Wat. Res. Vol. 31, No. 11, pp.

2775 2782, 1997

@ 1997ElsevierScienceLtd. All rights reserved
Pergamon Printed in Great Britain
PII: S0043-1354(97)00147-4 0043-1354/97 $17.00+ 0.00

LANDFILL LEACHATES PRETREATMENT BY

COAGULATION-FLOCCULATION
A. A M O K R A N E ~*, C. COMEL 2 and J. VERON I
'Institut National des Sciences Appliqures de Lyon, LCPAE. B~it.404.20, Av. A. Einstein. B~it.404. 69621
Villeurbanne Cedex, France and 2Universit6 d'Angers, Facult6 des Sciences Belle-Beille Laboratoire de
Chimie et Environnement, 2, Bd. Lavoisier 49045 Angers Cedex, France

(Received January 1996; accepted in revised form April 1997)

Abstract--After biological and/or physico-chemical treatment of stabilised landfill leachates, COD and
salinity content are often larger than reject requirements. In this case, reverse osmosis can be used to treat
effectively these residual COD and salinity. However, reverse osmosis feasibility is limited by the
membrane fouling. In order to reduce the landfill leachates high fouling power, coagulation-flocculation
is examined in this work as reverse osmosis pretreatment. Using the jar-test procedure, physico-chemical
conditions were optimised. It concerns the most effective coagulant between ferric chloride and aluminium
sulphate, the optimal pH and the most effective flocculant between anionic, cationic and nonionic
polymers. Although 97% reduction turbidity was achieved, the supernatant still presented a pronounced
fouling power (Fouling Index above 15 min-~), according to the large supernatant iron content. By adding
upstream coagulation phase both H202 as oxidant and lime for pH control, iron content and Fouling Index
supernatant were reduced underneath 2 mg/l -~ and 5 rain -~, respectively. Also, supernatant could be
treated by reverse osmosis without entailing an important membrane fouling. © 1997 Elsevier Science
Ltd.

Key words--landfill leachate, coagulation-flocculation, oxidation, optimisation, fouling reverse osmosis

INTRODUCTION Chemical oxidation

Several processes drawn from wastewater treatment
technology have been applied to renovate landfill
leachate: aerobic and anaerobic biological degra-
dation, chemical oxidation, chemical precipitation,
coagulation-floccutation, activated carbon adsorp-
tion and membrane processes (Enzminger et al.,
1987; Koch, 1991; Lisk, 1991).
Biological processes, as treatment lagoons (Uloth
and Mavinic, 1977; Robinson and Maris, 1983;
Chamalot et al., 1984; Robinson and Grantham,
1986), activated sludge process (Palit and Quasim,
1977; Keenan et al., 1984), trickle beds (Uloth and
Mavinic, 1977; Stegmann and Ehrig, 1980; Joly,
1988) and anaerobic fixed film reactors (Gourdon,
1987) are adapted to treat biodegradable organic
matters. The best results of biodegradation processes
are obtained generally with detention time of 5-85
days and temperature larger than 10°C. However,
strong contents in ammonia nitrogen constitute a
limiting factor. Furthermore, a contribution of
phosphorus is often necessary (landfill leachates are
generally showing deficit of phosphorus). Neverthe-
less, biological processes are especially efficient in
treatment of young landfill leachates that are rich in
volatile fatty acids (Table 1).
*Author to whom correspondence should be addressed.
Chlorine, ozone, hydrogen peroxide, potassium
permanganate and calcium hypochlorite are habitu-
ally used oxidants (Ho et al., 1974; Chian and
Dewalle, 1976; Fraser and Tytler, 1983; Fraser and
Sims, 1984). Chemical oxidation effects are princi-
pally odour and sulphide elimination. The percentage
removal of COD is generally in the order of 20-50%.
Chemical precipitation
Calcium hydroxide (lime) is the most used reactive
(Thornton and Blanc, 1973; Ho et al., 1974; Keenan
et al., 1983; Slater et al., 1983a; Millot, 1986).
Requiring generally 1-15g/l of lime in landfill
leachates treatment, chemical precipitation effects are
pH and hardness increasing, low percentage re-
duction of COD (20-40%), very good removal of
heavy metals (90-90%) and 70-90% removal of
colour, turbidity, suspended matter and dispersed oil.
Adsorption
Granular or powdered activated carbon is the
major used adsorbant (Imai et al., 1983; Suidan et al.,
1993). Carbon adsorption permits 50-70% removal
of both COD and ammonia nitrogen. Other
materials, tested as adsorbant, have given close
treatment performances to those obtained with
activated carbon. These are zeolite, vermiculite, illite,
keolinite, activated alumina and municipal waste

