Science of the Total Environment 333 (2004) 37 – 58

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Treatment of pulp and paper mill wastewater—a review

D. Pokhrel, T. Viraraghavan *
Department of Environmental and System Engineering, Faculty of Engineering, University of Regina,
3737 Wascana Parkway, Regina, SK, Canada S4S 0A2
Received 2 July 2003; received in revised form 29 January 2004; accepted 7 May 2004

Abstract

Pulp and paper mills generate varieties of pollutants depending upon the type of the pulping process. This paper is the state
of the art review of treatability of the pulp and paper mill wastewater and performance of available treatment processes. A
comparison of all treatment processes is presented. Combinations of anaerobic and aerobic treatment processes are found to be
efficient in the removal of soluble biodegradable organic pollutants. Color can be removed effectively by fungal treatment,
coagulation, chemical oxidation, and ozonation. Chlorinated phenolic compounds and adsorable organic halides (AOX) can be
efficiently reduced by adsorption, ozonation and membrane filtration techniques.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Pulp; Pulp and paper; Wastewater; Treatment

1. Introduction pollutants characterized by biochemical oxygen de-

The rapid increase in population and the increased
demand for industrial establishments to meet human
requirements have created problems such as overex-
ploitation of available resources, leading to pollution
of the land, air and water environments. The pulp and
paper industry is one of the most important industries
of the North American economy and ranks as the fifth
largest in the U.S. economy (Nemerow and Dasgupta,
1991). In Canada, the pulp and paper industry
accounts for a major portion of the country’s economy
in terms of value of production and total wages paid
(Sinclair, 1990). The wood pulping and production of
the paper products generate a considerable amount of
* Corresponding author. Tel.: +1-306-5854094; fax: +1-306-
5854855.
E-mail address: t.viraraghavan@uregina.ca (T. Viraraghavan).
mand (BOD), chemical oxygen demand (COD), sus-
pended solids (SS), toxicity, and color when untreated
or poorly treated effluents are discharged to receiving
waters.
The high water usage, between 20,000 and 60,000
gallons per ton of product, (Nemerow and Dasgupta,
1991) results in large amounts of wastewater genera-
tion. The pulp and paper industry is considered as the
third largest polluter in the United States (US). It has
been estimated that the pulp and paper industry is
responsible for 50% of all wastes dumped into Cana-
da’s waters (Sinclair, 1990). The effluents from the
industry cause slime growth, thermal impacts, scum
formation, color problems, and loss of aesthetic beauty
in the environment. They also increase the amount of
toxic substances in the water, causing death to the
zooplankton and fish, as well as profoundly affecting
the terrestrial ecosystem.

0048-9697/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2004.05.017
38 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58
The growing public awareness of the fate of these
pollutants and stringent regulations established by
the various governmental authorities such as provin-
cial and federal agencies are forcing the industry to
treat effluents to the required compliance level before
discharging them in to the environment. Many stud-
ies have been conducted so far on this sector regard-
ing the impacts as well as the control of the
pollutants. Berube and Kahmark (2001), Kahmark
and Unwin (1996, 1998, 1999), and Srinivasan and
Unwin (1995) have reviewed pollution control as-
pects of the pulp and paper industry. However, all
these reviews have focused on the state of the art in
integrated pollution management and lack a compara-
tive evaluation of various treatment processes partic-
ular to the water pollution control. This review,
therefore, would examine the pollution control sys-
tems and compare the performance of the effluent
treatment measures in use.
2. Process description
Pulping is the initial stage of the paper making
industry and provides the processed material. It is the
largest source of the pollution in the whole process of
papermaking. High amounts of wastewater are gene-
rated at different stages of this process.
2.1. Mechanical pulping
The yield of the pulp by this process is as high as
90– 95% (Smook, 1992) but the quality of the pulp is
of low grade, highly colored, and contains short
fibers.
2.2. Chemical pulping
The wood chips are cooked with appropriate
chemicals in an aqueous solution at an elevated
temperature and pressure to break chips into a fibrous
mass. The yield of the pulp by this process is about
40 – 50% of the original wood material (Smook,
1992). The chemical pulping is carried out in two
media: alkaline and acidic.
(a) Kraft process: The woodchips are cooked in a
solution of sodium hydroxide (NaOH) and
sodium sulfide (NaS2). This process is widely
used.
(b) Sulfite process: The wood chips are cooked in a
mixture of sulfurous acid (H2SO3) and bisulfide
ions (HSO3 ) to dissolve lignin.
2.3. Chemo-mechanical pulping (CMP)
The raw material is first treated chemically and
then subjected to drastic mechanical treatment to
separate the fibers. The efficiency of pulp obtained
ranges from 85 – 90% and the strength of the pulp is
relatively better than the pulp from the mechanical
pulping alone.
2.4. Thermo-mechanical pulping (TMP)
This process involves steaming the raw materials
under pressure for a short period, prior to and during
refining. The thermo-mechanical process is further
modified using chemicals during the steaming stage,
and the process is called chemi-thermomechanical
pulping (CTMP).
2.5. Papermaking
The paper making operation consists of two parts;
one is stock preparation by treating the pulp to the
required degree of fitness and the other is paper
making where the treated pulp is passed through
continuous moulds/wires to form sheets.
3. Sources of pollution
Each pulping process utilizes large amounts of
water, which reappear in the form of an effluent.
The most significant sources of pollution among
various process stages are wood preparation, pulping,
pulp washing, screening, washing, bleaching, and
paper machine and coating operations. Among the
processes, pulping generates a high-strength waste-
water especially by chemical pulping. This wastewa-
ter contains wood debris and soluble wood materials.
Pulp bleaching generates most toxic substances as it
utilizes chlorine for brightening the pulp. Pulp fibers
can be prepared from a vast majority of plants in
nature such as woods, straws and grasses, bamboos,
 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 39

or canes and reeds. Wood is the most abundant source
of papermaking fiber. Wood consists of various com-
pounds (lignin, carbohydrate, and extractives) which
are hard to biodegrade, and these derivatives are
washed away from the fibers during the washing,
dewatering, and screening processes. Depending upon
the type of the pulping process, various toxic chem-
icals such as resin acids, unsaturated fatty acids,
diterpene alcohols, juvaniones, chlorinated resin
acids, and others are generated in the pulp and paper
making process. The pollutants at various stages of
the pulping and paper making process are presented in
Fig. 1.
It is clear that an individual pulping stage gene-
rates different quantities, qualities and types of
pollutants. The wastewater pollution load from indi-
vidual pulping and papermaking process is given in
Table 1.
The amount of pollutants produced by an indivi-
dual mill is an important indicator to evaluate the

Fig. 1. Pollutants from various sources of pulping and papermaking (US EPA, 1995).
40 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

