Environ. Sci. Technol.
1999, 33, 3027-3032
Removal of Natural Organic Matter
by Coagulation-Flocculation: A
Pyrolysis-GC-MS Study
A S T R I D E V I L G EÄ - R I T T E R , †
A R M A N D M A S I O N , * ,†
T H I E R R Y B O U L A N G EÄ , †
DANIELLE RYBACKI,‡ AND
JEAN-YVES BOTTERO†
Géosciences de l’Environnement, CEREGE, UMR 6635
CNRS-Université Aix-Marseille III, BP 80, Europôle
Méditerranéen de l’Arbois, 13545 Aix-en-Provence Cedex 4,
France, and CIRSEE, Suez-Lyonnaise des Eaux, 38 rue du
président Wilson, 78230 Le Pecq, France
The removal of the natural organic matter (NOM) in the
Seine river water sampled at Le Pecq (France) was carried
out by using three coagulants: ferric chloride, aluminum
sulfate, and aluminum polychlorosulfate (PACS). The efficiency
of the coagulation-flocculation process depended on the
pH. The best results were obtained at pH ) 5.5 with ferric
chloride and pH ) 7.0 with the Al based coagulants
aluminum sulfate and PACS.The composition of NOM in
the raw and clarified water as well as in the flocs was
analyzed by pyrolysis-gas chromatography-mass spectrometry
(Py-GC-MS). Using this technique on the flocs formed
with ferric chloride, a selectivity of this coagulant for
polyhydroxyaromatics (PHA) was shown. A preferential
binding was also observed between PACS and polysaccha-
rides (PS). No such trend could be observed with aluminum
sulfate. These results were confirmed and refined by Py-
GC-MS analyses on the different mass fractions of the clarified
water obtained by gel permeation chromatography.
Introduction
The optimization of the drinking water treatment requires
an enhanced removal of natural organic matter (NOM). NOM
is partly responsible for the fouling of filtration membranes
and may form disinfection byproducts. Moreover oxidation
byproducts can favor bacterial regrowth in the distribution
network. Enhanced removal of the organics implies a better
knowledge of the chemistry of NOM. Surface waters include
diverse types of NOM originating from various environmental
systems (1).
Surface water NOM is mainly composed of variable
proportions of allochthonous and autochthonous com-
pounds. Various analytical techniques such as 13C magnetic
nuclear resonance (2, 3), transmission electron microscopy
(4), and NOM fractionation on XAD resins (5, 6) have been
used to characterize aquatic NOM.
Organic compounds in water and sediments are a mixture
of biopolymers such as carbohydrates, lipids, and proteins
as well as complex and less well characterized macromol-
ecules, generally referred to as humic substances (7).
* Corresponding author phone: +(33) (0) 442 97 15 34; fax: +(33)
(0) 442 97 15 40; e-mail: masion@cerege.fr.
† CNRS-Université Aix-Marseille III.
‡ CIRSEE.
10.1021/es981232p CCC: $18.00  1999 American Chemical Society
Published on Web 07/16/1999
TABLE 1. Characteristics of the Seine River Water at Le Pecqa
LE PECQ LE PECQ
TOC mg/L
DOC mg/L
4.0
3.8
NO2- mg/L
NH4+ mg/L
0.4
0.3
UV at 254 nm 0.058 SO42- mg/L 27
THMFP µg/L 223 Cl- mg/L 15
chloroform µg/L 52 Ca2+ mg/L 103
pH at 20 °C 7.7 Mg2+ mg/L 6
turbidity NTU 27 Fe µg/L 10
NO3- mg/L 23
a
THMFP: trihalomethane formation potential.
