three reactive fractions: labile (G1), slowly reacting

(G2) and non-reacting (G3).

These fluxes are then entered into mass balances to compute the concentration of

each fraction in the anaerobic layer. For example, for labile POC, a mass balance is

written as

H2

dPOC 2,G1

dt

T 20

J POC ,G1 k POC ,G1 POC

,G1 H 2 POC 2 ,G1 w2 POC 2 ,G1

(270)

where H2 = the thickness of the anaerobic layer [m], POC2,G1 = the concentration of the

labile fraction of POC in the anaerobic layer [gO2/m3], JPOC,G1 = the flux of labile POC

delivered to the anaerobic layer [gO2/m2/d], kPOC,G1 = the mineralization rate of labile POC

[d1], POC,G1 = temperature correction factor for labile POC mineralization

[dimensionless], and w2 = the burial velocity [m/d]. At steady state, Eq. 191 can be solved

for

POC 2,G1

J POC ,G1

T 20

k POC ,G1 POC

,G1 H 2 v b

(271)

90

The flux of labile dissolved carbon, JC,G1 [gO2/m2/d], can then be computed as

T 20

J C ,G1 k POC ,G1 POC

,G1 H 2 POC 2 ,G1

(272)

In a similar fashion, a mass balance can be written and solved for the slowly reacting

dissolved organic carbon. This result is then added to Eq. 193 to arrive at the total flux of

dissolved carbon generated in the anaerobic sediments.

J C J C ,G1 J C ,G 2

(273)

[gN/m2/d], and phosphorus JP [gP/m2/d].

Ammonium

Based on the mechanisms depicted in Figure 22, mass balances can be written for total

ammonium in the aerobic layer and the anaerobic layers,

H1

dNH 4,1

dt

K NH 4

o

na

NH 4,1 T 20

s

f da1 NH 4,1

NH 4

f da1 NH 4,1

s

K NH 4 NH 4,1 2 K NH 4,O 2 o

1000

(274)

H2

dNH 4, 2

dt

w2 NH 4,1 NH 4, 2

(275)

where H1 = the thickness of the aerobic layer [m], NH4,1 and NH4,2 = the concentration of

total ammonium in the aerobic layer and the anaerobic layers, respectively [gN/m3], na =

the ammonium concentration in the overlying water [mgN/m3], NH4,1 = the reaction

velocity for nitrification in the aerobic sediments [m/d], NH4 = temperature correction

factor for nitrification [dimensionless], KNH4 = ammonium half-saturation constant

[gN/m3], o = the dissolved oxygen concentration in the overlying water [gO2/m3], and

KNH4,O2 = oxygen half-saturation constant [mgO2/L], and JN = the diagenesis flux of

ammonium [gN/m2/d].

The fraction of ammonium in dissolved (fdai) and particulate (fpai) form are computed

as

QUAL2K

91

f dai

1

1 mi ai

(276)

f pai 1 f dai

(277)

where mi = the solids concentration in layer i [gD/m3], and ai = the partition coefficient

for ammonium in layer i [m3/gD].

The mass transfer coefficient for particle mixing due to bioturbation between the

layers, 12 [m/d], is computed as

12

T 20

D p Dp

POC 2,G1 / roc

H2

POC R

o

K M , Dp o

(278)

[dimensionless], POCR = reference G1 concentration for bioturbation [gC/m3] and KM,Dp =

oxygen half-saturation constant for bioturbation [gO2/m3].

The mass transfer coefficient for pore water diffusion between the layers, KL12 [m/d],

is computed as,

K L12

T 20

D d Dd

H2 / 2

(279)

[dimensionless].

The mass transfer coefficient between the water and the aerobic sediments, s [m/d], is

computed as

s

SOD

o

(280)

At steady state, Eqs. 195 and 196 are two simultaneous nonlinear algebraic equations.

The equations can be linearized by assuming that the NH4,1 term in the Monod term for

nitrification is constant. The simultaneous linear equations can then be solved for NH4,1

and NH4,2. The flux of ammonium to the overlying water can then be computed as

n

J NH 4 s f da1 NH 4,1 a

1000

(281)

92

Nitrate

Mass balances for nitrate can be written for the aerobic and anaerobic layers as

H1

dNO3,1

dt

nn

NO3,1

1000

2

NO

o

3,1 T 20

f da1 NH 4,1

NO 3 NO3,1

2 K NH 4,O 2 o

s

2

NH

4 ,1

T 20

NH

4

K NH 4

K NH 4 NH 4,1

(282)

H2

dNO3, 2

dt

T 20

J N K L12 NO3,1 NO3, 2 w2 NO3,1 NO3, 2 NO 3, 2 NO

3 NO3, 2

(283)

where NO3,1 and NO3,2 = the concentration of nitrate in the aerobic layer and the anaerobic

layers, respectively [gN/m3], nn = the nitrate concentration in the overlying water

[mgN/m3], NO3,1 and NO3,2 = the reaction velocities for denitrification in the aerobic and

anaerobic sediments, respectively [m/d], and NO3 = temperature correction factor for

denitrification [dimensionless].

In the same fashion as for Eqs. 195 and 196, Eqs. 203 and 204 can be linearized and

solved for NO3,1 and NO3,2. The flux of nitrate to the overlying water can then be

computed as

n

J NO 3 s NO3,1 n

1000

(284)

equation,

5CH 2 O 4NO 3 4H 5CO 2 2N 2 7H 2 O

(285)

The carbon requirement (expressed in oxygen equivalents per nitrogen) can therefore be

computed as

rondn 2.67

gO 2 5 moleC 12 gC/moleC

gO 2

1 gN

0.00286

gC 4 moleN 14 gN/moleN 1000 mgN

mgN

(286)

Therefore, the oxygen equivalents consumed during denitrification, JO2,dn [gO2/m2/d], can

be computed as

J O 2, dn 1000

QUAL2K

2

NO

mgN

3,1

T 20

T 20

rondn

NO

3 NO3,1 NO 3, 2 NO 3 NO3, 2

gN

s

93

(287)

Methane

The dissolved carbon generated by diagenesis is converted to methane in the anaerobic

sediments. Because methane is relatively insoluble, its saturation can be exceeded and

methane gas produced. As a consequence, rather than write a mass balance for methane in

the anaerobic layer, an analytical model developed by Di Toro et al. (1990) is used to

determine the steady-state flux of dissolved methane corrected for gas loss delivered to

the aerobic sediments.