Table 1 Table 3
Typical wastewater generation and pollution load from pulp and Comparison of actual emissions from pulp mills (TAPPI, 1990)
paper industry (Rintala and Puhakka, 1994) Country Parameters
Process Wastewater SS COD SS BOD COD AOX N P
(m3/adt pulp (kg/adt (kg/adt (kg/adt) (kg/adt) (kg/adt) (kg/adt) (kg/adt) (kg/adt)
or paper) pulp) pulp)
Bleach kraft
Wet debarking 5 – 25 nr 5 – 20
USA 5 5 – 2.2 – –
Groundwood pulping 10 – 15 nr 15 – 32 Sweden 3.8 12 68 2 0.23 0.09
TMP -unbleached 10 – 30 10 – 40 40 – 60
TMP-bleached 10 – 30 10 – 40 50 – 120 Bleached sulfite
CTMP-unbleached 10 – 15 20 – 50 70 – 120
Sweden 6.8 17.8 145 1.8 0.3 0.10
CTMP-bleached 10 – 15 20 – 50 100 – 180
NSSC 20 – 80 3 – 10 30 – 120
Ca-sulfite (unbleached) 80 – 100 20 – 50 nr
Ca-sulfite (bleached) 150 – 180 20 – 60 120 – 180 Sweden for selected process are presented in Table
Mg-sulfite (unbleached) 40 – 60 10 – 40 60 – 120 3. The pollutant load discharge guidelines for the pulp
Kraft-unbleached 40 – 60 10 – 20 40 – 60
Kraft-bleached 60 – 90 10 – 40 100 – 140
and paper industry of some countries are presented in
Paper making 10 – 50 nr nr Table 4.
Agrobased small 200 – 250 50 – 100 1000 – 1100
paper mill
nr—not reported; adt—air dry ton; NSSC—neutral sulfite semi- 4. Wastewater characteristics
chemicals.
The characteristics of the wastewater generated
from various processes of the pulp and paper industry
performance of the system as well as a crosscheck depend upon the type of process, type of the wood
whether the mills have followed the guidelines. Table materials, process technology applied, management
2 provides performance data of selected processes and practices, internal recirculation of the effluent for
mills. recovery, and the amount of water to be used in the
The environmental guidelines on discharge vary particular process. As an example, Mohamed et al.
with countries. The emission data from USA and (1989) reported that the load of chlorinated phenols
and acids in the wastewaters of hardwood kraft mill
was three to eight times lower than it was in the soft
Table 2 wood kraft mill. The general characteristics of the
Typical pollution load per ton of production (kg/ton)
Process Pollutants
SS BOD COD Color Reference Table 4
Deinking – 11 54 –
Vlyssides and Discharge limits (monthly, semiannual, or annual verges) for
Economides bleached kraft pulp
(1997) Country Parameters
Wood yard 3.75 1 – 2 Springer (2000)
Pulping 13.5 5 – 1.5 Springer (2000) SS BOD COD AOX Reference
Bleaching 6 15.5 – 40 Springer (2000) (kg/adt) (kg/adt) (kg/adt) (kg/adt)
Papermaking 30.8 10.8 – 1.5 Springer (2000) Canada 9.5 – 14.5 5.5 – 30 – 1.4 – 1.5 TAPPI, 1990
Riocell 0.4 – 0.5 0.2 – 0.3 5 – 5.5 19 – 20a Foelkel (1989) Finland 5 – 15 6.8 – 34 90 1.4 TAPPI, 1990
(Brazil) Norway 5 – 90 6 TAPPI, 1990
Large mill 31.2 13 82.4 – Srivastava et al. Sweden 0.3 – 5.8 7.5 – 17 39 – 107 1.5 – 2 TAPPI, 1990
(India) (1990) Belgium 7 – 14.4 2.3 – 5.4 22 – 63 1.5 TAPPI, 1990
Small mill 140.3 152.26 639.4 – Srivastava et al. France 6.5 – 10 3.3 – 30 48 – 95 – TAPPI, 1990
(India) (1990) USA 3.86 2.41 Reserved 0.272 US EPA, 2000
Sweden 0.7 0.2 7.6 – Carlson et al. (8.47) (4.52) (0.476)
(2000) The U.S. EPA values are monthly average values for new bleached
a
Pt – Co (kg/ton). kraft mill. The values in the ( ) are daily maximum allowable.
 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 41

Table 5
Typical characteristics of wastewater (mg/l) at different processes (Bajpai, 2000)
Process Parameters
pH SS BOD5 COD Carbohydrate Acetic Methanol N P S
acid
TMP (1) – 383 2800 7210 2700 235 25 12 2.3 72
TMP (2) 4.2 810 2800 5600 1230 – – – – –
CTMP – 500 3000 – 4000 6000 – 9000 1000 1500 – – 167
Kraft bleaching 10.1 37 – 74 128 – 184 1124 – 1738 – 0 40 – 76 – – –
Kraft foul (1) 8.0 16 568 1202 – – 421 – – 5.9
Kraft foul (2) 10.2 0 10,700 16,000 – – – 306 1 91
Kraft foul (3) 9.5 – 10.5 0 5500 – 8500 10,000 – 13,000 – – 7500 – 8500 350 – 600 0.02 – 1.55 120 – 375
Sulfite 2.5 – 2000 – 4000 4000 – 8000 – – 250 – – 800 – 850
condensate (1)
Sulfite 2.8 – 5.9 – 3700 – 5110 9800 – 27,100 – – – – – 840 – 1270
condensate (2)
NSSC Pulping:
Spent liquor – 253 13,300 39,800 6210 3200 90 55 10 868
Chip wash – 6095 12,000 20,600 3210 820 70 86 36 315
Paper mill – 800 1600 5020 610 54 9 11 0.6 97

wastewater produced at various process stages and
pollution sources are given in Tables 5, 6 and 7.
5. Fate and effects on the environment
The pollutants discharged from the pulp and paper
industry affect all aspects of the environment such as
water, air and land. Makris and Banerjee (2002)
studied the fate of the resin acid in the secondary
treatment system. Various authors at different times
reported the appearance of toxic effects on various fish
species due to exposure of pulp and paper mill efflu-
ents. Many authors reported the presence of toxic
pollutants in fish or toxic effects on fish such as
respiratory stress, mixed function oxygenase activity,
toxicity and mutagenicity, liver damage, or genotoxic
effects, and lethal effects on the fishes exposed to pulp
and paper mill wastewaters (Owens et al., 1994; Vass
et al., 1996; Schnell et al., 2000b; Lindstrom-Seppa et
al., 1998; Leppanen and Oikari, 1999; Johnsen et al.,
1998; Erisction and Larsson, 2000). Baruah (1997)
reported on serious concerns related to the surface
plankton population change in Elengabeel’s wetland
ecosystem in India due to untreated paper mill effluent
discharge into the system. Yen et al. (1996) reported on
the possibility of the sub-lethal effects to the aquatic
organisms in the Dong Nai River in Vietnam due to the
effluents discharged from a pulp and paper mill.
However, there are also some contradictory reports
by other authors. Kovacs et al. (2002) reported no
significant evidence of depressed plasma steroids nor
increase in mixed function oxygenase (MFO) activity
in fish associated with pulp mill effluent. D’surney et
al. (2002) and Felder et al. (1998) indicated no
significant adverse effect in sediments, and river biota

Table 6
Characteristics of wastewater (mg/l) at various pulp and paper processes
Process Parameters References
TS SS BOD5 COD AOX Resin Color
(Ag/l) (Pt – Co)
Wood preparation 1160 600 250 – – – Nemerow and
Dasgupta (1991)
Drum debarking 2017 – 3171 – 480 – 987 – – 20 – 50 Springer (2000)
Bleach kraft mill – 34 23 – 12.5 69 – Wayland et al. (1998)
Newsprint mill 3750 250 – 3500 – 16 1000 Tardif and Hall (1997)
42 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