2775
2776 A. Amokrane et al.

incinerator bottom ash (Chian and DewaUe, 1976;
Pillay, 1985).
Coagulation-flocculation
Aluminium sulphate (alum), ferrous sulphate,
ferric chloride and ferric chlorosulphate are com-
monly used coagulants (Thornton and Blanc, 1973;
Cook and Foree, 1974; Ho et al., 1974; Keenan et al.,
1983; Slater et al., 1983a; Stegrnann and Ehrig, 1980;
Chamalot et al., 1984; Ehrig, 1984; Millot, 1986).
Iron salts seem more efficient than aluminium ones.
The percentage removal of COD and TOC obtained
by coagulation-flocculation is generally 10-25% with
young leachates, but are highest (50-65%) with
leachates of low BODs/COD ratio (stabilised
leachates or leachates pretreated by biological
processes). Nonionic, cationic or anionic polyelec-
trolyte can be used as coagulant aids to increase floc
settling rate, without improving really turbidity
removal efficiency.
Membrane processes
Microfiltration, ultrafiltration and reverse osmosis
are membrane processes applied in landfill leachates
treatment (Chian and Dewalle, 1976; Syzdek and
Ahlert, 1984; Slater et al., 1983b; Krug and
McDougail, 1988; Koch et al., 1990; Bilstad and
Madland, 1992; Parveau, 1993; Amokrane, 1994).
Microfiltration and ultrafiltration were tested princi-
pally as reverse osmosis pretreatment, whereas
reverse osmosis was studied for removing landfill
leachates salinity and residual COD. Using fiat,
tubular or spiral wound configurations and cellulose
biological degradation, physico-chemical treatment
and activated carbon adsorption are rarely suited to
treat effectively these leachates. On the contrary,
reverse osmosis allows at least 95% reduction in both
COD and Total Dissolved Solid (Krug and
McDougall, 1988; Koch et al., 1990; Bilstad and
Madland, 1992; Parveau, 1993; Amokrane, 1994).
However, landfill leachate reverse osmosis feasi-
bility is highly conditioned by the choice of the feed
pretreatment mode. Biological pretreatment are often
proved ineffective as reverse osmosis pretreatment
(Chian and Dewalle, 1976; Holz and Weber, 1990;
Koch et al., 1990). On the contrary, lime precipi-
tation or coagulation-flocculation would be adapted
(Chian and Dewalle, 1976; Slater et al., 1983a). In
the same way, microfiltration and ultrafiltration
have proved to be suitable, provided that they
are preceded by physico-chemical processes as
coagulation-flocculation or lime precipitation (Slater
et al., 1983b; Syzdek and Ahlert, 1984; Krug and
McDougall, 1988).
However that may be, coagulation-flocculation is
the suited pretreatment mode for removal colloidal
particles that are the principal reverse osmosis
foulant of landfill leachates. However, this treatment
process is often recommended for stabilised leachate
COD removal (Stegrnann and Ehrig, 1980; Chamalot
et al., 1984; Ehrig, 1984; Millot, 1986).
In this work, coagulation-flocculation is examined
and optimised as an appropriate reverse osmosis
pretreatment of stabilised landfill leachates.
EXPERIMENTAL PROCEDURE

acetate or aromatic polyamide membranes, reverse Coagulation-flocculation experiments were performed