First, the carbon diagenesis flux is corrected for the oxygen equivalents consumed

during denitrification,

J CH 4,T J C J O 2, dn

(288)

where JCH4,T = the carbon diagenesis flux corrected for denitrification [gO2/m2/d]. In other

words, this is the total anaerobic methane production flux expressed in oxygen

equivalents.

If JCH4,T is sufficiently large ( 2KL12Cs), methane gas will form. In such cases, the flux

can be corrected for the gas loss,

J CH 4,d

(289)

2 K L12 C s J CH 4 ,T

where JCH4,d = the flux of dissolved methane (expressed in oxygen equivalents) that is

generated in the anaerobic sediments and delivered to the aerobic sediments [gO2/m2/d],

Cs = the saturation concentration of methane expressed in oxygen equivalents [mgO2/L].

If JCH4,T < 2KL12Cs, then no gas forms and

J CH 4, d J CH 4,T

(290)

H

20 T

C s 100 1

1.024

10

(291)

A methane mass balance can then be written for the aerobic layer as

H1

dCH 4,1

dt

J CH 4, d s c f CH 4,1

2

CH

4 ,1

T 20

CH

4 CH 4,1

(292)

where CH4,1 = methane concentration in the aerobic layer [gO2/m3], cf = fast CBOD in the

overlying water [gO2/m3], CH4,1 = the reaction velocity for methane oxidation in the

94

steady, state, this balance can be solved for

J CH 4, d sc f

CH 4,1

2

CH

4 ,1

(293)

T 20

CH

4

The flux of methane to the overlying water, JCH4 [gO2/m2/d], can then be computed as

J CH 4 s CH 4,1 c f

(294)

SOD

The SOD [gO2/m2/d] is equal to the sum of the oxygen consumed in methane oxidation

and nitrification,

SOD CSOD NSOD

(295)

[gO2/m2/d] and NSOD = the amount of oxygen demand generated by nitrification

[gO2/m2/d]. These are computed as

CSOD

2

CH

4 ,1

NSOD ron

T 20

CH

4 CH 4 ,1

2

NH

4,1

T 20

NH

4

(296)

K NH 4

o

f da1 NH 4,1

K NH 4 NH 4,1 2 K NH 4,O 2 o

(297)

where ron = the ratio of oxygen to nitrogen consumed during nitrification [= 4.57

gO2/gN].

Inorganic Phosphorus

Mass balances can be written total inorganic phosphorus in the aerobic layer and the

anaerobic layers as

H1

dPO4,1

dt

w2 PO4,1

QUAL2K

95

pi

s

f da1 PO4,1

1000

(298)

H2

dPO4, 2

dt

w2 PO4,1 PO4, 2

(299)

where PO4,1 and PO4,2 = the concentration of total inorganic phosphorus in the aerobic

layer and the anaerobic layers, respectively [gP/m3], pi = the inorganic phosphorus in the

overlying water [mgP/m3], and JP = the diagenesis flux of phosphorus [gP/m2/d].

The fraction of phosphorus in dissolved (fdpi) and particulate (fppi) form are computed

as

f dpi

1

1 mi pi

f ppi 1 f dpi

(300)

(301)

The partition coefficient in the anaerobic layer is set to an input value. For the aerobic

layer, if the oxygen concentration in the overlying water column exceeds a critical

concentration, ocrit [gO2/m3], then the partition coefficient is increased to represent the

sorption of phosphorus onto iron oxyhydroxides as in

p1 p 2 PO 4,1

(302)

where PO4,1 is a factor that increases the aerobic layer partition coefficient relative to

the anaerobic coefficient.

If the oxygen concentration falls below ocrit then the partition coefficient is decreased

smoothly until it reaches the anaerobic value at zero oxygen,

p1 p 2 PO 4,1 o / ocrit

(303)

Equations 219 and 220 can be solved for PO4,1 and PO4,2. The flux of phosphorus to

the overlying water can then be computed as

p

J PO 4 s PO4,1 i

1000

(304)

Solution Scheme

96

Although the foregoing sequence of equations can be solved, a single computation will

not yield a correct result because of the interdependence of the equations. For example,

the surface mass transfer coefficient s depends on SOD. The SOD in turn depends on the

ammonium and methane concentrations which themselves are computed via mass

balances that depend on s. Hence, an iterative technique must be used. The procedure

used in QUAL2K is

1. Determine the diagenesis fluxes: JC, JN and JP.

2. Start with an initial estimate of SOD,

SODinit J C ron' J N

(305)

where ron = the ratio of oxygen to nitrogen consumed for total conversion of

ammonium to nitrogen gas via nitrification/denitrification [= 1.714 gO2/gN]. This

ratio accounts for the carbon utilized for denitrification.

3. Compute s using

s

SODinit

o

(306)

4. Solve for ammonium, nitrate and methane, and compute the CSOD and NSOD.

5. Make a revised estimate of SOD using the following weighted average

SOD

2

(307)

a

SOD SODinit

100%

SOD

(308)

7. If a is greater than a prespecified stopping criterion s then set SODinit = SOD and

return to step 2.

8. If convergence is adequate (a s), then compute the inorganic phosphorus

concentrations.

9. Compute the ammonium, nitrate, methane and phosphate fluxes.

Supplementary Fluxes

QUAL2K

97

Because of the presence of organic matter deposited prior to the summer steady-state

period (e.g., during spring runoff), it is possible that the downward flux of particulate

organic matter is insufficient to generate the observed SOD. In such cases, a

supplementary SOD can be prescribed,

SODt SOD SOD s

(309)

where SODt = the total sediment oxygen demand [gO2/m2/d], and SODs = the

supplementary SOD [gO2/m2/d]. In addition, prescribed ammonia and methane fluxes can

be used to supplement the computed fluxes.

98

REFERENCES

Adams, E.E., D. J. Cosler, and K.R. Helfrich. 1987. "Analysis of evaporation data from

heated ponds", cs-5171, research project 2385-1, Electric Power Research Institute,

Palo Alto, California 94304. April.

Andrews and Rodvey, 1980. Heat exchange between water and tidal flats. D.G.M 24(2).

(in German)

Asaeda, T., and T. Van Bon, Modelling the effects of macrophytes on algal blooming in

eutrophic shallow lakes. Ecol Model 104: 261-287, 1997.

Baly, E.C.C. 1935. The Kinetics of Photosynthesis. Proc. Royal Soc. London Ser. B,

117:218-239.