Table 7
Characteristics of wastewater at various pulp and paper processes
Process Parameters References
pH TS SS BOD5 COD Color
(mg/l) (mg/l) (mg/l) (mg/l) (Pt – Co)
Large mills (India) 11.0 5250 1233 983 2530 black Srivastava et al. (1990)
Small mills (India) 12.3 15,120 4890 2628 6145 DB Srivastava et al. (1990)
Digester house 11.6 51,589 23,319 13,088 38,588 16.6a Singh et al. (1996)
Combined effluent 7.6 3318 2023 103 675 1.0a Singh et al. (1996)
TMP whitewater 4.7 – 91 1090 2440 – Jahren et al. (1999)
TMP whitewater 4.7 – 105 1125 2475 – Jahren et al. (2002)
Kraft mill 8.2 8260 3620 – 4112 4667.5 Rohella et al. (2001)
Pulping 10 1810 256 360 – – Dilek and Gokcay (1994)
Kraft mill (unbleached) 8.2 1200 150 175 – 250 Nemerow and Dasgupta (1991)
Bleached pulp mill 7.5 – 1133 1566 2572 4033 Yen et al. (1996)
Bleaching 2.5 2285 216 140 – – Dilek and Gokcay (1994)
Pulp and paper 7.8 4200 1400 1050 4870 DB Mandal and Bandana (1996)
News air and land paper 8.3 450 400 16 78 – Vlyssides and
deinking Economides (1997)
Paper making 7.8 1844 760 561 953 Black Gupta (1997)
Paper mill 8.7 2415 935 425 845 DB Dutta (1999)
Paper machine 4.5 – 503 170 723 243 Yen et al. (1996)
Paper machine 8.3 – 1032 240 – – Dilek and Gokcay (1994)
a
Unit [Optical Density (O.D) at 465 nm]; ‘DB’ means dark brown; ‘LY’ means light yellow.