Pyrolysis-gas chromatography-mass spectrometry (Py-
GC-MS) has been used to characterize numerous NOM
samples from a variety of sources, such as wood (8, 9), fossil
objects (10), soil sediments (11, 12), and aquatic systems (7,
13-15). Only few investigators have compared the different
water treatment processes using Py-GC-MS (16, 17). Gray
(16) showed that Py-GC-MS is a powerful analytical technique
to study the organic matrix and that the efficiency of the
treatment processes changes according to the composition
of NOM in the water. Using the same technique, Widrig (17)
examined the role played by algal populations and water
quality in DOC removal during ozonation and coagulation
processes. They have shown that although the pyrolysis
profile before and after coagulation of algal organic matter
with FeCl3 is dominated by aromatic nitrogen-containing
fragments, coagulation may have produced some preferential
removal of the parent material producing the aliphatic nitrile
pyrolysis fragments. While after ozonation, there was a
dramatic change in the pyrolysis-GC-MS fingerprint of this
organic matrix.
Coagulation-flocculation is the most important process
in the drinking water treatment industry considering the mass
of removed matter. Coagulation has historically been em-
ployed in water treatment practice to primary decrease levels
of turbidity.
In the present paper, gel permeation chromatography
(GPC) and Py-GC-MS are used to study the coagulation-
flocculation of the NOM in the Seine river at Le Pecq (France)
by three common coagulants.
Materials and Methods
All experiments described hereafter were done in duplicate
or triplicate and were reproducible (standard deviation <10%
of the mean value). The data presented in this study represent
the mean value of the determinations.
Jar Tests. The raw water was collected in the Seine river
(Le Pecq France) and stored at 4 °C. Table 1 summarizes its
global characteristics. This water usually used as resource
for drinking water is weakly organic charged (DOC ) 3.8 mg
C/L) and strongly mineralized (turbidity ) 27 NTU); its pH
value is 7.7 (Table 1).
Three coagulants were used: aluminum sulfate (Al2(SO4)3‚
14H2O) (Rhône Poulenc, France), aluminum polychloro-
sulfate (PACS) (Aln(OH)mCl3n-m-2k(SO4)k) (WAC HB, Elf
Atochem, France), and ferric chloride (FeCl3‚6H2O) (Elf
Atochem, France).
The coagulant doses ranged from 0.5 × 10-4 to 3 × 10-4
M for Fe and from 0.32 × 10-4 to 1.6 × 10-4 M for Al, which
correspond, in the notation used in the water treatment
industry, to doses of the commercial product ranging from
20 to 120 mg/L for ferric chloride and from 20 to 100 mg/L
for the Al based coagulants.
VOL. 33, NO. 17, 1999 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3027
FIGURE 1. Pyrochromatogram of the raw water.
The clarification of the raw water is carried out at room
temperature using a jar test setup. The coagulation occurred
under rapid mix conditions (3 min at 140 rpm), during which
the coagulant was added to 500 mL of raw water, and the pH
was adjusted at set values with NaOH and HCl (0.1 N). The
chosen pH values were 5.5, 6.5, and 7.5 for ferric chloride,
and 6.0, 7.0, and 8.0 for aluminum sulfate and PACS. These
values of pH were chosen to scan the typical range usually
used in water treatment. The low pH value (5.5) could be
justified by some literature results which prove that this pH
corresponds to the optimal value for removing dissolved
organics (18, 19).
Flocculation occurred during the slow mix regime (40
rpm, 30 min). Jars were then removed from the stirrer, and
the flocs were allowed to settle for 30 min. Finally the
supernatant was collected using a siphon, and the flocs were
freeze-dried.
The raw water and the clarified water were analyzed using
different methods. The turbidity is measured using a HACH
2100AN turbidimeter. The concentrations of NOM are
determined by (i) UV absorbance at 254 nm (Hitachi U1100
spectrophotometer) in a 1 cm quartz cell and (ii) total and
dissolved organic carbon (TOC and DOC) measurements on
a Shimadzu 5000 carbon analyzer. The CO2 formed after a
catalytic oxidation at 680 °C is detected in a nondispersive
infrared gas analyzer. The samples are acidified to pH ) 2
with HCl 6 N and sparged during 10 min before analysis.
DOC is measured on water after filtration at 0.45 µm (Millipore
Millex-HV, filters made in “durapore” polyvinylede fluoride).
Gel Permeation Chromatography. The different mass
fractions of NOM of our raw and clarified water samples
were separated by GPC on a dextran gel (Sephadex G25) (20,
21).