Banks, R. B. 1975. "Some Features of Wind Action on Shallow Lakes." J. Environ Engr.

Div. ASCE. 101(EE5): 813-827.

Banks, R. B. and Herrera, F. F. 1977. "Effect of Wind and Rain on Surface Reaeration."

J. Environ Engr. Div. ASCE. 103(EE3): 489-504.

Barnwell, T.O., Brown, L.C., and Mareck, W. 1989). Application of Expert Systems

Technology in Water Quality Modeling. Water Sci. Tech. 21(8-9):1045-1056.

Bejan, A. 1993. Heat Transfer. Wiley, New York, NY.

Bencala, K.E. and R.A. Walters. 1983. Simulation of solute transport in a mountain

pool-and-riffle stream: a transient storage model. Water Resources Research 19:718724.

Bowie, G.L., Mills, W.B., Porcella, D.B., Campbell, C.L., Pagenkopf, J.R., Rupp, G.L.,

Johnson, K.M., Chan, P.W.H., Gherini, S.A. and Chamberlin, C.E. 1985. Rates,

Constants, and Kinetic Formulations in Surface Water Quality Modeling. U.S. Envir.

Prot. Agency, ORD, Athens, GA, ERL, EPA/600/3-85/040.

Brady, D.K., Graves, W.L., and Geyer, J.C. 1969. Surface Heat Exchange at Power Plant

Cooling Lakes, Cooling Water Discharge Project Report, No. 5, Edison Electric Inst.

Pub. No. 69-901, New York, NY.

Bras, R.L. 1990. Hydrology. Addison-Wesley, Reading, MA.

Brown, L.C., and Barnwell, T.O. 1987. The Enhanced Stream Water Quality Models

QUAL2E and QUAL2E-UNCAS, EPA/600/3-87-007, U.S. Environmental Protection

Agency, Athens, GA, 189 pp.

Brunt, D. 1932. Notes on radiation in the atmosphere: I. Quart J Royal Meteorol Soc

58:389-420.

Brutsaert, W. 1982. Evaporation into the atmosphere: theory, history, and applications.

D.Reidel Publishing Co., Hingham MA, 299 p.

Butts, T. A. and Evans, R. L. 1983. Effects of Channel Dams on Dissolved Oxygen

Concentrations in Northeastern Illinois Streams, Circular 132, State of Illinois, Dept.

of Reg. and Educ., Illinois Water Survey, Urbana, IL.

Carslaw, H.S. and Jaeger, J.C. 1959. Conduction of Heat in Solids, Oxford Press, Oxford,

UK, 510 pp.

Cengel, Y.A. 1998 Heat Transfer: A Practical Approach. New York, McGraw-Hill.

Chapra and Canale 2002. Numerical Methods for Engineers, 4th Ed. New York, McGrawHill.

Chapra, S.C. 1997. Surface water quality modeling. New York, McGraw-Hill.

Chow, V.T., Maidment, D.R., and Mays, L.W. 1988. Applied Hydrology. New York,

McGraw-Hill, 592 pp.

Chapra, S.C. 1997. Surface Water Quality Modeling. McGraw-Hill, New York.

Chapra S.C. and R.P. Canale. 2002. Numerical Methods for Engineers. McGraw-Hill,

New York.

Chapra, S.C. and G.J. Pelletier. 2003. QUAL2K: A Modeling Framework for Simulating

River and Stream Water Quality (Beta Version): Documentation and Users Manual.

Civil and Environmental Engineering Dept., Tufts University, Medford,

MA.Churchill, M.A., Elmore, H.L., and Buckingham, R.A. 1962. The prediction of

stream reaeration rates. J. Sanit. Engrg. Div. , ASCE, 88{4),1-46.

Charbonneau, P., and Knapp, B. 1995, A User's guide to PIKAIA 1.0, NCAR Technical

Note 418+IA (Boulder: National Center for Atmospheric Research).

(http://www.hao.ucar.edu/public/research/si/pikaia/pikaia.html)

Coffaro, G. and A. Sfriso, Simulation model of Ulva rigida growth in shallow water of

the Lagoon of Venice. Ecol Model, 102: 55-66, 1997.

Covar, A. P. 1976. "Selecting the Proper Reaeration Coefficient for Use in Water Quality

Models." Presented at the U.S. EPA Conference on Environmental Simulation and

Modeling, April 19-22, 1976, Cincinnati, OH.

Crawford, T.M. and C.E. Duchon. 1999. An improved parameterization for estimating

effective atmospheric emissivity for use in calculating daytime downwelling

longwave radiation. J.Appl.Meteorol. 38, 474-480.

Culf, A.D. and J.H.C. Gash. 1993. Longwave radiation from clear skies in Niger: a

comparison of observations with simple formulas. J.Appl.Meteorol. 32, 539-547.

Di Toro, D. M. and J. F. Fitzpatrick. 1993. Chesapeake Bay sediment flux model. Tech.

Report EL-93-2, U.S. Army Corps of Engineers, Waterways Experiment Station,

Vicksburg, Mississippi, 316 pp.

Di Toro, D.M, Paquin, P.R., Subburamu, K. and Gruber, D.A. 1991. Sediment Oxygen

Demand Model: Methane and Ammonia Oxidation. J. Environ. Eng., 116(5):945-986.

Di Toro, D.M. 1978. Optics of Turbid Estuarine Waters: Approximations and

Applications. Water Res. 12:1059-1068.

Di Toro, D.M. 2001. Sediment Flux Modeling. Wiley-Interscience, New York, NY.

Droop, M.R. 1974. The nutrient status of algal cells in continuous culture.

J.Mar.Biol.Assoc. UK 54:825-855.

Ecology. 2003. Shade.xls - a tool for estimating shade from riparian vegetation.

Washington State Department of Ecology.

http://www.ecy.wa.gov/programs/eap/models/

Edinger, J.E., Brady, D.K., and Geyer, J.C. 1974. Heat Exchange and Transport in the

Environment. Report No. 14, EPRI Pub. No. EA-74-049-00-3, Electric Power

Research Institute, Palo Alto, CA.

Fernald, A.G. P.J. Wiginton, and D.H. Landers. 2001. Transient storage and hyporheic

flow along the Willamette River, Oregon: field measurements and model estimates.

Water Resources Research 37(6):1681-1694.