or on fish attributable to the treated mill effluent.
Stepanova et al. (2000) reported no clear evidence of
mutagens in most of aquatic animals studied in Lake
Baikal due to Baikalsk pulp and paper mill wastewater
discharged to the lake. Wayland et al. (1998) reported
no effect on the tree shallow, which feed on the insects
downstream of the pulp mill.
Howe and Michael (1998) studied the effects of the
treated pulp mill effluent on irrigated soil in northern
Arizona, which showed serious soil chemistry change.
Dutta (1999) investigated the toxic effect of the paper
mill effluent (treated) applied to a paddy field in
Assam, India. Gupta (1997) and Singh et al. (1996)
reported high loads of organic pollutants derived from
the paper mill wastewater in Tamilnadu, and Punjab,
India, respectively. Singh et al. indicated high level of
coliform bacteria in the effluent too. However, Archi-
bald (2000) indicated that the presence of coliform
bacteria in the pulp and paper effluent did not neces-
sarily mean a health hazard to the environment unless
pathogens were observed. Skipperud et al. (1998) and
Holmbom et al. (1994) reported the presence of various
trace metals in the pulp and paper mill effluents at low
levels. King et al. (1999) reported elevated levels of Mn
accumulation in the Crayfish exposed to the paper mill
wastewater. Mandal and Bandana (1996) reported on
health impacts such as diarrhea, vomiting, headaches,
nausea, and eye irritation on children and workers due
to the pulp and paper mill wastewater discharged to the
environment. High carbon dioxide level in the pulp and
paper mill effluents as a potential source of distress and
toxicity to rainbow trout was reported by O’connor et
al. (2000).
6. Wastewater treatment
Pollution from the pulp and paper industry can be
minimized by various internal process changes and
management measures such as the Best Available
Technology (BAT). Dube et al. (2000) reported a
60% reduction in effluent BOD due to an internal
process change in Irving Pulp and Paper Limited,
Canada. The estimated data by Springer (2000)
showed that the water use in the US in 1959 was about
250 m3/adt whereas water use in 1995 was reduced to
50 m3/adt. However, the average water use for the pulp
and paper mills in India was still 200 –259 m3/ton of
paper production (Gune, 2000). Several authors have
suggested internal process change as a measure to
 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58
control pollution (Reilama and Ilomaki, 1999; Webb,
1994; Dey et al., 1991). Raghuveer and Sastry (1990)
reported BOD, COD, and color reduction by internal
management measures. However, the treatment of the
wastewater by various external processes is essential.
Since pulp and paper industry discharges varieties of
pollutants, the treatment methods also vary.
6.1. Physicochemical treatment
Physicochemical treatment processes include re-
moval of suspended solids, colloidal particles, floating
matters, colors, and toxic compounds by either sedi-
mentation, flotation, screening, adsorption, coagula-
tion, oxidation, ozonation, electrolysis, reverse osmo-
sis, ultra-filtration, and nano-filtration technologies.
6.1.1. Sedimentation/flotation
Suspended matters present in the pulp and paper
wastewater are comprised primarily of bark particles,
fiber, fiber debris, filler and coating materials. Thomp-
son et al. (2001) stated that sedimentation was the
preferred option within the paper mills in the UK, and
contributed to more than 80% removal of the sus-
pended solids on an average. Rajvaidya and Markan-
dey (1998) stated that the design value of the primary
clarifier was 70 – 80% in average. Azevedo et al.
(1999) reported on the effect of pH on pulp settal-
ability. Gubelt et al. (2000) reported 65 – 95% removal
of TSS by dissolved air flotation and it was an
unstable unit. However, Wenta and Hartmen (2002)
mentioned that dissolved air flotation was able to
remove 95% of the TSS.
6.1.2. Coagulation and precipitation
Coagulation and flocculation is normally employed
in the tertiary treatment in the case of pulp and paper
mill wastewater treatment and not commonly adopted
in the primary treatment. Tong et al. (1999) and
Ganjidoust et al. (1997) carried out a comparative
study of horseradish peroxide (chitosan) and other
coagulants such as (Al2(SO4)3), hexamethylene di-
amine epichlorohydrin polycondensate (HE), poly-
ethyleneimine (PEI), to remove adsorbable organic
halides (AOX), total organic carbon (TOC), and color.
The authors indicated that modified chitosan was far
more effective in removing these pollutants than other
coagulants. Wagner and Nicell (2001) investigated the
43
treatment of foul condensate, defined by phenolic
compounds, and toxicity using microtox assay from
kraft pulping by horseradish peroxide and H2O2 and
found a total phenol reduction below 1 mg/l and
toxicity (microtox assay) reduction by 46%. Dilek
and Gokcay (1994) reported 96% removal of COD
from the paper machine, 50% from the pulping, and
20% for bleaching effluents by using alum as a
coagulant. Rohella et al. (2001) stated polyelectrolytes
were better than the conventional coagulant alum to
remove turbidity, COD, and color. Sheela and Distidar
(1989) reported on black liquor treatment by precipi-
tation with CaSO4
2H2O in the presence of CO2. The
removal of dissolved solids was reported to be 63%.
However, Wang and Pan (1999) reported that the use
of coagulants such as polyethylene oxide (PEO),
worsened the settlability and increased COD levels,
turbidity, and suspended solids of the treated effluent
when the dose was between 25 and 250 ppm. Cher-
noberezhskii et al. (1994) reported that coagulation
with aluminum sulfate or modified adsorbents was the
best option for color removal from the sulfate and
sulfite wood pulp and paper industry.
6.1.3. Adsorption
Murthy et al. (1991) reported a high removal of
color by activated charcoal, fuller’s earth, and coal ash.
Shawwa et al. (2001) reported 90% removal of color,
COD, DOC, and AOX from bleached wastewater by
the adsorption process, using activated coke as an
adsorbent. Sullivan (1986) concluded that the waste-
water produced by the Union Camp Facility at Frank-
lin, VA, can be treated by activated carbon and ion
exchange to reduce color and chloride to levels ac-
ceptable for reuse. Das and Patnaik (2000) investigated
the lignin removal efficiency of the blast furnace dust
(BFD) and slag by the adsorption mechanism. Their
study showed 80.4% and 61% removal of lignin by
BFD and slag, respectively. Narbaitz et al. (1997)
reported that PACTk process was an effective process
to remove AOX from the kraft mill effluent to meet
Ontario’s year 2000 regulation (AOX: 0.8 kg Cl/adt of
production).
6.1.4. Chemical oxidation
Balcioglu and Ferhan (1999) reported on photo-
catalytic oxidation of kraft pulp bleaching wastewater
showing that the removal largely depended on the
44 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58
concentration of COD and chloride below a certain
level. Zamora et al. (1998) reported on the use of
horseradish peroxide to decolorize kraft effluent by
50% within three hours of reaction time. The degra-
dation of phenolic and polyphenolic compounds pres-
ent in the bleaching effluent was studied using
advanced oxidation systems such as photocatalysis
with O2/ZnO/UV, O2/TiO2/UV, O3 and O3/UV. The
authors concluded that O2/ZnO/UV and O2/TiO2/UV
were the best systems to oxidize the effluent in a short
period of time. Perez et al. (2002c) reported that the
combination of Fenton and photo-fenton reactions
proved to be highly effective for the treatment of
bleaching kraft mill effluent. Verenich et al. (2000)
reported on the improvement in biodegradability of an
effluent from 30% to 70% by wet oxidation method.
Hassan and Hawkyard (2002) studied the removal of
color by combined oxidation with ozone and Fenton’s
reagent and stated that 100% color removal was
achieved at a pH of 4 – 5 in the case of ferral (derived
from natural clay sources, which contains 2% ferric
sulfate and 6% aluminum sulfate) and ferric sulfate.
Dufresne et al. (2000) reported on the oxidation of
total reduced sulfur (TRS) giving odor free products
by catalytically enhanced oxidation.
6.1.5. Membrane filtration
Jonsson et al. (1996) reported on the treatment of
paper coating color effluent treatment by membrane
filtration suggesting that the composition of the color
had a significant influence on the performance. Mem-
brane separation techniques were reported to be
suitable for removing AOX, COD, and color from
pulp and paper mills (Zaidi et al., 1992; Afonso and
Pinho, 1991, Falth, 2000). De Pinho et al. (2000)
compared the efficiency of (1) ultrafiltration and (2)
ultrafiltration plus dissolved air flotation. The results
showed 54%, 88%, 100% removal of TOC, color,
and SS, respectively by ultrafiltration alone. Ultrafil-
tration plus dissolved air flotation resulted in 65%,
90% and 100% removal of TOC, color, and SS,
respectively. Dube et al. (2000) reported that 88%
and 89% removal of BOD, and COD, respectively
was achieved by reverse osmosis (RO). Merrill et al.
(2001) stated that membrane filtration (MF), and
granular membrane filtration (GMF) were suitable
for removing heavy metals from the pulp and paper
mill wastewaters.
6.1.6. Ozonation
Yeber et al. (1999) reported that a substantial
removal of COD, TOC, and toxicity from pulp mill
effluent and increased biodegradability of the effluent
were achieved after treatment with ozone. Korhonen
et al. (2000) reported a 90% removal of ethylenedia-
minetetraacetic acid (EDTA) and a 65% removal of
COD by ozone treatment of the pulp mill effluent.
Hinck et al. (1997) reported that neither EDTA nor
diethylene triamine pentaacetic acid (DTPA) are bio-
degraded in aerobic conditions. Oeller et al. (1997)
reported high removal of COD and DOC from the
pulp effluent by ozone treatment. Freire et al. (2000)
reported a 12% reduction of total organic carbon, total
phenols reduced to 70%, and effluent colors to 35% of
bleached pulp mill effluent after 60 min of ozonation.
Several authors reported on toxic compounds, COD,
and color removal by ozone treatment (Hostachy et
al., 1997; Zhou and Smith, 1997; Yamamoto, 2001).
Roy-Arcand and Archibald (1996) reported that bio-
treated kraft effluents yielded a substantial decrease in