Liquid water samples were concentrated by vacuum rotary
evaporation at 30 °C to obtain a final DOC around 100 ppm
of C. Ten milliliters of the concentrates was injected to the
GPC column and eluted with ultrapure water at a rate of 150
mL/h. GPC profiles were recorded by measuring UV absor-
bance at 254 nm and DOC. The Sephadex G25 gel allows the
fractionation of the sample according to molecular weight:
the larger molecules move only outside the gel particles,
whereas smaller molecules can also diffuse inside the gel
particles. Three fractions are collected according to their
molecular weight: G1 (apparent molecular weight > 5000
Daltons), G3 (1500 < apparent molecular weight < 5000
Daltons), and G5 (apparent molecular weight < 1500
Daltons).
3028 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 33, NO. 17, 1999
This GPC method concentrates the soluble salts in the G5
fraction (22). Since these salts may affect the Py-GC-MS
analysis (23), results obtained by using this technique on
fraction G5 were not taken into account in the present study.
Since sorption effects on the gel may affect GPC, the data
will only be used to analyze trends and not in a quantitative
manner.
Pyrolysis-Gas Chromatography-Mass Spectrometry. Py-
GC-MS was performed on the GPC fractions G1 and G3 of
the clarified water samples and on the freeze-dried flocs using
a pyroprobe 100 filament pyrolyzer (CDS, Oxford) connected
with the split injection port of a Carlo Erba 4160 gas
chromatograph interfaced with a NERMAG R-10-10 C quad-
rupole mass spectrometer.
The GPC fractions were concentrated by vacuum rotary
evaporation down to a few milliliters and reduced to 100 µL
under a nitrogen stream. Fifty microliters of this concentrate
was injected in quartz tube and dried slowly at room
temperature. Freeze-dried floc samples (about 1 mg) were
put directly in the quartz tube.
The quartz tubes were submitted to a flash pyrolysis; the
platinum filament was programmed to a final temperature
of 640 °C at a heating rate of 20 °C/ms and held at this
temperature for 20 s. The pyrolysis products were separated
on a DB-WAX column programmed from 30 to 220 °C at a
rate of 3 °C/min and held at this temperature for 20 min.
Pyrolysis products were detected by the mass spectrometer
operated at 70 eV and scanned from 20 to 450 amu at 1
scan/s.
Interpretation of Pyrolysis Data. The peaks of the
pyrochromatogram correspond to compounds which are
identified by comparison with the built-in spectrum library
or the literature data. The relative amount of the pyrolysis
products is determined from the chromatogram peak areas.
Interpretation of the pyrolysis data can done by the global
description of the pyrolysis byproducts and the comparison
of the pyrochromatograms or by grouping the thermal
degradation fragments into categories. In our case, the shape
of the pyrochromatograms (Figure 1) of the raw or clarified
waters was similar; all the main thermal degradation
byproducts listed by Bruchet et al. (7) were detected in the
samples. Therefore the pyrolysis products were grouped into
biopolymer classes to perform a semiquantitative analysis.
The four major biopolymers usually found in natural water
are polysaccharides (PS), proteins (PR), aminosugars (AS),
and polyhydroxyaromatics (PHA). Attribution of the identified

FIGURE 2. Evolution of turbidity versus the dose of coagulants.
FIGURE 3. Proportion of NOM remaining (UV and DOC measure-
ments) versus added coagulant at different pH: (a) for ferric chloride,
(b) for aluminum sulfate, and (c) for PACS.
compounds to one of these categories and the calculation
of their relative proportion were carried out according to the
method developed by Bruchet et al. (7). Unidentified or
unattributable compounds are listed as miscellaneous (Misc.).
Results and Discussion
Removal of Organic Matter: Jar Test. With all three
coagulants and at each pH value, the turbidity of the water
was decreased from 27 NTU (Table 1) to less than 1 NTU
when the coagulant dose was larger than 1 × 10-4 M. For a
better readability of Figure 2, only one value of pH was
presented. This figure shows a typical evolution of the residual
turbidity versus the coagulant doses and pH. There is no
regrowth of residual turbidity with the increase of coagulant
concentration (Figure 2).