Finnemore, E.J. and Franzini, J.B. 2002. Fluid Mechanics with Engineering Applications,

10th Ed. New York, McGraw, Hill.

Geiger, R. 1965. The climate near the ground. Harvard University Press. Cambridge,

MA.

100

Gooseff, M.N., S.M. Wondzell, R. Haggerty, and J. Anderson. 2003. in press. Advances

in Water Resources, special issue on hyporheic zone modeling.

(cc.usu.edu/~gooseff/web_cv/ gooseff_etal_AWR_paper_color.PDF)

Gordon, N.D, T.A. McMahon, and B.L. Finlayson. 1992. Stream Hydrology, An

Introduction for Ecologists. Published by John Wiley and Sons.

Grigull, U. and Sandner, H. 1984. Heat Conduction. Springer-Verlag, New York, NY.

Grimm, N.B., and S.G. Fisher. 1984. Exchange between interstitial and surface water:

implications for stream metabolism and nutrient cycling. Hydrobiologia 111:219228.

Hamilton, D.P., and S.G. Schladow, Prediction of water quality in lakes and reservoirs. 1.

Model description. Ecol Model, 96: 91-110, 1997.

Harbeck, G. E., 1962, A practical field technique for measuring reservoir evaporation

utilizing mass-transfer theory. US Geological Survey Professional Paper 272-E, 1015.

Harned, H.S., and Hamer, W.J. 1933. The Ionization Constant of Water. J. Am., Chem.

Soc. 51:2194.

Hart, D.R. 1995. Parameter estimate and stochastic interpretation of the transient storage

model for solute transport in streams. Water Resources Research 31:323-328.

Harvey, J.W. and B.J. Wagner. 2000. Quantifying hydrologic interactions between

streams and their subsurface hyporheic zones. In: Streams and Groundwaters. Edited

by J.B. Jones and P.J. Mulholland. Academic Press.

Hatfield, J.L., R.J. Reginato, and S.B. Idso. 1983. Comparison of longwave radiation

calculation methods over the United States. Water Resources Research, 19 (1) 285288.

Helfrich, K.R., E.E. Adams, A.L. Godbey, and D.R.F. Harleman. 1982. Evaluation of

models for predicting evaporative water loss in cooling impoundments. Report CS2325, Research project 1260-17. Electric Power Research Institute, Pala Alto, CA.

March 1982.

Hellweger, F/L., K.L. Farley, U. Lall, and D.M. DiToro. 2003. Greedy algae reduce

arsenate. Limnol.Oceanogr. 48(6), 2003, 2275-2288.

Hutchinson, G.E. 1957. A Treatise on Limnology, Vol. 1, Physics and Chemistry. Wiley,

New York, NY.

Idso, S.B. 1981. A set of equations for full spectrum and 8-14 m and 10.5-12.5 m

thermal radiation from cloudless skies. Water Resources Research, 17, 295-304.

Idso, S.B. and R.D. Jackson. 1969. Thermal radiation from the atmosphere.

J.Geophys.Res., 74, 3397-5403.

Ikusima, I. (1970). Ecological studies on the productivity of aquatic plant communities

IV: Light conditions and community photosynthetic prodcution. Bot. Mag. Tokyo,

83, 330-341.

Jobson, H.E. 1977. Bed Conduction Computation for Thermal Models. J. Hydraul. Div.

ASCE. 103(10):1213-1217.

Kasahara, T. and S.M. Wondzell. 2003. Geomorphic controls on hyporheic exchange

flow in mountain streams. Water Resources Research 39(1)1005.

Koberg, G.E. 1964. Methods to compute long-wave radiation from the atmosphere and

reflected solar radiation from a water surface. US Geological Survey Professional

Paper 272-F.

QUAL2K

101

Kreith, F. and Bohn, M.S. 1986. Principles of Heat Transfer, 4th Ed. Harper and Row,

New York, NY.

Laws, E. A. and Chalup, M. S. 1990. A Microalgal Growth Model. Limnol. Oceanogr.

35(3):597-608.

Leichtfried, M. 1988. Bacterial substrates in gravel beds of a second order alpine stream

(Project Ritrodat-Lunz, Austria). Verh. Internat. Verein. Limnol. 23:1325-1332.

Leichtfried, M. 1991. POM in bed sediments of a gravel stream (Ritrodat-Lunz Study

area, Austria). Verh. Internat. Verein. Limnol. 24:1921-1925.

LI-COR, 2003. Radiation Measurement Instruments, LI-COR, Lincoln, NE, 30 pp.

Likens, G. E., and Johnson, N. M. (1969). "Measurements and analysis of the annual heat

budget for sediments of two Wisconsin lakes." Limnol. Oceanogr., 14(1):115-135.

Mackay, D. and Yeun, A.T.K. 1983. Mass Transfer Coefficient Correlations for

Volatilization of Organic Solutes from Water. Environ. Sci. Technol. 17:211-233.

Marciano, J.K. and G.E. Harbeck. 1952. Mass transfer studies in water loss investigation:

Lake Hefner studies. Geological Circular 229. U.S. Geological Survey, Washington

DC.

Meeus, J. 1999. Astronomical algorithms. Second edition. Willmann-Bell, Inc.

Richmond, VA.

Melching, C.S. and Flores, H.E. 1999. Reaeration Equations from U.S. Geological

Survey Database. J. Environ. Engin., 125(5):407-414.

Mills, A.F. 1992. Heat Transfer. Irwin, Homewood, IL.

Moog, D.B., and Iirka, G.H. 1998. Analysis of reaeration equations using mean

multiplicative error. J. Environ. Engrg., ASCE, 124(2), 104-110.

Mulholland, P.J., E.R. Marzolf, J.R. Webster, D.R. Hart, and S.P. Hendricks. 1997.

Evidence that hyporheic zones increase heterotrophic metabolism and phosphorus

uptake in forest streams. Limnol. Ocean. 42(3):443-451.

Naegili, M.W., and U. Uehlinger. 1997. Contribution of the hyporheic zone to

ecosystem metabolism in a prealpine gravel-bed river. J. N. Am. Benthol. Soc.

16(4):794-804.

Nakshabandi, G.A. and H. Kohnke. 1965. Thermal conductivity and diffusivity of soils as

related to moisture tension and other physical properties. Agr. Met. Vol 2.

O'Connor, D.J., and Dobbins, W.E. 1958. Mechanism of reaeration in natural streams.

Trans. ASCE, 123, 641-684.