osmosis permits removing of at least 95% of
dissolved solids and COD.
Several authors (Chian and Dewalle, 1976; Scott,
1981; Friant, 1983; Granet et al., 1986; Krug and
McDougall, 1988) have correlated treatment
efficiency of these processes with landfill age for
removal leachate organic content (Table 1).
For many landfills that are l0 years old or more in
France and elsewhere in Europe and America,
leachates become increasingly stabilised. Processes as
with a Bioblock flocculator that comprises six paddle rotors
(24.5 mm x 63.5 mm) for 1 liter high shape beakers.
According to a jar test procedure, aluminium sulphate
(20 g AI 1-~) or ferric chloride (119.3 g Fe 1-~), was added to
a 500-ml raw leachate sample and mixed for 3 min at
200 rpm. The coagulant doses of alum or ferric chloride
used range from 0 to 0.07 mol 1-~ of AI or Fe, at varying
increments. Later on, using 2 g 1-t of nonionic, anionic or
cationic polymer, flocculant dosage, ranging from 0 to
100 mg 1-~ at varying increments, was added and mixed for
15 min at 40 rpm. The formed floc sizes were appreciated
visually, and diameters were determined using technical

Table 1. Landfillleachateprocessestreatment(removalefficiencyoforganiccontent).*VFA:
volatile fatty acids
Landfill age (years) <5 (young) 5-10 (medium) >10 (old)
Leachate type 1 (biodegradable) ii (intermediate) III (stabilised)
pH < 6.5 6.5-7.5 > 7.5
COD (g/l) > 10 < 10 <5
COD/TOC < 2.7 2.0-2.7 > 2.0
BODs/COD < 0.5 0.1~).5 < 0.1
VFA* (% TOC) > 70 5-30 <5
Processes Treatment el~ciency
Biologicaltreatment Good Fair Poor
Chemical oxidation Fair-poor Fair Fair
Chemical precipitation Fair-poor Fair Poor
Activatedcarbon Fair-poor Good-fair Good
Coagulation-floeeulation Fair-poor Good-fair Good
Reverse osmosis Fair Good Good
 Pretreatment of landfill leachates 2777