The DOC and UV measurements on the clarified water
showed that the efficiency of NOM removal depends on the
pH of coagulation (Figure 3): for ferric chloride, the best
results were obtained at pH 5.5 (about 60% of C removal),
and the proportion of remaining C showed only little
TABLE 2. Distribution of DOC (%) in the GPC Fractions
[Al] or [Fe] ×10-4 mol/L
ferric chloride aluminum sulfate PACS
pH 5.5 pH 7.5 pH 6 pH 8 pH 6 pH 8
raw
percent water 0.5 2 0.5 2 0.32 1.3 0.32 1.3 0.35 1.4 0.35 1.4
G1 35 19 17 29 28 30 20 15 21 12 12 11 16
G3 36 26 32 28 31 36 33 20 25 30 22 28 22
G5 28 55 50 43 41 34 45 65 54 58 66 61 62
dependence on the dose of Fe added (Figure 3a). This is in
agreement with previous findings showing that the optimum
coagulation pH values are 5.5 for iron chloride (18, 24). With
the Al based coagulants (aluminum sulfate and PACS), the
lowest levels of remaining C were observed at pH 7 (based
TOC removal) (Figure 3b,c). On the other hand, in terms of
UV absorbance decrease, the lowest levels of remaining
organic matter were observed in a pH 6-7 range for
aluminum sulfate (Figure 3b) and in a pH 7-8 range for
PACS (Figure 3c). For Al salts, the optimum pH for removal
of NOM is usually reported to be in the 5-6 range (25-27).
This range of pH is lower than the optimum value found in
the present work.
At optimum pH, the highest efficiency in organic C
removal was observed with ferric chloride (approximately
35% of remaining C at [Fe] ) 1 × 10-4 M vs 75-80% with the
Al salts at the same molar concentration) (Figure 3).
In all cases, the decrease of UV absorbance between raw
and clarified water samples is stronger than the decrease of
DOC (Figure 3). Similar results have been reported previously
(28). Since the UV absorbance is due essentially to the
presence of aromatic compounds, its stronger decrease
compared to DOC indicates that, in our water samples, this
category of organic molecules is preferentially removed by
the coagulation-flocculation process.
Selectivity of Coagulants for NOM. Characterization of
NOM (Py-GC-MS and GPC) was performed on samples
resulting from the coagulation by Al and Fe salts at low and
high coagulant concentrations ([Fe3+] ) 0.5 × 10-4 M and 2
× 10-4 M, [Al3+] ) 0.32 × 10-4 M and 1.3 × 10-4 M for
aluminum sulfate and 0.35 × 10-4 M and 1.4 × 10-4 M for
PACS, corresponding for each coagulant to 20 mg/L and 80
mg/L) and pH values (5.5 and 7.5 for ferric chloride or 6 and
7 for aluminum sulfate and PACS).
Influence of the Apparent Molecular Weight. The analysis
of the GPC fractions on the raw and clarified water allows
for determination of the role played by each mass fraction
in the coagulation-flocculation process. DOC measurements
on the raw water (Table 2) revealed that the G1 and G3 mass
fractions of the Seine river water contain comparable
amounts of organic C (approximately 35%), the G5 fraction
representing a slightly lower proportion (28%). In the clarified
water samples, the NOM in the different fractions is not evenly
affected: in all cases, the proportions of DOC in the G1 and
G3 fractions are lower than in the raw water (Table 2), which
means that the coagulation primarily eliminates the mol-
ecules with an apparent molecular weight larger than 1500
D. This is in agreement with previous studies demonstrating
that the predominant part of flocculated NOM consist of
large biopolymers (29-31). In our case, the G1 fraction (>5000
D) always was the most affected by the coagulation, and in
particular in the water clarified with PACS, where the G1
fraction never represented more than 16% of the DOC vs
35% in the raw water (Table 2).
Selectivity of Coagulants for Biopolymers. Py-GC-MS
analyses of freeze-dried raw water yielded the following NOM
composition: PR correspond to 3% of NOM, AS 41%, PHA
14%, PS 21%, and miscellaneous compounds 21% (Table 3).