the biologically recalcitrant residual adsorbable or-
ganic halogens (AOX), converted COD to BOD and
yielded large decrease in color. Laari et al. (2000)
investigated the removal of lipophilic wood extrac-
tives from TMP wastewater by ozonation. The authors
indicated that a high dosage of ozone (100 –300 mg/
dm3) was required to remove 50% of lippphilic wood
extractives. Korhonen and Tuhkanen (2000) reported
that ozone doses of 0.2 mgO3/initial mgCOD elimi-
nated over 90% resin acid. Torrades et al. (2001)
reported high removals of TOC, COD, AOX, and
color from bleached kraft mill effluent (BKME1)
using heterogeneous photocatalysis and ozone treat-
ment. Sevimli and Sarikaya (2002) reported a 95–
97% color removal for high doses of ozone in 15 min
of ozonation. Kallas and Munter (1994) suggested
post treatment of bleached mill effluent by ozonation
and adsorption.
6.2. Biological treatment
6.2.1. Aerobic treatment
6.2.1.1. Activated sludge process. The performance
variation of the activated sludge due to the changes in
pH, temperature, and H2O2 and DTPA was reported
by Ginkel et al. (1999), Norris et al. (2000), and
 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58
Larisch and Duff (1997, 2000), respectively. Knudsen
et al. (1994) reported a high reduction of BOD and
soluble COD by a two-stage activated sludge process.
Shere and Daly (1982) claimed that TMP wastewater
was readily degradable by the activated sludge pro-
cess. Hansen et al. (1999) suggested upgrading the
activated sludge plant by the addition of Floobeds
(floating biological bed) in series that increased COD
and BOD removal from 51% to 90% and 70% to
93%, respectively. Chandra (2001) reported efficient
removal of color, BOD, COD, phenolics, and sulfide
by microorganisms such as Pseudomonas putida,
Citrobacter sp., and Enterobacter sp. in the activated
sludge process. Mohamed et al. (1989) reported
removal of chlorinated phenols, 1,1-dichlorodimethyl
sulfone (DDS), and chlorinated acetic acids in an
oxygen activated sludge effluent treatment plant.
Demirbas et al. (1999) reported AOX removal by
the activated sludge process. Junna and Ruonala
(1991) reported 90% BOD7, 70% COD, 40 – 60%
AOX, and 60 – 95% chlorinated phenols removal by
the activated sludge process. Bryant et al. (1992)
reported AOX removal of 46% on average from
two activated sludge systems studied. Andreasan et
al. (1999) suggested the addition of an anoxic selector
before the activated sludge plant to improve the
sludge settlability problem. Raghuveer and Sastry
(1991) reported that a minimum of mixed liquor
suspended solids (MLSS) of 2000 –2500 mg/l and
an aeration time of 6– 8 h were required to remove
83 – 88% of BOD. High removals of BOD, COD,
AOX, and chlorinated phenolics have been achieved
in the activated sludge process (Saunamaki, 1997;
Schnell et al., 2000a). Kennedy et al. (2000) reported
that the activated sludge was successful in removing
nearly all detectable Microtoxk toxicity from
bleached kraft pulp mills at low level whereas the
PACTk was slightly better in removing highly toxic
concentrated effluents.
6.2.1.2. Aerated lagoons. Stuthridge and Mcfarlane
(1994) stated that 70% removal of the AOX from the
aerated lagoon was attributed to a short residence
time section of the treatment system where the
chlorinated stage effluents were mixed with general
mill wastewaters. The effect of simple mixing was
reported to be responsible for 15 – 46% removal.
Bryant et al. (1997) reported 67% removal of am-
45
monia from black liquor spill at temperatures of 22 –
35 jC, pH near 7.3 in an aerated lagoon. Chernysh
et al. (1992) reported large variations in AOX and
TOC removal in a controlled batch study of bleached
kraft effluent in an operating lagoon under both
aerobic and anaerobic conditions. Welander et al.
(1997) reported COD removal of 30– 40% in a full-
scale lagoon and 60 – 70% in a pilot-scale plant.
Stuthridge et al. (1991) reported 65% removal of
AOX from bleached kraft pulp and paper mill
effluent. Junna and Ruonala (1991) reported removal
of BOD7 ranging between 50% and 75% and chlo-
rinated phenolics 10 – 50% by an aerated lagoon.
Achoka (2002) reported that an oxidation pond
removed chemical compounds greater than 50%.
Schnell et al. (2000a) reported removals of BOD,
AOX, chlorinated phenolics, and polychlorinated
phenolics respectively from an aerated lagoon.
6.2.1.3. Aerobic biological reactors. Many authors
have reported high removals of organic pollutants of
kraft mill wastewater by sequencing batch reactor
(SBR) treatment (Franta et al., 1994; Franta and
Wilderer, 1997; Milet and Duff, 1998). Reid and
Simon (2000) reported 100% removal of methanol
and 90% removal of CODsol by SBR. Substantial
removal of COD, TOC, BOD (Magnus et al.,
2000a), lignin and resin acids (Magnus et al.,
2000b) of TMP wastewater using high rate compact
reactors (HCRs) at a retention time of 1.5 h had
been reported. Removal of COD by a moving bed
bifilm reactor (MBBR) had been demonstrated (Jah-
ren et al., 2002; Borch-Due et al., 1997). Magnus et
al. (2000c) reported 93% and 65% removal of BOD
and COD, respectively by a biological compact
reactor. Berube and Hall (2000) showed that approx-
imately 93% removal of TOC could be achieved by
a membrane bioreactor. Asselin et al. (2000) con-
cluded that suspended carrier biofilm reactor (SCBR)
was highly efficient in removing chronic toxicity
from the effluent. Rovel et al. (1994) achieved
76%, 62%, 81%, and 48% removal of BOD,
COD, SS, and AOX, respectively, using a biofilter.
Rudolfs and Amberg (1953) demonstrated that aer-
obic treatment of whitewater (high strength) was
able to achieve 70 –80% removal of BOD. Typical
efficiencies of aerobic systems are presented in
Table 8.
46 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58
Table 8
Typical efficiencies of aerobic systems (Springer, 2000; *Kantar-
djieff and Jones, 1997)
System Aeration Organic loading
time (day) (lb BOD/1000 ft3)
Aerobic biofilters – 3.4 kg/m3/day
(sulfite mill)*
Aerobic biofilters – –
(TMP)*
Aerobic stabiliztion 5 – 10 50
basin
Activated sludge 3–8 h 50
6.2.2. Anaerobic treatment
An anaerobic process is considered more suitable
to treat high strength organic effluents. Before 1980s,
the treatment of pulp mill effluents by anaerobic
means was limited, as most of the pulp mill effluents
at that time were less concentrated (300 – 2000 mg/
l BOD) (Bajpai, 2000) and were not suitable for
anaerobic treatment. Anaerobic filter, upflow sludge
blanket (UASB), fluidized bed, anaerobic lagoon, and
anaerobic contact reactors are anaerobic processes,
that are commonly used to treat pulp and paper mill
effluents. Pretreatment of the kraft mill black liquor
was investigated by Poggi-Varaldo et al. (1996) and
they reported that continuous anaerobic treatment of
wastewater contaminated with black liquor was fea-
sible at low to medium loading rates, with a total COD
removal of 48– 80% and biodegradable COD reduc-
tion of 87 – 96%. Jahren et al. (1999) compared
anaerobic and aerobic treatment for TMP mill effluent
and found that 84% and 86% removal of COD from
anaerobic and aerobic treatment systems, respectively,
was achieved. Rajeshwari et al. (2000) reported that
chlorine bleaching effluents were not suitable for
anaerobic treatment due to their low biodegradability
and presence of toxic substances that affects metha-
nogens. Sandquist and Sandstrom (2000) developed a
new treatment technology [the process consists of
three steps: (1) stripping of sulfides and other volatile
components from condensate; (2) regenerative ther-
mal oxidation of stripper off gases; (3) adsorption of
sulfur oxide] to treat foul condensate (sulfide) from
the black liquor. Removal efficiency for foul conden-
sate was reported to be more than 99% at a pH of 4
and removal of methanol was 90% at a low liquid/gas
ratio. Jackson-Moss et al. (1992) found 50% removal
of COD and color by anaerobic biological granular
activated carbon. Dufresne et al. (2001) observed that
undiluted foul condensates at Windsor mill were toxic
to anaerobic biomass. Chen and Horan (1998) stated
Efficiency
that COD, and sulfate removals of 66% and 73%,
(%)
respectively, were obtained using a UASB reactor
74 – 92
with a hydraulic retention time of 6 h. Peerbhoi
74 – 90 (2000) investigated anaerobic treatability of black
liquor by a UASB reactor in her study at the Univer-
80 – 90 sity of Roorkee, India. The author concluded that
anaerobic biological treatment of black liquor was
80 – 85
not feasible, as the pollutants were not readily de-
gradable. Perez et al. (1998) evaluated two anaerobic
systems (anaerobic filters and fluidized bed) in labo-
ratory-scale reactors and reported that 81.5% organic
removal efficiency was obtained in the case of fluid-
ized bed with porous packing and 50% removal was
obtained in the case of anaerobic filters on corrugated
plastic tubes. Rajeswori et al. (2000) reported a 50%
reduction of BOD of debarking wastewater by a
fluidized bed reactor. Thompson et al. (2001) reported
that COD removal efficiency of 80% was constantly
achievable but the residual COD was around 800 mg/
l meaning that additional treatment was essential.
Schnell et al. (1992) concluded that anaerobic treat-
ment systems were less suitable for treatment of
sulfite-spent liquor compared to an aerobic system.
The anaerobic treatability of different processes are
given in Table 9.
6.3. Fungal treatment
Taseli and Gokcay (1999) isolated fungal specie
(Pencillium sp.) which was able to remove 50% of the
AOX, and color from the soft-wood bleachery efflu-
ents in a contact time of 2 days. Several authors
reported on the capacity of different fungal species
to remove color from kraft mill effluent (Gokcay and
Dilek, 1994; Duran et al., 1994; Sakurai et al., 2001).
Prasad and Gupta (1997) reported on a substantial
reduction of color and COD by the use of white rot
fungi T. versicolor and P. chrysosporium. Saxena and
Gupta (1998) showed that white-rot fungi P. chrys-
osporium in combination with other white-rot fungi
(P. sanguineus, P. ostreatus and H. annosum) and with
the use of the surfactants were able to remove color,
COD, and lignin content. Choudhury et al. (1998)
found that lignin, BOD, COD and color removal were
achieved to the extent of 77%, 76.8%, 60%, and 80%,
 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 47