image treatment assisted by computer. Images acquisition of Table 2. Raw leachate average analysis and Jeandelaincourt Reject
formed flocs were carried out using a CCD-MICAM VHR Requirements (JRR). *mg 1-~, except pH, Redox potential (mV),
monochrome camera under normal reflexion lighting A-turbidity (NTU) and Fouling Index (min-I)
produced by a 1000W lamp. Each image was then Parameter* Raw leachate JRR
transferred to a computer and treated by NOESIS- pH 8.2 5.5-8.5
VISILOG 3.6 image treatment software (Amokrane, 1994). Redox potential - 217 --
After sedimentation and when sludge height was definitely Suspended matter 200 30
stabilised, sedimentation time and sludge amount were A-turbidity 1800 --
noted, and a 100-ml supernatant was siphoned off and N-turbidity 30 --
analysed for pH, redox, turbidity, COD, TOC, silica, Fe, AI Silica (mg ~) 20.4 -
and Fouling Index (FI). TOC analysis was carried out using Fouling Index < 15 --
a Beckman Tocamaster model 915B carbon analyser. Using BOD5 200 50
COD 4100 150
a Hach Model DR/2 absorption spectrophotometer, COD, TOC 1430
silica, AI and Fe (ferrous iron and total iron) analysis were Volatile fatty acids < 10
performed, respectively, using the dichromate reactor digest, NO3 124 15
molybdosilicate, aluminon and phenanthroline methods. NH4 1040 10
For FI determinations, conventional filtration test was used PO3 8.4
with a 0.45-/~m Millipore filter run at 1 bar for 5 min. This so~- 550 250
method consists of determining the amount of time taken to F 4.2 15
collect a 100-ml sample at the start of the 5-min test and CI- 5420 250
Ca2+ 68 --
comparing this time to the amount of time taken to collect Mg2+ 110 --
a 100-ml sample at the end of the 5-rain period. The sample K+ 880 --
would be considered foulant or not foulant, depending on Na + 3000
FL values greater or smaller than 5 min -I. Taking t~ and tr Fe 0.91 5
as the time required to collect, respectively, the first and final AI 0.68 -
samples, FI is determined by the use of the following Pb 0.46 I
equation: Zn 0.73 1
Cu 0.39 1
FL (min-') = (100/5) (1 - t,/tf). Ni 0.81 1
Cd 0.10 0.1
Turbidity was determined by two methods, noting either
A-turbidity or N-turbidity. In A-turbidity analysis, the
absorption method (using a Hach Model DR/2 spectropho-
tometer calibrated at 450 nm-wavelength) accounts for both
colloid turbidity and colour. In N-turbidity analysis, colour capacity so they must be pretreated before reverse
interference is eliminated by using Hach 2100A nephelomet- osmosis treatment to avoid rapid and irreversible
ric turbidimeter calibrated at a wavelength of 720 nm. We reverse osmosis membrane fouling.
note that N-turbidity was determined on raw leachates and
only on supernatant obtained with optical conditions of pH, Optimal coagulant dose (OpCD)
ferric chloride, nonionic flocculant and peroxide hydrogen.
N-turbidity determination was proved necessary in order to Several coagulant doses were tested at free pH
compare supernatant turbidity content to turbidity critical without adding flocculant. The results of experiment
value (that is fouling limit values beyond which reverse are presented in Figs 1 and 2.
osmosis membrane has tendency to be foul). We remind that Corresponding to a maximum A-turbidity removal
colour interference is eliminated in turbidity critical value
analysis (analysis performed at a wavelength of 720- (Fig. 1), the O p C D (Optimal Coagulant Dose) was
750 nm). similar for aluminium sulphate and ferric chloride
(about 0.035 mol 1-~ of A1 or Fe). However, ferric
RESULTS AND DISCUSSION chloride proved more effective than aluminium
sulphate in both A-turbidity (94% on 87%) and
Leachate characterisation C O D removal (55% on 42%).
The leachate treated in this study originated from With increasing coagulant dose, the percentage
waste landfill located in the Jeandelaincourt town sludge volume (ml of sludge per 100 ml of leachate)
(Meurthe-et-Moselle Department, France). Table 2 increased gradually, gave a maximum (45%) for
lists the average analysis results performed on coagulant dose near optimal coagulant dose and
samples. Contrary to low heavy metal content, decreased beyond (Fig. 2).
salinity is very high, especially chlorides, potassium, Supernatant pH decreased continually with in-
sodium, sulphates, nitrates and ammonia. In the creasing coagulant dose and gave a value of 5.1 or 5.5
same way, organic pollution is much greater than with O p C D of ferric chloride or aluminium sulphate.
BOD and C O D J R R (Jeandelaincourt Reject This p H decrease can be explained by the acidic
Requirements). However, leachates are very stabil- character of Fe 3+ or AI 3+ (acid of Lewis). By reacting
ised ( B O D d C O D = 0.05), so biological processes with O H - ions of leachage, aluminium or iron
would not be adapted. Effectively, it was obtained precipitate in form of Fe(OH)3 or AI(OH)3 (O'melia,
less than 20% C O D reduction using activated sludge 1969).
technology and a fungal approach (Manf~, 1993). With increasing coagulant dose, the dark brown
After all, regarding high values of raw leachate colour of raw leachate turned, after sludge separ-
suspended matter (200 mg 1-J), turbidity (1800 N T U ation, to a clear brown, then to yellow and became
for A-turbidity and 30 N T U for N-turbidity) and F L clear yellow for the coagulant dose near the optimal
( > 15 mion-~), leachates have an appreciated fouling coagulant dose.
2778 A. Amokrane et al.

100 ¸
,a' ~ • . e = A-t~ Ore)
90 • • ~ ~ - A-tudbidity (/J)
mY F /" ~ ~, - *- co,(,~)
, i \ ,,~ i co.(~
70

60
.Y \
i-
.~ 40
q ..""~ .A ",,
30 ..',y ..i" \\ '.,,.
2O

10
• . 4[..-.~- " ",
0 I I I I I I

o,ol 0,02 0,03 0,04 O,OS 0,06 0,oI

Coagulant dose (mol/L o f Fe or AI)

Fig. 1. Percentage reduction A-turbidity and COD vs. coagulant dose. Coagulation-flocculation tests
performed at free pH.