Owens, M., Edwards, R.W., and Gibbs, J.W. 1964. Some reaeration studies in streams.

Int. J. Air and Water Pollution, 8, 469-486.

Pelletier, G.J., S.C. Chapra, and H.Tao. QUAL2Kw a framework for modeling water

quality in streams and rivers using a genetic algorithm for calibration. Environmental

Modelling and Software. 21(2006):419-425.

Plummer, L.N. and Busenberg, E. 1982. The Solubilities of Calcite, Aragonite and

Vaterite in CO2-H2O Solutions Between 0 and 90 oC, and an Evaluation of the

Aqueous Model for the System CaCO3CO2H2O. Geochim. Cosmochim. 46:10111040.

Poole, G.C., and C. Berman. 2001. An ecological perspective on in-stream temperature:

natural heat dynamics and mechanisms of human-caused thermal degradation.

Environmental Management 27(6):787-802.

Raudkivi, A. I. 1979. Hydrology. Pergamon, Oxford, England.

102

Redfield, A.C., Ketchum, B.H. and Richards, F.A. 1963. The Influence of Organisms on

the Composition of Seawater, in The Sea, M.N. Hill, ed. Vol. 2, pp. 27-46, WileyInterscience, NY.

Riley, G.A. 1956. Oceanography of Long Island Sound 1952-1954. II. Physical

Oceanography, Bull. Bingham Oceanog. Collection 15, pp. 15-16.

Rosgen, D. 1996. Applied river morphology. Wildland Hydrology publishers. Pagosa

Springs, CO.

Rutherford, J.C., S. Blackett, C. Blackett, L. Saito, and R.J Davies-Colley. 1997.

Predicting the effects of shade on water temperature in small streams. New Zealand

Journal of Marine and Freshwater Research, 1997, Vol. 31:707-721.

Rutherford, J.C., Scarsbrook, M.R. and Broekhuizen, N. 2000. Grazer Control of Stream

Algae: Modeling Temperature and Flood Effects. J. Environ. Eng. 126(4):331-339.

Ryan, P.J. and D.R.F. Harleman. 1971. Prediction of the annual cycle of temperature

changes in a stratified lake or reservoir. Mathematical model and users manual.

Ralph M. Parsons Laboratory Report No. 137. Massachusetts Institute of Technology.

Cambridge, MA.

Ryan, P.J. and K.D. Stolzenbach.1972. Engineering aspects of heat disposal from power

generation, (D.R.F. Harleman, ed.). R.M. Parson Laboratory for Water Resources and

Hydrodynamics, Department of Civil Engineering, Massachusetts Institute of

Technology, Cambridge, MA

Shanahan, P. 1984. Water temperature modeling: a practical guide. In: Proceedings of

stormwater and water quality model users group meeting, April 12-13, 1984. USEPA,

EPA-600/9-85-003. (users.rcn.com/shanahan.ma.ultranet/TempModeling.pdf).

Smith, E.L. 1936. Photosynthesis in Relation to Light and Carbon Dioxide. Proc. Natl.

Acad. Sci. 22:504-511.

Spacil, R. and M. Rulik. 1998. Measurements of proteins in the hyporheic zone of Sitka

Stream, Czech Republic. Acta Univ. Palack. Olomuc. Fac. Rerum. Naturalium.

36:75-81.

Sridhar, V., and R.L. Elliott. 2002. On the development of a simple downwelling

longwave radiation scheme. Agriculture and Forest Meteorology, 112 (2002) 237-243.

Steele, J.H. 1962. Environmental Control of Photosynthesis in the Sea. Limnol.

Oceanogr. 7:137-150.

Stumm, W. and Morgan, J.J. 1996. Aquatic Chemistry, New York, Wiley-Interscience,

1022 pp.

Thackston, E. L., and Dawson, J.W. III. 2001. Recalibration of a Reaeration Equation. J.

Environ. Engrg., 127(4):317-320.

Thackston, E. L., and Krenkel, P. A. 1969. Reaeration-prediction in natural streams. J.

Sanit. Engrg. Div., ASCE, 95(1), 65-94.

Titus, J. E. and M. S. Adams (1979). Coexistence and the comparitive light relations of

the submerged macrophytes Myriophyllum spicatum L. and Vallisneria americana

Michx. Oecologia, 40, 273-286.

Tsivoglou, E. C., and Neal, L.A. 1976. Tracer Measurement of Reaeration. III. Predicting

the Reaeration Capacity of Inland Streams. Journal of the Water Pollution Control

Federation, 48(12):2669-2689.

Thomann, R.V. and Mueller, J.A. 1987. Principles of Surface Water Quality Modeling

and Control. New York, Harper-Collins.

QUAL2K

103

TVA, 1972. Heat and mass transfer between a water surface and the atmosphere. Water

Resources Research, Laboratory Report No. 14. Engineering Laboratory, Division of

Water Control Planning, Tennessee Valley Authority, Norris TN.

Van der Bijl, L., K. Sand-Jensen, and A. L. Hjermind (1989). Photosynthesis and canopy

structure of a submerged plan, Potamogeton pectinatus, in a Danish lowland stream.

Journal of Ecology, 77, 947-962.

Wanninkhof, R., Ledwell, I. R., and Crusius, I. 1991. "Gas Transfer Velocities on Lakes

Measured with Sulfur Hexafluoride." In Symposium Volume of the Second

International Conference on Gas Transfer at Water Surfaces, S.C. Wilhelms and I.S.

Gulliver, eds., Minneapolis, MN .

Wood, K.G. 1974. Carbon Dioxide Diffusivity Across the Air-Water Interface. Archiv fr

Hydrobiol. 73(1):57-69.