Table 9
Anaerobic degradability of pulp and paper mill effluent (Rintala and Puhakka, 1994)
Wastewater from COD (mg/l) Anaerobic Inhibitors
degrad. (%)
Wet debarking 1300 – 4100 44 – 78 Resin acids
Thermomechanical 1000 – 5600 60 – 87 Resin acids
pulping
Chemothermomechanical 2500 – 13,000 40 – 60 Resin acids,
pulping fatty acids, sulfur, DTPA
NSSC-spent liquor 40,000 nr Tannins
NSSC-condensate 7000 nr Sulfur, ammonia
Kraft condensate 1000 – 33,600 83 – 92 Sulfur, resin acids,
fatty acids, terpenes
Spent condensate 7500 – 50,000 50 – 90 Sulfur, organic sulfur
Chlorine bleaching 900 – 2000 30 – 50 Chlorinated phenols,
resin acids
Sulfite spent liquor 120,000 – 220,000 nr nr

respectively, by the fungal specie Pleurotus ostreatus.
Zhang et al. (2000a) examined the removal of most of
the detrimental organics from whitewater by com-
bined enzyme and fungal treatment. The removal of
lignin was >90% whereas resin and fatty acids were
reduced by 20%. Zhang et al. (2000b) showed that
fungus such as T. versicolor and fungal culture filtrate
(FCF) obtained from these organisms were able to
efficiently degrade the dissolved and colloidal sub-
stances. Mendonca et al. (2002) suggested fungal
pretreatment of P. taeda wood chips by C. subvermis-
pora. The performance of fungal treatment is summa-
rized in Table 10.
6.4. Integrated treatment processes
An integrated or hybrid system is designed to take
advantage of unique features of two or more process-
es. A combination of coagulation and wet oxidation
removed 51% of COD (Verenich et al., 2001); and
83% of color and 75% of lignin (Verenich and Kallas,
2001). A combination of ozone and biofilm reactor
removed 80% COD (Helble et al., 1999). A combi-
nation of chemical oxidation with ozone removed
90% of wood extractives and 50% of the COD from
TMP wastewater at 150 jC (Laari et al., 1999).
Athanasopoulos (2001) suggested post treatment
methods such as electrolysis or ozonation to reduce
COD, and NH4+ – N concentration to the permitted
level. Nakamura et al. (1997) reported on efficient
degradation of lignin using a combined treatment of
ozone and activated sludge process. Jokela and Keski-
talo (1999) reported that a combination of dissolved
air flotation and chemical precipitation removed 93%
SS, 50% BOD7, 57% COD, 92% phosphorus, and
52% nitrogen.
A combination of activated sludge and with
ozonation (as tertiary treatment) removed 87 –97%
COD, and 97% BOD (Schmidt and Lange, 2000).
Kabdash et al. (1996) showed that a combination of

Table 10
Performance of fungal treatment
Treatment process Parameters Reference
COD Lignin Color
Influent % Influent % Influent %
(mg/l) Removal (mg/l) Removal (mg/l) Removal
White rot fungi 39,012 40.74 2870 16.38 34,940 34.49 Saxena and Gupta (1998)
White rot + surfactants 39,012 75.35 2870 65.84 34,940 81.29 Saxena and Gupta (1998)
White rot (T. versicolor) – 77.7 – – 1875 93.8 Prasad and Gupta (1997)
White rot (P. chrysosporium) – 79.4 – – 1875 83.5 Prasad and Gupta (1997)
 48
Table 11
Performance of physicochemical treatment processes
Treatment process Parameters Reference

D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

TSS COD TOC AOX Color Lignin/Resin*
or Fatty# acid
Influent % Influent % Influent % Influent % Influent % Influent %
(mg/l) Removal (mg/l) Removal (mg/l) Removal (mg/l) Removal (Pt – Co) Removal (mg/l) Removal
Coagulation:
Polyelectrolyte 3620 100 4112 55.65 – – – – 4667.5 82.58 480 98.91 Rohella et al. (2001)
Chitosan – – – – – 70 – – – 90 – – Ganjidoust et al. (1997)
PE/PEI – – – – – 30 – – – 80 – – Ganjidoust et al. (1997)
Alum – – – – – 40 – – – 80 – – Ganjidoust et al. (1997)
Adsorption:
Charcoal #1 – – – – – – – – 3.9 mg/l 98.13 – – Murthy et al. (1991)
Coal ash #2 – – – – – – – – 3.9 mg/l 98.5 – – Murthy et al. (1991)
Fuller earth #3 – – – – – – – – 3.9 mg/l 99.21 – – Murthy et al. (1991)
Activated coke #4 – – 2126 >90 – – 80.2 >90 2300 >90 – – Shawwa et al. (2001)
Oxidation: – – 10,000~19,000 80 3500~4100 80 – – – – Verenich et al. (2000)
(Wet oxidation)
(Ozone + Fenton) – – – – – – – – – ~100 Hassan and
Hawkyard (2002)
Ozonation:
Ozone + UV – – ~550 82 – – – – – – Oeller et al. (1997)
Photocat. + ozone – – 515 85 306 88 27.7 92.5 250 100 Torrades et al. (2001)
Photocat. + ozone – – 3700 57.5 1380 38 69.8 50 7030 65 Torrades et al. (2001)
Membrane:
Ultrafiltrtion – – – 85 – 90 – – 85 – 91 93 – 98 Zaidi et al. (1992)
Nanofiltration – – – – – – – 93 – 96 99.2 – 99.9 Zaidi et al. (1992)
Dissolved air + UF 397 100 – – 828 65 – – 1747 90 De Pinho et al. (2000)
Microfiltration + UF 397 100 – – 828 54 – – 1747 88 De Pinho et al. (2000)
(#1) Charcoal dose 0.4 g/l and pH 2.0; (#2) Coal ash dose 12 g/l and pH 2.0; (#3) Fuller earth dose 4 g/l and pH 2.0; (#4) activated coke dose 15,000 mg/l.
 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 49

Table 12
Performance of aerobic biological treatment processes
Treatment process Parameters Reference
TSS BOD COD AOX Chlorinated phenolics
Influent % Influent % Influent % Influent % Influent %
(mg/l) Removal (mg/l) Removal (mg/l) Removal (mg/l) Removal (mg/l) Removal
Activated sludge
Paper mill 1435 90.6 512 94.2 1210 82.4 – – – – Saunamaki (1997)
Pulp mill 738 76.4 336 93.8* 1192 57.1 11.7 55 – – Saunamaki (1997)
Kraft mill – – 270 >95* 660 (F) 60 22.5 36 0.255 74 Schnell et al.
(period 1) (2000a)
(period 2) – – 270 >98 660 (F) 70 22.5 40 0.255 83 Schnell et al.
(2000a)
Pulp and – – – 96.63 – 96.8 – – – 96.92 Chandra (2001)
paper mill
Paper mill – – 1000 99 1533a 85 – – – – Knudsen et al.
(1994)