For each coagulant dose tested, flocs were less than be considered more reverse osmosis-foulant (FI~
0.1 mm in diameter, and sedimentation times value greater than 15 min-~).
required were important (2 h).
With OpCD of ferric chloride, the supernatant p H influence
ferrous and ferric content were, respectively, 18 and Lime milk (50gl -~) and sodium hydroxide
10 mg 1-~ (Table 3). In the same way, the aluminium solution (NaOH 8 N) were used for pH control tests
content was significant (16mgl -~) with OpCD of performed with, respectively, ferric chloride and
aluminium sulphate. In any case, supernatant would aluminium sulphate optimal dose.

D,~ . a- Slad~ Ore)

&
......... ~- ©- a ql~d~' a = Sl.dise (,~d) 8

40 ¸ " - ~ °" J \ " t:, ...... " ...... v.o~) 7

35

S I:

"" ......, ..
,I
10 .:I i "o, 2

$ °.'/ k. "° 1

o I t I I I I 0
o o,ot 0,02 0,o3 0,04 o,os 0,06 0,07

Co•lpud~t dole (uwi/L o f Fe or AI)

Fig. 2. pH supernatant and percentage sludge volume (ml 100ml -~ of leachate) vs. coagulant dose.
Coagulation-flocculation tests performed at free pH.
 Pretreatment of landfill leachates 2779
Table 3. Coagulation-flocculation to optimal dose of ferric chloride precipitate more, and then iron removal is more
and aluminium sulphate
efficient (than that in 4.5-5.5 pH), but A-turbidity
Supernatant
reduction is less considerable so that supernatant
Analysis Jeandelaincourt Ferric
Parameter raw leachate chloride Alum
could foul a reverse osmosis membrane by its residual
turbidity. However, because of its alkaline pH, the
pH 8.8 5.6 5.1
Redox potential (mV) -220 +207 supernatant would foul reverse osmosis membrane by
+ 334 CaCO3 scaling. In this case, supernatant must be
A-turbidity (NTU) 1350 75 175
COD (mg 1-~) 3800 1700 2200
pretreated once again (before subsequent reverse
AI (mg 1-') 0.85 0.35 16.3 osmosis process) to remove residual turbidity and
Fe 2. (mg 1-~) 1.35 18,0 1.05 especially to remove CaCO3 by, for example, CO:
Fe 3~ (rag 1 ~) 2.17 10,8 1.21
Total iron (rag I ') 3.52 28,8 2.26 adding until pH9 (to precipitate CaCO3) and
FI5 (min ') >15 >15 >15 acificiation (by HC1 adding) until a pH of 4.5-6.5 is
achieved (Slater, 1983b; Krug and McDougall, 1988).
Therefore, we have decided to perform coagulation-
Using optimal coagulant dose, experiment results,
flocculation at optimal pH so as to reduce efficiently
listed in Fig. 3, indicate that A-turbidity and COD
turbidity. Nevertheless, we have tempted to remove
removal decrease with pH increasing. By considering
residual iron by optimising subsequent oxidation.
optimal pH as being the pH at which maximum
A-turbidity removal is obtained, it seems that optimal Flocculation improvement with polymer
pH is influenced by OpCD, i.e. optimal pH
In all coagulation-flocculation tests described
corresponds to pH achieved at OpCD (4.9 with
previously, flocs obtained were less than 0.1 mm,
ferric chloride and 5.5 with aluminium sulphate).
and the sludge needed more than 2 h for sedimen-
A-turbidity reduction is less efficient in the alkaline
tation.
region than that in the 4.5-5.5 pH region. This is in
To improve flocculation quality, the optimal
accordance with results obtained by several authors
coagulant dose (0.035 mol 1-~ of AI or Fe) was used,
in their leachate coagulation-flocculation exper-
and three organic polymers, manufactured by
iments (Stegmann and Ehrig, 1980; Chamalot et al.,
SNFloerger, were tested. These are:
1984; Ehrig, 1984; Millot, 1986). Again, note that
organic colloids are favourably flocculated for pH • AH912BPM and AH912SH non-ionic polymers
between 4 and 4.5 with ferric salts and between 5 and (polyacrylamides with molecular weights of 5 and
6 with aluminium salts (Babcock and Singer, 1979; 20 million, respectively),
Semmens and Field, 1980; Lefebvre and Legube, • AN934BPM and AN934BPM anionic polymers
1990; Blanc and Navia, 1991). (copolymers of acrylamide and acrylic acid, with
If coagulation-flocculation is carried out in the molecular weights of 5 and 20 million and with
alkaline region (pH > 9), Fe(OH)3 and Fe(OH)2 34% molar anionicity, respectively),