VOL. 33, NO. 17, 1999 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3029
 G1 and the G3 fraction. In the other PACS samples, the
TABLE 3. Proportion (Percent of DOC) of the Different Types of decrease of the PS proportion in the G1 and G3 fractions is
Biopolymers in Freeze-Dried Raw Water and in Freeze-Dried also almost identical: approximately 40% for pH 6.0 and [Al]
Flocs ) 1.4 × 10-4 M, 50-60% for pH 8.0 and [Al] ) 0.35 × 10-4
[Al] or [Fe] ×10-4 mol/L M, and 30% for pH 8.0 and [Al] ) 1.4 × 10-4 M. Therefore,
ferric chloride aluminum sulfate PACS it can be assumed that the PS in the G1 and G3 fractions
differ only in polymer molecular weight and not in chemical
pH 5.5 pH 7.5 pH 6 pH 8 pH 6 pH 8 nature.
raw
percent water 0.5 2 0.5 2 0.32 1.3 0.32 1.3 0.35 1.4 0.35 1.4 Ferric Chloride and Aluminum Sulfate. The PS are not
PS 21 23 13 13 37 21 17 40 9 68 27 60 42 efficiently coagulated by these two coagulants. The flocs
PR 3 10 6 0 11 11 5 11 0 8 3 13 13 formed with aluminum sulfate or ferric chloride, except [Fe]
AS 41 2 51 7 1 38 36 3 1 0 6 8 8 ) 2 × 10-4 M at pH ) 7.5 and [Al] ) 0.32 × 10-4 M at pH
PHA 14 47 27 61 34 26 39 42 87 16 54 10 29 ) 8, contain a proportion of PS comparable or lower than
MISC 21 18 3 19 17 4 3 4 3 8 10 9 8 in the raw water (Table 3). Correlatively, the proportion of
PS in the fractions G1 and G3 in the clarified water is usually
significantly higher than in the raw water and does not follow
TABLE 4. Proportion (Percent of DOC) of the Different Types of any trend (Table 4). Unlike the case of PACS, no preferential
Biopolymers in Raw Water and in Clarified Waters binding or high affinity for PS could be observed with iron
[Al] or [Fe] ×10-4 mol/L chloride and aluminum sulfate.
ferric chloride aluminum sulfate PACS Selectivity of Coagulants for PR. PR molecules cor-
respond to a low proportion of DOC in the raw water (3%)
pH 5.5 pH 7.5 pH 6 pH 8 pH 6 pH 8 (Table 3). The proportion of PR in the flocs formed with each
raw
percent water 0.5 2 0.5 2 0.32 1.3 0.32 1.3 0.35 1.4 0.35 1.4 coagulant are low and close to the initial value (Table 3).
G1 Moreover for all the coagulants (ferric chloride, aluminum
PS 11 45 12 23 17 49 43 39 35 9 7 4 8 sulfate, and PACS), the proportion of PS in the clarified water
PR 3 6 4 4 5 7 7 7 5 3 3 3 2 (fractions G1 and G3) is the same as in the raw water (Table
AS 59 22 24 41 52 4 14 26 21 45 55 66 51 4). This suggests that PR molecules of Seine river water are
PHA 9 7 18 8 10 16 16 13 15 6 10 4 11 not coagulated by Al or Fe salts.