104

APPENDIX A: NOMENCLATURE

Symbol

Aacres ,i

[CO2]s

[CO32]

[H+]

[H2CO3*]

[HCO3]

[OH]

a

a"

a

a1

Aa

Ab

ab

Ac

ad

Alk

ap

ap

at

atc

B

b

B0

bd

c1

cf

cf

Cgb(T)

CH4,1

CL

cnps,i,j

Cp

cps,i,j

cs

Definition

surface area of reach i

saturation concentration of carbon dioxide

carbonate ion

hydronium ion

sum of dissolved carbon dioxide and carbonic acid

bicarbonate ion

hydroxyl ion

velocity rating curve coefficient

mean atmospheric transmission coefficient after

scattering and absorption

mean atmospheric transmission coefficient

atmospheric molecular scattering coefficient for

radiation transmission

atmospheric long-wave radiation coefficient

atmospheric long-wave radiation coefficient

bottom algae

cross-sectional area

coefficient correcting dam reaeration for water

quality

alkalinity

phytoplankton

phytoplankton concentration

atmospheric attenuation

atmospheric transmission coefficient

average reach width

velocity rating curve exponent

bottom width

coefficient correcting dam reaeration for dam type

Bowen's coefficient

fast reacting CBOD

fast CBOD in the overlying water

temperature-dependent maximum photosynthesis

rate

methane concentration in the aerobic sediment layer

fraction of sky covered with clouds

jth non-point source concentration for reach i

specific heat of water

jth point source concentration for reach i

slowly reacting CBOD

Units

acres

mole/L

mole/L

mole/L

mole/L

mole/L

mole/L

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

mmHg-0.5 or mb-0.5

gD/m2

m2

dimensionless

eq L1 or

mgCaCO3/L

mgC/L

mgA/m3

dimensionless

dimensionless

m

dimensionless

m

dimensionless

0.47 mmHg/oC

mgO2/L

gO2/m3

gD/(m2 d)

gO2/m3

dimensionless

o

C

cal/(g oC)

o

C

mgO2/L

Cs

CSOD

cT

c'T,i1

d

Dd

Dp

Ei

eair

elev

En

Ep,i

eqtime

es

f

fdai

fdpi

FLp

Foxcf

Foxdn

Foxna

Foxrb

Foxrp

fpai

fppi

Fu

g

gX

H

H

Hd

Hi

Hsed

I(0)

I0

the amount of oxygen demand generated by

methane oxidation

total inorganic carbon

concentration of inorganic carbon entering reach

below a dam

dust attenuation coefficient

pore water diffusion coefficient

diffusion coefficient for bioturbation

bulk dispersion coefficient between reaches i and i +

1

air vapor pressure

elevation above sea level

numerical dispersion

longitudinal dispersion between reaches i and i + 1

equation of time: the difference between mean solar

time and true solar time when located on the

reference longitude of the time zone considered

saturation vapor pressure at water surface

photoperiod

fraction of ammonium in dissolved form in sediment

layer i

fraction of inorganic phosphorus in dissolved form

in sediment layer i

phytoplankton growth attenuation due to light

attenuation of CBOD oxidation due to low oxygen

enhancement of denitrification at low oxygen

concentration

attenuation due to low oxygen

attenuation due to low oxygen

attenuation due to low oxygen

fraction of ammonium in particulate form in

sediment layer i

fraction of inorganic phosphorus in particulate form

in sediment layer i

fraction unionized ammonia

acceleration due to gravity

mass of element X

water depth

water depth

drop in water elevation for a dam

thickness of sediment layer i

sediment thickness

solar radiation at water surface

extraterrestrial radiation

mgO2/L

gO2/m2/d

mole L1

mgO2/L

dimensionless

m2/d

m2/d

m3/d

mm Hg

m

m2/d

m2/s

minutes

mmHg

fraction of day

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

= 9.81 m/s2

g

m

m

m

m

cm

cal/cm2/d

cal/cm2/d

106

Jan

Jbr

Jc

JC,G1

JCH4

JCH4,d

JCH4,T

Je

Jh

JN

JO2,dn

JP

JPOC,G1

JPOM

Jsi

Jsn

k(T)

K1

K2

Ka

ka(T)

kac(T)

kdb(T)

kdc(T)

kdn(T)

kdp(T)

kdt(T)

kdx(T)

ke

keb

kgp(T)

KH

khc(T)

khn(T)

khnxb

khnxp

QUAL2K

longwave back radiation flux from water

conduction flux

flux of labile dissolved carbon

Flux of methane from sediments to the overlying

water

flux of dissolved methane generated in anaerobic

sediments corrected for methane gas formation

carbon diagenesis flux corrected for denitrification

evaporation flux

air-water heat flux

nitrogen diagenesis flux

oxygen equivalents consumed during denitrification

phosphorus diagenesis flux

the flux of labile POC delivered to the anaerobic

sediment layer

the downward flux of POM

sediment-water heat flux

net solar shortwave radiation flux

temperature dependent first-order reaction rate

acidity constant for dissociation of carbonic acid

acidity constant for dissociation of bicarbonate

equilibrium coefficient for ammonium dissociation

temperature-dependent oxygen reaeration

coefficient

temperature-dependent carbon dioxide reaeration

coefficient

temperature-dependent bottom algae death rate

temperature-dependent fast CBOD oxidation rate

temperature-dependent denitrification rate

temperature-dependent phytoplankton death rate

temperature-dependent detritus dissolution rate

temperature-dependent pathogen die-off rate

light extinction coefficient

a background coefficient accounting for extinction

due to water and color

maximum photosynthesis rate at temperature T

Henry's constant

temperature-dependent slow CBOD hydrolysis rate

temperature-dependent organic nitrogen hydrolysis

rate

preference coefficient of bottom algae for

ammonium

preference coefficient of phytoplankton for

107

cal/(cm2 d)

cal/(cm2 d)

cal/(cm2 d)

gO2/m2/d

gO2/m2/d

gO2/m2/d

gO2/m2/d

cal/(cm2 d)

cal/(cm2 d)

gN/m2/d

gO2/m2/d

gP/m2/d

gO2/m2/d

gD m2 d1

cal/(cm2 d)

cal/(cm2 d)

/d

/d

/d

/d

/d

/d

/d

/d

/d

/m1

/m

/d

mole/(L atm)

/d

/d

mgN/m3

mgN/m3

July 16, 2004

khp(T)

KL12

KLb

KLp

KM,Dp

kna(T)