100

9O O~u . 0,, .11~_ . u ,,0 m

8O

70

6O []

50

4O

3O

2O

10 . ~. COD(Ire)
.L COD (AI)
0
4,5 S 5~ 6 6,5 ? 7,5 8

plI

Fig. 3. Percentage removal A-turbidity and C O D vs. supernatant pH. Coagulation-flocculation tests
performed at optimal coagulant dose (0.035 mol I ] of Fe or AI).
2780 A. Amokrane et al.

Table 4. Coagulationto optimaldose of ferricchlorideand alum. Floeculationwith polymers.*Used floeeulantdoses are

0, 8, 16, 23, 31, 39, 46, 57, 68, 76, 94 and ll2mgl -~
Coagulant Aluminium sulphate Ferric chloride
(dose used) (0.035 mol AI 1-~) (0.035 ml Fe I -~)

Polymer Nonionic Anionic Cationic Nonionic Anionic Cationic

Doses tested (rag 1-~)* 0--90 0-90 0-90 0-110 0-110 0-110
Optimal dose (mg I -~) -- 40 -- 40 -- --
Flocs size ( m m ) < 1 2--4 < I 2-4 < 1 < 1
Sedimentation time (min) 120 30 120 30 120 120
Percentage C O D reduction 35-45 35-45 35-45 45-55 45-50 40-55
Percentage A-turbidity reduction 85-90 90 90 95 95 95
F h (min -~) > 15 > 15 > 15 > 15 > 15 > 15

• FO7140, FO8400 and FO8990 cationic polymers
(copolymers of acrylamide and dimethyl-
aminoethyl acrylate, with molecular weights of
11, 6 and 10 million and 14, 40 and 99% molar
cationicity, respectively).
Testing several flocculant doses, ranging from 0 to
100 mg 1-~ at varying increments (Table 4), it appears
that cationic polymers are not effective. Size flocs and
sedimentation time sludge are identical to those
obtained without polymer. However, the best results
(flocs of greater size and lower sedimentation time)
were obtained with aluminium sulphate/anionic
polymer and ferric chloride/nonionic polymer combi-
nations. According to the nature of the most effective
flocculant (anionic with alum and nonionic with
ferric chloride), the supernatant's zeta potential was
probably negative or zero when alum or ferric
chloride were respectively used. Nevertheless, with a
polymer dose of 40 mg 1- ~and above, flocs have a size
of 2 - 4 m m , and the required time sedimentation
was reduced to 30 min. We noted that 20% sludge
floats on the surface of the supernatant for a polymer
dose greater than 60 mg 1-~. It is possible that flocs
have a low apparent density and probably contained
a large amount of interstitial water. In any case,
FI5 were greater than 15min -1. However, ferric
chloride produced the best results, and ulterior tests
are being conducted with ferric chloride as the
coagulant and AH912BPM nonionic polymer as the
flocculant.
Pre-oxidation
Because of its high Fouling Index (FI > 15 min-~),
supernatant can be considered more reverse osmosis-
foulant. This may be correlated to the large
supernatant iron content (about 3 0 m g l -~) whose
important part is in the ferrous state (18 mgl-~).
Ferrous iron probably originated from ferric
coagulant reduction by the strong reduction power of
the leachate ( - 2 2 0 mV).
Thereby, pre-oxidation tests were carried out by
adding H202 (333gi -~) to a 500-ml sample raw
leachate and mixing for 3 rain at 200 rpm in the
upstream coagulation phase. After coagulation-floc-
culation (0.034mol F e l -~ ferric chloride and
40 mg 1-~ nonionic polymer) and 30-min sedimen-
tation, supernatant samples were withdrawn for
analysis. Listed in Table 5 are results showing that the
supernatant FI5 and ferrous content were less than
that without addition of H202.
By using 1-2 g H2021 -~, 85-90% reduction in iron
content and 42% reduction in FI5 were obtained.
However, with a decrease in pH, resulting from
the addition of H2Oz, the supernatant quality
deteriorated (with an A-turbidity increase of 55-
125 NTU).
Therefore, lime milk ( 2 0 g l -~) was added after
H202 addition to control pH. The experiment results
are presented in Table 6. It appears that the best
results were obtained at a pH of 4.5-5.0. In that case,
a maximum reduction A-turbidity was achieved,
whereas iron content and FI5 were reduced,
respectively, to below 2 mg 1-~ and 5 min-~.
Using an optimal dose of ferric chloride (0.035 mol
Fe 1- ~) and AH912BPM nonionic polymer
(40 mg 1-1), the supernatant was analysed for several
parameters in the first case without pre-oxidation and
in the second case with the addition of both HzO2