Aerobic stabilization basin

Kraft mill – – 270 >95 660 (F) 62 22.5 53 0.255 85 Schnell et al.
(period 1) (2000a)
(period 2) – – 270 >98 660 (F) 73 22.5 55 0.255 86 Schnell et al.
(2000a)
–
Kraft mill – – – – 20 – 65 – 17 – 70 – – Chernysh et al.
(1992)
(1) ‘‘F’’ means fraction of COD or soluble COD.
(2) Period 1: operating conditions for activated sludge-HRT 2 days, SRT 25 days, Temp. 30 jC, VSS 1800 mg/l.
(3) Period 1: operating conditions for aerated stabilization basin-HRT 15 days, SRT 15 days, Temp. 30 jC, VSS 60 mg/l.
(4) Period 2: operating conditions for activated sludge-HRT 1 day, SRT 25 days, Temp. 30 jC, VSS 2800 mg/l.
(5) Period 2: operating conditions for aerated stabilization basin-HRT 15 days, SRT 15 days, Temp. 20 jC, VSS 70 mg/l.
a
Means soluble COD and * means BOD7.

chemical and biological methods (bioferic) resulted (1999) found that Kaldnes (anaerobic followed by
in 40– 50% additional removal of COD compared to aerobic) moving bed biofilm reactor at 55 jC re-
the activated sludge system. Jahren and Oedegaard moved about 60% of soluble COD from TMP

Table 13
Performance of biological treatment processes
Treatment process Parameters Reference
BOD COD Methanol Color
Influent % Influent % Influent % Influent %
(mg/l) Removal (mg/l) Removal (mg/l) Removal (mg/l) Removal
Biological reactors
HRC (TMP Mill) 1150 98 3340 79 – – – – Magnus et al. (2000a)
Total plant 1490 99 5000 86 – – – – Magnus et al. (2000a)
efficiency
MBBR – 65 – 75 – 85 – 95 – – – – Borch-Due et al. (1997)
(HRT 4.5 hrs)
SBR – 98 – 85 – 93 – – – – Franta and Wilderer (1997)
Anaerobic (GAC) – – 1400 50 – – 1300 50 Jackson-Moss et al. (1992)
Kraft mill Windsor 1429a 69 2036a 59 1095a 84 – – Dufresne et al. (2001)
a
Unit in g/d.
50 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

whitewater. A combined anaerobic – aerobic treat-
ment system was suggested to treat bleached kraft
pulp and paper mill effluents (Duncan and Thia,
1992; Wang et al., 1997). Lescot and Jappinen
(1994) showed that a combination of an aerated
lagoon and a secondary clarifier was able to treat
bleached kraft mill effluent in Finland resulting in
87%, 96%, 65%, 53%, and 22% removal of SS,
BOD7, COD, AOX, and color, respectively. Carlson
et al. (2000) reported that 77%, 98 –99%, 72%, and
81% removal of COD, BOD, TN, and TP, respec-
tively, was achieved after upgrading the aerated
basin at Monsteras mill. The system comprised of
an anoxic selector, an aerated basin, and a secondary
clarifier in series. The removals of extractives, resin
and fatty acids were 96% and 98%, respectively,
whereas the system reduced Microtoxk by 99%.
Welander et al. (2000) reported on the performance
of an aerobic biological process called LSP (low
sludge production) to lower the biological sludge by
80 – 90%. The system configuration was primary
clarifier, aeration basin, and secondary clarifier. A
combination of physicochemical, biological, and ef-
fluent polishing in the aerated lagoon removed 98–

Table 14
Selected anaerobic process performance (Bajpai, 2000)
Mill location Wastewater source Loading rate BOD5 COD TSS BOD5 COD
(kg COD/m3/d) (mg/l) (mg/l) (mg/l) Removal% Removal%
Anaerobic contact reactor
Hylte Bruk TMP, 2.5 1300 3500 520 71 67
AB, Sweden groundwood, deink
SAICA, Waste paper alkaline 4.8 10,000 30,000 – 94 66
Zaragoza, Spain cooked straw
Hannover paper, Sulfite effluent 4.2 3000 6000 – 97 85
Alfred, Germany condensate
Niagara of Wisconsin CTMP 2.7 2500 4800 3300 96 77
of USA
SCA Ostrand, CTMP 6 3700 7900 – 50 40
Ostrand, Sweden
Alaska Pulp Sulfite condensate, 3 3500 10,000 – 85 49
Corporation, Sitka bleach caustic and
pulp whitewater