KNH4

KNH4,O2

kPOC,G1

krb(T)

krp(T)

ksNb

ksNp

Ksocf

Ksodn

Ksona

ksPb

ksPp

Kw

Lat

Llm

localTime

Lsm

m

mgY

mi

mi

mo

mo

n

na

na

nau

nfac

NH4,i

nn

nn

ammonium

temperature-dependent organic phosphorus

hydrolysis rate

pore water diffusion mass transfer coefficient

bottom algae light parameter

phytoplankton light parameter

oxygen half-saturation constant for bioturbation

temperature-dependent nitrification rate for

ammonia nitrogen

ammonium half-saturation constant

oxygen half-saturation constant

the mineralization rate of labile POC

temperature-dependent bottom algae respiration rate

temperature-dependent phytoplankton respiration

rate

nitrogen half-saturation constant for bottom algae

nitrogen half-saturation constant for phytoplankton

parameter for oxygen dependency of fast CBOD

oxidation

parameter for oxygen dependency of denitrification

parameter for oxygen dependency of nitrification

phosphorus half-saturation constant for bottom algae

phosphorus half-saturation constant for

phytoplankton

acidity constant for dissociation of water

latitude

longitude of local meridian

local standard time

longitude of standard meridian

optical air mass

mass of element Y

inorganic suspended solids

the solids concentration in sediment layer i

detritus

detritus concentration

Manning roughness coefficient

ammonia nitrogen

the ammonium concentration in the overlying water

unionized ammonia nitrogen

atmospheric turbidity factor

the concentration of total ammonium in sediment

layer i

nitrate nitrogen

nitrate concentration in the overlying water

/d

m/d

ly/d

gO2/m3

/d

gN/m3

mgO2/L

d1

/d

/d

gN/L

gN/L

gP/L

gP/L

radians

degrees

minutes

degrees

dimensionless

mg

mgD/L

gD/m3

mgD/L

gD/m3

mgN/L

mgN/m3

mgN/L

dimensionless

gN/m3

mgN/L

mgN/m3

108

no

NO3,i

npai

npsi

NSOD

o

o

oi1

ocrit

os(T, elev)

P

Pab

pai

Pap

PAR(z)

patm

pCO2

pi

pi

po

PO4,i

POC2,G1

POCR

psi

pwc

Q

Qab,i

Qi

Qin,i

Qnpa,i,j

Qnps,i,j

Qpa,i,j

Qps,i,j

QUAL2K

organic nitrogen

nitrate concentration in layer i

total number of non-point abstractions outflows

from reach i

total number of non-point sources inflows to reach i

the amount of oxygen demand generated by

nitrification

dissolved oxygen

the dissolved oxygen concentration in the overlying

water

oxygen concentration entering a reach below a dam

critical oxygen concentration for sediment

phosphorus sorption

saturation concentration of oxygen at temperature,

T, and elevation above sea level, elev

wetted perimeter

preference for ammonium as a nitrogen source for

bottom algae

total number of point abstractions from reach i

preference for ammonium as a nitrogen source for

phytoplankton

photosynthetically available radiation (PAR) at

depth z below water surface

atmospheric pressure

atmospheric partial pressure of carbon dioxide

inorganic phosphorus

the inorganic phosphorus in the overlying water

organic phosphorus

the concentration of total inorganic phosphorus in

sediment layer i

the concentration of the labile fraction of POC in the

anaerobic sediment layer

reference G1 concentration for bioturbation

total number of point sources to reach i

mean daily atmospheric precipitable water content

flow

total outflow from reach due to point and nonpoint

abstractions

outflow from reach i into reach i + 1

total inflow into reach from point and nonpoint

sources

jth non-point abstraction outflow from reach i

jth non-point source inflow to reach i

jth point abstraction outflow from reach i

jth point source inflow to reach i

109

mgN/L

gN/m3

dimensionless

dimensionless

gO2/m2/d

mgO2/L

gO2/m3

mgO2/L

gO2/m3

mgO2/L

m

dimensionless

dimensionless

dimensionless

ly/d

mm Hg

atm

gP/L

mgP/m3

gP/L

gP/m3

gO2/m3

gC/m3

dimensionless

m3/s or m3/d

m3/d

m3/d

m3/d

m3/d

m3/d

m3/d

m3/d

July 16, 2004

r

rcndn

rd

rda

RL

roc

roca

rocn

ron

ron'

ron

Rs

S

s

s

S0

Sb,i

Si

SOD

SODs

SODt

ss

t

T

T

T,w,f

Ta

Tair

Tair,f

Td

actual earth-sun distance to mean earth-sun distance

ratio of oxygen equivalents lost per nitrate nitrogen

that is denitrified

ratio of deficit above and below dam

the ratio of dry weight to chlorophyll a

longwave reflection coefficient

ratio of oxygen consumed per organic carbon

oxidized to carbon dioxide

ratio of oxygen generated per organic carbon

produced by photosynthesis when nitrate is taken up

ratio of oxygen generated per organic carbon

produced by photosynthesis when ammonia is taken

up

the ratio of oxygen to nitrogen consumed during

nitrification

ratio of oxygen consumed per ammonia nitrogen

converted by nitrification/denitrification to nitrogen

gas

the ratio of oxygen to nitrogen consumed for total

conversion of ammonium to nitrogen gas via

nitrification/denitrification

albedo or reflectivity (fraction of solar radiation that

is reflected)

channel slope

chloride

mass transfer coefficient between the water and

the aerobic sediments

bottom slope

sources and sinks of constituent due to reactions for

bottom algae

sources and sinks of constituent due to reactions and

mass transfer mechanisms for water constituents

the sediment oxygen demand

the supplemental sediment oxygen demand

total sediment oxygen demand = SOD + SODs

channel side slope

time

water temperature

water temperature

water temperature

absolute temperature

air temperature

air temperature

dew-point temperature

dimensionless

gO2/gN

dimensionless

gD/mgA

dimensionless

gO2/gC

gO2/gC

gO2/gC

= 4.57 gO2/gN

gO2/gN

= 1.714 gO2/gN

dimensionless

dimensionless

mgCl/L

m/d

m/m

gD/m2/d

g/m3/d or

mg/m3/d

gO2/m2/d

gO2/m2/d

gO2/m2/d

m/m

d

o

C

o

C

o

F

K

o

C

o

F

o

C

110

Ti

timezone

Tnps,i,j

Tps,i,j

trueSolarTim

e

Ts,i

tsr

tss

Tstd

tt,i

U

Ui*

Uw

Uw,mph

Uw,z

va

va

vdt

vdt

vi

Vi

vp

vpc

W0

w2

Wh,i

Wi

x

zw

QUAL2K

temperature in reach i

time zone indicates local time zone in relation to

Greenwich Mean Time (GMT) (negative in western

hemisphere)

jth non-point source temperature for reach i

jth point source temperature for reach i

time determined from actual position of the sun in

the sky

temperature of bottom sediment

time of sunrise

time of sunset

standard time

travel time from headwater to end of reach i

mean velocity

shear velocity

wind speed

wind speed

wind speed at height zw above water surface

phytoplankton settling velocity

phytoplankton settling velocity

detritus settling velocity

detritus settling velocity

inorganic suspended solids settling velocity

volume of ith reach

pathogen settling velocity

non-living particulate organic carbon settling

velocity

solar constant

the burial velocity

net heat load from point and non-point sources into

reach i

external loading of constituent to reach i

pathogen

height above water for wind speed measurements

111

C

hours

o

C

C

minutes

o

C

Hr

Hr

Hr

D

m/s

m/s

m/s

mph

m/s

m/d

m/d

m/d

m/d

m/d

m3

m/d

m/d

2851 cal/cm2/d

m/d

cal/d

g/d or mg/d

cfu/100 mL

m

Greek:

Symbol

d

s

0

1

2

i

o

p

pn

PO4,1

v

ts

xi

clear

sky

a

Lb

Lp

Nb

Np

p

Definition

depth rating curve coefficient

suns altitude

suns altitude

sediment thermal diffusivity

fraction of total inorganic carbon in carbon dioxide

fraction of total inorganic carbon in bicarbonate

fraction of total inorganic carbon in carbonate

effect of inorganic suspended solids on light

attenuation

effect of particulate organic matter on light

attenuation

linear effect of chlorophyll on light attenuation

non-linear effect of chlorophyll on light attenuation

depth rating curve exponent

solar declination

factor that increases the aerobic sediment layer

partition coefficient relative to the anaerobic

coefficient

virtual temperature difference between the water

and air

difference between standard and local civic time

length of ith reach

emissivity of water

emissivity of longwave radiation from the sky with

no clouds

emissivity of longwave radiation from the sky with

clouds

estimated error

bottom algae light attenuation

phytoplankton light attenuation

bottom algae nutrient attenuation factor

phytoplankton nutrient attenuation factor

phytoplankton photosynthesis rate

density of water

Stefan-Boltzmann constant

local hour angle of sun

residence time of ith reach

temperature coefficient for zero and first-order

reactions

Units

dimensionless

radians

degrees

cm2/s

dimensionless

dimensionless

dimensionless

L/mgD/m

L/mgD/m

L/gA/m

(L/gA)2/3/m

dimensionless

radians

dimensionless

F

hr

m

dimensionless

0-1

0-1

%

0-1

0-1

0-1

0-1

/d

g/cm3

11.7x10-8 cal/(cm2 d K4)

radians

d

dimensionless

112

am

12

ai

pi

CH4

Dd

Dp

NH4

NO3

POC,G1

CH4,1

NH4,1

NO3,i

QUAL2K

the bioturbation mass transfer coefficient between

the sediment layers

the partition coefficient for ammonium in sediment

layer i

the partition coefficient for inorganic phosphorus in

sediment layer i

temperature correction factor for sediment methane

oxidation

temperature coefficient for porewater diffusion

temperature coefficient for bioturbation diffusion

temperature correction factor for sediment

nitrification

sediment denitrification temperature correction

factor

temperature correction factor for labile POC

mineralization

the reaction velocity for methane oxidation in the

aerobic sediments

the reaction velocity for nitrification in the aerobic

sediments

denitrification reaction velocity sediment layer i

113

m/d

m3/gD

m3/gD

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

dimensionless

m/d

m/d

m/d

EXCHANGE

Although the omission of sediment-water heat exchange is usually justified for deeper systems, it can

have a significant impact on the heat balance for shallower streams. Consequently, sediment-water heat

exchange is included in QUAL2K.

A major impediment to its inclusion is that incorporating sediment heat transfer often carries a heavy

computational burden. This is because the sediments are usually represented as a vertically segmented

distributed system. Thus, inclusion of the mechanism results in the addition of numerous sediment

segments for each overlying water reach.

In the present appendix, I derive a computationally-efficient lumped approach that yields comparable

results to the distributed methods.

The conduction equation is typically used to simulate the vertical temperature distribution in

a distributed sediment (Figure 24a)

T

2T

2

t

x

(310)

T (0, t ) T Ta cos (t )

T ( , t ) T

where T = sediment temperature [oC], t = time [s], = sediment thermal diffusivity [m2 s1], and

z = depth into the sediments [m], where z = 0 at the sediment-water interface and z increases

downward, T = mean temperature of overlying water [oC], Ta = amplitude of temperature of

overlying water [oC], = frequency [s1] = 2/Tp, Tp = period [s], and = phase lag [s]. The first

boundary condition specifies a sinusoidal Dirichlet boundary condition at the sediment-water

interface. The second specifies a constant temperature at infinite depth. Note that the mean of the

surface sinusoid and the lower fixed temperature are identical.

Page 114

z

(a) distributed

(b) Lumped

Figure 24. Alternate representations of sediments: (a) distributed and (b) lumped.

Applying these boundary conditions, Eq. (231) can be solved for (Carslaw and Jaeger 1959)

T ( z , t ) T Ta e ' z cos (t ) ' z

(311)

'

(312)

The heat flux at the sediment water interface can then be determined by substituting the

derivative of Eq. (232) into Fouriers law and evaluating the result at the sediment-water

interface (z = 0) to yield

J (0, t ) C p Ta cos (t ) / 4

(313)

An alternative approach can be developed using a first-order lumped model (Figure 24b),

H s s C ps

dTs s s C ps

T Ta cos (t ) Ts

dt

Hs / 2

where Hsed = the thickness of the sediment layer [m], s = sediment density [kg/m3], and Cps =

sediment heat capacity [joule (kg oC)]1]. Collecting terms gives,

Page 115

dT

k h T k h T k hTa cos (t )

dt

where

kh

2 s

H sed

After initial transient have died out, this solution to this equation is

T T

kh

kh 2

2

Ta cos (t ) tan 1 ( / k h )

(314)

2

J

C p Ta cos (t )

H sed

kh

2

kh

cos (t ) tan ( / k h )

1

(315)

It can be shown that Eqs. (232) and (235) yield identical results if the depth of the single layer

is set at

H sed

1

'

(316)

Water quality models typically consider annual, weekly and diel variations. Using = 0.0035

cm2/s (Hutchinson 1957), the single-layer depth that would capture these frequencies can be

calculated as 2.2 m, 30 cm and 12 cm, respectively.

Because QUAL2K resolves diel variations, a value on the order of 12 cm should be selected

for the sediment thickness. We have chosen of value of 10 cm as being an adequate first estimate

because of the uncertainties of the river sediment thermal properties (Table 4).

Page 116

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