Table 5. Pre-oxidation with H202 without pH control

H20~ pH A-turbidity Fe z* Fe 3+ Total iron Fh
(g l -L) (--) (NTU) (rag 1-~) (mg 1-') (mg I-~) (rain-')
0 4.5 55 18.6 10.1 28.7 16.1
0.33 4.3 60 1.55 2.32 3.87 --
0~66 4.1 65 1.52 2.17 3.69 14.4
0.98 3.9 65 1.47 1.97 3.44 11.7
1.31 3.8 75 1.56 2.03 3.59 --
1.63 3.7 95 1.21 1.94 3.15 --
1.96 3.7 125 1.06 1.83 2.89 9.3
2.28 3.6 125 1,13 2.21 3.34 --
2.61 3.6 125 1,15 2.14 3.29 10.1
2.93 3.5 145 1,13 2.24 3.37 --
3.25 3.5 145 1.08 2.06 3.14 9.9
3.57 3.4 155 1.12 2.13 3.25 --
 Pretreatment of landfill leachates 2781

Table 6. Pre-oxidationwith H_,O2and pH control with limemilk

H202 Ca(OH): pH A-turbidity Fe2+ Fe3+ Totaliron Fh
(g I ') (g 1-~) (--) (NTU) (mg 1-9 (rag I ') (mg 1-') (rain-')
1.30 0.08 4.0 70 1.41 2.07 3.48 --
0,16 4.3 65 1.17 1.72 2.89 10.1
0.20 4.4 55 1.08 1.11 2,19 --
0.23 4,6 55 0.83 1.14 1.97 --
0.27 4.8 55 0.66 I.I 7 1.83 4.7
0.31 4.9 65 0,63 1.12 1.75 4.2
0.39 5,13 65 0,54 1,11 1.65 4.7
1.94 0.19 4.0 65 0.97 1.51 2.48 7,6
0.23 4,3 55 0.77 1.23 2.00 4.9
0.27 4,4 55 0.59 1.07 1.66 --
0.31 4.6 50 0.43 0.92 1.35 --
0.35 4.8 55 0.42 1.03 1.45 --
0.39 5.0 50 0.49 1.03 1.52 --
0.42 5.2 65 0.46 1.06 1.52 4.5