MISC 18 20 42 24 16 24 20 15 24 37 25 23 28
Selectivity of Coagulants for PHA. Ferric Chloride. All
G3 the flocs formed with ferric chloride were enriched in PHA:
PS 28 39 62 12 22 29 40 35 36 22 16 15 20 the proportion of this NOM category in the flocs ranged from
PR 4 9 3 1 7 8 5 5 4 4 6 4 4
AS 28 12 5 56 16 17 23 6 9 41 40 53 38 27% (pH 5.5, [Fe] ) 2.0 × 10-4 M) to 61% (pH 7.5, [Fe] ) 0.5
PHA 30 22 14 10 8 14 20 8 17 14 20 12 17 × 10-4 M), whereas the PHA represented only 14% of the
MISC 10 18 16 21 47 32 12 46 34 19 18 16 21 NOM in the raw water (Table 3). Thus, ferric chloride seems
to exhibit a selectivity for the PHA compounds. For a given
coagulant dose, the proportion of PHA in the flocs increased
This distribution of NOM was considerably modified in the between pH ) 5.5 and pH ) 7.5. Enhanced binding of the
flocs resulting from the coagulation by the Al and Fe salts. PHA with increasing pH can be easily explained by their
In the following sections, the results and discussion are higher reactivity due to the deprotonation of phenolic OH
presented according to the behavior of coagulants toward groups. Indeed, previous studies on natural organics showed
the biopolymers. that the titration of phenolic protons occurs quantitatively
Selectivity of Coagulants for PS. PACS. All the flocs formed at pH values around 8, whereas this phenomenon is negligible
with PACS contain a higher proportion of PS than the raw at lower pH (32, 33). At each pH, the proportion of PHA
water (Table 3). At low concentration ([Al] ) 0.35 × 10-4 M), within the flocs decreased with increasing ferric chloride
the PS represent 60% or more of the NOM within the flocs dose (Table 3). This supports the hypothesis that ferric
(Table 3). At higher concentration ([Al] ) 1.4 × 10-4 M), their chloride selectively removes the PHA from the raw water:
relative proportion (27-42%) remains higher than in the raw at low ferric chloride concentration (0.5 × 10-4 M), the high
water (21%) but is decreased compared to the lower PACS affinity of Fe for PHA compounds and the limited amount
dose. This probably results from the enhanced binding of of Fe binding sites result in high proportions of PHA in the
other types of biopolymers due to the increased number of flocs. At higher ferric chloride concentration (2 × 10-4 M),
available Al sites. These high PS proportions and their the increased number of Fe binding sites enables the binding
evolution with the coagulant dose are indicative of a selectivity of other categories of NOM which translates to a lower relative
of PACS for this type of molecules. proportion of PHA in the flocs.
A strong decrease of the proportion of DOC in the G1 The analysis of the NOM in the clarified water also
fraction of water clarified by PACS was observed (Table 2). confirmed the selectivity of ferric chloride toward PHA
An explanation of this strong decrease in the case of PACS compounds. However, in our water sample, this preferential
was provided by a more detailed analysis of the NOM in the binding is evident only in the G3 fraction in which the
GPC fractions. Py-GC-MS data indicate that 11% of the G1 proportion of PHA is decreased by 20% (pH 5.5, [Fe] ) 0.50
fraction and 28% of the G3 fraction of the raw water × 10-4 M) to 75% (pH 7.5, [Fe] ) 2.0 × 10-4 M) with respect
correspond to PS compounds (Table 4). These proportions to the G3 fraction of the raw water (Table 4). The proportion
drop respectively to 4-9% and 15-22% in the G1 and G3 of PHA in the G1 fraction remains relatively unaffected. This
fractions of the water clarified with PACS (Table 4). This strongly suggests that, contrary to the PS, the G1 and G3
confirms the preferential binding of PS molecules by PACS, fractions contain PHA compounds of different chemical
which was already hypothesized from the analysis of the nature and reactivity and thus presumably of different origin,
NOM in the flocs (Table 3). Furthermore, the comparison of the more reactive molecules being in the G3 fraction.
the initial PS proportions in the fractions with those obtained Aluminum Sulfate. Large proportions of PHA (26-87%)
after coagulation shows that the PS are removed to the same are also present in the flocs formed by coagulation with
extent irrespective of the apparent molecular weight (Table aluminum sulfate (Table 3). Unlike ferric chloride, the
4). At pH 6.0 and [Al] ) 0.35 × 10-4 M, the proportion of PS proportion of PHA in the flocs formed with aluminum sulfate
in the clarified water is decreased by about 20% in both the increased with both pH and coagulant dose. As stated above,

3030 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 33, NO. 17, 1999
the increase of the PHA proportion at higher pH is consistent
with a higher reactivity of this type of molecules due to
deprotonation. The interpretation of the increase of the PHA
proportion with the aluminum sulfate dose at a same pH is
not straightforward. It may denote a differential reactivity
among the PHA molecules (e.g. COOH vs OH groups), the
less stable complexes being formed only at higher Al
concentration. Therefore, although the high proportion of
PHA in the flocs indicates a certain affinity, aluminum sulfate
may not be considered as selective toward PHA.