Upflow anaerobic sludge blanket

Celtona, Holland Tissue 3 600 1200 – 75 60
Southern paper Wastepaper 10 – 10,000 – > 80 > 80
converter, Australia
Davidson, Linerboard 9 1440 2880 – 90 75
United Kingdom
Chimicadel, Sulfite 12.5 12,000 15,600 – 90 80
Friulli, Italy condensate
Quesnel River TMP/CTMP 18 3000 7800 – 60 50
Pulp, Canada
Lake Utopia NSSC 20 6000 16,000 – 80 55
Paper, Canada
EnsoGutzeit, Finland Bleached 13.5 1800 4000 – 75 60
TMP/CTMP
McMillan Bloedel, NSSC/CTMP 15 7000 17,500 – 80 55
Canada
Anaerobic filter: CTMP 12.7 4000 7900 – 85 70
Lanaken, Belgium
Anaerobic fluidized Paperboard 35 1500 3000 – 83.3 72.2
bed: D’ Aubigne, France
 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58
99% BOD, 91% COD, 97% SS, and 90% color of a
pulp and paper mill in Brazil (Foelkel, 1989). Rusten
et al. (1994) reported that a combination of a biofilm
reactor followed by one anaerobic and two aerobic
reactors was found to remove 50% COD, 80– 90%
BOD7, 50% AOX, 90% ClO3. Shaw et al. (2002)
showed that a combination of aerobic reactor fol-
lowed by anaerobic reactor removed 94% color, and
66% TOC. Schnell et al. (1997) found that 87– 95%,
70 –77%, and 80 –94% removal of BOD, COD, and
resin and fatty acids was provided by biological
treatment. Tardif and Hall (1997) reported 100%,
96%, 76%, and 34% removal of resin acid (RA),
fatty acid (FA), dissolved chemical oxygen demand
(DCOD), and total dissolved solids (TDS), respec-
tively at temperatures 20– 40 jC by an SBR. An
MBR removed 100% RA and FA, 84% DCOD, and
37% TDS at 40 – 50 jC. Malmquist et al. (1999)
reported a COD removal of 70 –90% of whitewater
by biological treatment. Badar (1996) suggested a
number of methods to improve the integrated paper
mill wastewater effluent treatment: (1) increasing the
capacity of the aeration basin; (2) installing an extra
dissolved air flotation clarifier; (3) adding chlorine
gas to improve bulking of sludge problem and (4)
injecting oxygen to treat BOD during heavy rain and
flooded conditions. Graves and Joyce (1994)
reviewed the ability of biological treatment systems
to remove chlorinated organic compounds discharged
from pulp and paper industry. AOX removal of 32%
(aerated lagoon) and 10 –65% by activated sludge
plant was reported. Gupta et al. (2001) isolated
bacterial specie Aeromonas formicans suitable to
treat black liquor from kraft pulp and paper mills.
Performances of various treatment processes are
summarized in Tables 11 –14.
7. Discussion
The literature review showed that an internal
process change is one of the options to be adopted
by the pulp and paper industry to reduce the pollution
at the source. A recent comprehensive study carried
out in a large number of pulp and paper mills in the
US found that the effluent discharge has been reduced
by 30%; TSS and BOD have been reduced by 45%
and 75%, respectively (Das and Jain, 2001) even
51
when the production has been increased. Trotter
(1990a,b) evaluated biotechnological applications
such as genetic modification of plant, biopulping,
and biobleaching to reduce chlorinated organic com-
pounds as an emerging technology for internal pollu-
tion control. Enzyme treatment for pulp dissolving,
improving tensile properties by treating mechanical
pulp with white rot organisms and enzymatic beating
of chemical pulps, hemicellulose, and decolorization
by white rot fungi were given as possible biotechno-
logical options.
Among the various treatment processes currently
used for pulp and paper effluent treatment, only a few
are commonly adopted by pulp and paper industry
especially for tertiary treatment. Some of the treatment
processes such as ozonation, fenton’s reagent, adsorp-
tion, and membrane technology are efficient but are
more expensive. Sedimentation is the most commonly
adopted process by the pulp and paper industry to
remove suspended solids. The performance data given
by Springer (2000) showed 80 – 90% removal of
initial suspended solids from most of the mills except
a deinking mill. Flotation is also commonly used in
the pulp and paper industry but most of the time as a
tertiary treatment. Coagulants are a preferred option
for removing turbidity and color from the wastewater.
Reported results have shown that they are also capable
in reducing COD, TOC, and AOX to some extent.
Among the coagulants, modified chitosan showed the
highest performance for color and TOC removal.
Polyelectrolytes are better than alum and they produce
less sludge and pose less problems with sludge
dewaterability than alum. Adsorption processes are
useful to remove color, COD, and AOX. They are
rather expensive and it is not known whether the pulp
and paper industry are employing them widely. How-
ever, laboratory-scale experiments are usually
reported. Activated charcoal, fuller’s earth, and coal
ash showed better results for color removal. Activated
coke alone was able to remove 90% of the COD,
AOX, DOC, and color.
Chemical oxidants such as ozone + photocatalysis,
and ozone + UV are reported to be efficient in
removing COD and TOC and color. However, the
efficiency largely depends upon the concentration of
the COD. Ozone alone is able to remove 90% of
EDTA and AOX, and over 80% of COD. However,
it is rather expensive (Perez et al., 2002b). Ozonation
52 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58
is not commonly adopted in most countries, not even
in Europe but it is emerging in North America.
Membrane processes are efficient in reducing over
90% of color, TSS, and AOX in most of the cases.
Fouling of membranes is a problem in the case of
soft wood effluent treated by membrane filtration. In
secondary treatment processes, activated sludge is
the most commonly used. UASB and fluidized beds
are also gaining in use recently. The problem with
activated sludge is sludge bulking. Reported results
have shown that activated sludge can remove all
types of the pollutants pertaining to the pulp and
paper industry. However, the removal of AOX is
below 50%, BOD around 95% in most of the mills,
and COD removal averages around 70%. This sys-
tem is also efficient in removing chlorinated phenolic
compounds (over 75%) most of the time. Dalentoft
and Thulin (1997) reported that Kaldnes (anaero-
bic + aerobic) process in series with an activated
sludge, could be an efficient, stable, and a compet-
itive combination process, considering both invest-
ment and operating costs. Aerated lagoons are
efficient in removing BOD over 95% in most of
the reported results. COD removals are moderate
between 60% and 70%, AOX around 50%, and a
high removal (85%) for chlorinated phenolics. An-
aerobic contact reactors are efficient in removing
biodegradable organic compounds such as BOD,
and COD. The performance data from various mills
showed that anaerobic contact reactors were able to
remove over 90% of BOD and 65% of COD in most
of the cases. Anaerobic filters and fluidized bed
reactors are suitable in reducing organic pollutants
only. Both the reactors achieve almost same efficien-
cy in terms of BOD (>80%), and COD (>70%)
removal (refer to Table 14 for details). UASBs are
able to remove over 80% of BOD and 50 – 80% of
COD in most of the mills (refer to Table 14 for
details). Fungi are efficient in removing especially
color and COD from the pulp mill wastewater.
Removal of color using white rot fungi was above
80% in most of the reported cases and COD removal
was above 75%. White rot fungi particularly P.
chrysosporium and C. versicolor are suitable for
efficient degradation of the refractory material (Baj-
pai and Bajpai, 1994). The reported results have
shown that high removals are achieved in the case
of the combination of two or more physicochemical
processes or combination of physicochemical and
biological processes. The confirmation of the reported
results, their applicability in the real field, and eco-
nomic evaluations are very important in adopting the
process. For example, the anaerobic treatment process
for pulp and paper mill effluents is still in an initial
application phase.
However, comprehensive evaluations made by var-
ious authors lead to a better understanding of the
various treatment processes and their adaptability.
For example, Jemaa et al. (2000) stated that chemical
precipitation, evaporation, membrane technology, and
ion exchange were the established options for the
removal of colloids and metal ions. Perez et al.
(2002a) conducted an economic evaluation of various
advanced oxidation processes to remove organic con-
taminants. Ozonation was stated to be effective but
rather an expensive process. Rintala and Puhakka
(1994) stated that operation costs of the activated
sludge was about three times greater than that of
anaerobic systems. Bajpai (2000) presented compara-
tive costs of the anaerobic and activated sludge treat-
ment, which showed that activated sludge was almost
twice as expensive as anaerobic reactors. The recent
paper by Perez et al. (2002b) reported a high efficiency
of COD and TOC removal when iron ion was used
with ozone/UV treatment system. The authors showed
that the presence of iron ion in the ozone/UV treatment
brought a complete removal of COD in 90 min while
TOC removal was higher than 90%. The report stated
that the overall cost was reduced by 50%, which is
encouraging news for the industry. Mobius and
Cordes-Tolle (1994) suggested that sand filters, bio-
filters, low capacity trickling filters, flocculation and
precipitation with inorganic salts in combination with
filtration or flotation are the emerging systems for
adoption by pulp and paper mills.
8. Conclusions
Based on the above literature review, the following
conclusions are drawn:
(i) Both aerobic and anaerobic treatment systems
are feasible to treat wastewater from all types
of pulp and paper mills except that bleaching
kraft effluents are less suitable for treatment by
 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58
anaerobic means, as they are more toxic to
anaerobic bacteria.
(ii) The anaerobic treatment of high strength
wastewater requires further treatment as it
contains high residual COD.
(iii) A combination using an anaerobic process
followed by an aerobic treatment system is a
better option, as it can make use of the
advantages of both the treatment processes.
(iv) Color is removed efficiently by fungal treat-
ment, coagulation, chemical oxidation, and
ozonation.
(v) Chlorinated phenolic compounds and AOX can
be removed by adsorption, ozonation and
membrane filtration.
(vi) Combinations of two or more physicochemical
processes produce a high removal of toxic
pollutants.
(vii) Combinations of physicochemical and biolog-
ical treatment processes with optimization of
the process provide a long-term solution for
pulp and paper mill effluent treatment.
(viii) More studies are needed on the removal of
AOX and chlorinated phenolic compounds.
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