Table 7. Coagulation-flocculation with and without pre-oxidation Although their optimal doses are identical
at optimal conditions of pH, FeCI3, polymer and H20:. Supernatant
analysis. *mg I -~, except pH, turbidity ( N T U ) and FI~ (rain-'). (0.035 m o l l - ' of Fe or AI), ferric chloride has
tCritical values are fouling limit values beyond which reverse produced better results than aluminium sulphate in
osmosis m e m b r a n e has a tendency to be foul (Bates et al., 1988)
the removal of A-turbidity (95% on 87%) and COD
Analysis Raw Without With Critical (55% on 42%). In any case, the optimal pH
parameter* leachate pre-oxidation pre-oxidation valuest
corresponded to pH values achieved at the optimal
pH 9.2 4.8 4.7 --
A-turbidity 1500 55 50 -- coagulant dose (5 with ferric chloride and 5.5 with
N-turbidity 30 1.22 0.86 1 aluminium sulphate). Flocculation improvement was
Silica 20.7 7.7 6.3 100 possible if ferric chloride was combined with
AI 0.81 0.34 0.16 1
Fe 2÷ 0.48 18. I 0.39 0.3 40 mg 1-' of nonionic polymer and aluminium
Fe ~+ 0.45 10.3 0.87 - sulphate with 40 mg 1-' of anionic polymer. However,
Total iron 0.93 28.4 1.26 0.3
Fh > 15 16.2 3.9 5
fouling index ( > 15 min-') was much greater than
COD 3950 1800 1700 -- 5 min -~ (the limit beyond which reverse osmosis
TOC 1200 320 324 -- membrane has a tendency to be foul). This is
probably because of the large amount of aluminium
(about 16 mg 1-') or total iron (about 30 mg 1-') in
(1.94g1-') and lime milk (0.31 g l - ' ) . Experiment the supernatant when aluminium sulphate or ferric
results are listed in Table 7. chloride is respectively used.
It appears that the pre-oxidation-coagulation-floc- It would have been possible to reduce more
culation supernatant was less foulant than the residual iron or aluminium content, by carrying out
supernatant obtained without pre-oxidation. coagulation-flocculation in the alkaline region
Residual N-turbidity content is less than 1-2 NTU, (pH > 9). However, residual A-turbidity content is
whereas the residual A-turbidity value is about greater than that obtained by coagulation performed
50 NTU. A-turbidity readings are very likely a rather at optimal pH (5 with ferric chloride and 5.5 with
residual colour absorbance (98-99%). aluminium sulphate). If coagulation-flocculation is
Percentage removals of COD are similar with carried out at alkaline pH, however, the obtained
(57%) and without (54%) the addition of H,O> supernatant could foul a reverse osmosis membrane
Similarly, the addition of H202 leads to a percentage by CaCO3 scaling. In these conditions the super-
removal of TOC (73%) that is identical to that natant must be additionally pretreated to remove
without the addition of H202 (73%). CaCO3 (by carrying out, upstream subsequent reverse
We note that the H202 dose was optimised so osmosis step CO2 recarboration and HC1 acidification
as to remove maximum residual iron, without until a pH of 4.5-6.5 is raised).
being preoccupied with additional COD removal. Finally, by carrying out coagulation-flocculation
It would have been possible to optimise H,O2 with ferric chloride (0.035 mol 1-' of Fe) and nonionic
addition to remove maximum COD equally, but the polymer ( 4 0 m g l - ' of polyacrylamide), it was
required H202 doses in this case would be too high, possible to obtain a low residual iron content (below
so that the supernatant would damage reverse 2 mg 1-~), by using peroxide hydrogen (1.94 g 1-~)
osmosis membranes that are sensitive to oxidants as before coagulation and by adjusting pH coagulation
H202. to 4.7 with lime milk. In this case, the iron content
and fouling index of the supernatant were reduced to
CONCLUSIONS below, respectively, 2 m g l ' and 5 min-'. Thus,
supernatant would be less reverse osmosis-foulant.
Coagulation-flocculation was studied as a landfill This is in accordance with results obtained in
ieachate reverse osmosis pretreatment of stabilised supernatant reverse osmosis treatment tests
landfill leachates. (Amokrane, 1994).
WR 31;ll E
2782 A. Amokrane et al.
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