The analysis of the NOM in the clarified water also
confirmed the better affinity of PHA for aluminum sulfate.
Similarly to the case of ferric chloride, the proportions of
PHA in the G1 fractions remains relatively unaffected by
coagulation with aluminum sulfate (9% in the raw water and
>7% in the clarified water). Only the PHA of the G3 fraction
are removed (30% in the raw water and <20% in the clarified
water) (Table 4). This is in agreement with the fact that the
PHA compounds are different in chemical nature and in
reactivity according to their molecular weight.
PACS. In the case of the flocs formed with PACS, the
evolution of the proportion of PHA shows some differences
compared to aluminum sulfate: (i) the proportions of PHA
are generally much lower, and (ii) surprisingly, the proportion
of PHA does not increase with the pH (Table 4). Similar to
aluminum sulfate, the proportion of PHA increases with the
dose of PACS. Analysis of the NOM in the water clarified with
PACS confirms the trend observed with the two other
coagulant, viz. the PHA compounds of the G1 fraction are
much less affected by the coagulation than the PHA of the
G3 fraction (Table 4).
Selectivity of Coagulants for AS. The proportion of AS
within the flocs is always decreased by comparison with the
raw water (41%), except for ferric chloride pH 5.5 and 2 ×
10-4 mol/L of Fe3+ (Table 3). It appears that AS molecules
generally are not well coagulated by any of the three
coagulants. Nevertheless the variations of the AS proportions
in the flocs are important (1-51%), and this erratic variation
is not reproduced in the analysis of the clarified waters (Table
4). The results of Py-GC-MS in the clarified water indicate
that AS are the least affected by PACS: in both mass fractions,
the percentage of AS in the clarified water is similar or higher
than in the raw water (Table 4). The proportions of AS are
more extensively affected by ferric chloride and aluminum
sulfate. However, no clear trend can be defined in terms of
selectivity. For ferric chloride, the low dose is more effective
for the AS of the G1 fraction, whereas, in the G3 fraction, the
high dose gives the better results. For aluminum sulfate also,
the effectiveness of AS removal does not follow any trend.
It appears that ferric chloride and aluminum sulfate exhibit
a moderate affinity for AS biopolymers, whereas PACS does
not bind to this type of molecule.
The Py-GC-MS analysis of NOM of Seine river water
samples showed major differences in NOM removal accord-
ing to the nature of the coagulant. The iron based coagulant
removed preferentially the PHA. The analysis of GPC fractions
revealed that in the studied water, there are differences in
the chemical nature of the PHA according to the apparent
molecular weight. A selectivity for PS molecules was observed
with PACS. In this case, the preferential binding did not
depend on the mass fraction. No selectivity for a given type
of biopolymers was observed with aluminum sulfate. How-
ever, this coagulant showed a high affinity toward the PHA.
In certain experimental conditions, the AS compounds were
very effectively removed by ferric chloride and aluminum
sulfate, but no selectivity or high affinity was observed. Finally,
none of the three coagulants showed an affinity for PR
molecules.
Acknowledgments
This work benefited from the financial support of the Centre
International de Recherche sur l’Eau et l’Environnement
(CIRSEE), Suez-Lyonnaise des Eaux, France.
Nomenclature
AS aminosugar
DOC dissolved organic carbon
GPC gel permeation chromatography
Misc. miscellaneous
NOM natural organic matter
NTU nephelometric turbidity unit
PACS aluminum polychlorosulfate
PHA polyhydroxy aromatics
PR protein
PS polysaccharide
Py-GC-MS pyrolysis-gas chromatography-mass spec-
trometry
TOC total organic carbon
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Received for review November 30, 1998. Revised manuscript
received May 20, 1999. Accepted May 25, 1999.
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