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

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


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-

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

0048-9697/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
38 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

The growing public awareness of the fate of these sodium sulfide (NaS2). This process is widely
pollutants and stringent regulations established by used.
the various governmental authorities such as provin- (b) Sulfite process: The wood chips are cooked in a
cial and federal agencies are forcing the industry to mixture of sulfurous acid (H2SO3) and bisulfide
treat effluents to the required compliance level before ions (HSO3 ) to dissolve lignin.
discharging them in to the environment. Many stud-
ies have been conducted so far on this sector regard- 2.3. Chemo-mechanical pulping (CMP)
ing the impacts as well as the control of the
pollutants. Berube and Kahmark (2001), Kahmark The raw material is first treated chemically and
and Unwin (1996, 1998, 1999), and Srinivasan and then subjected to drastic mechanical treatment to
Unwin (1995) have reviewed pollution control as- separate the fibers. The efficiency of pulp obtained
pects of the pulp and paper industry. However, all ranges from 85 – 90% and the strength of the pulp is
these reviews have focused on the state of the art in relatively better than the pulp from the mechanical
integrated pollution management and lack a compara- pulping alone.
tive evaluation of various treatment processes partic-
ular to the water pollution control. This review, 2.4. Thermo-mechanical pulping (TMP)
therefore, would examine the pollution control sys-
tems and compare the performance of the effluent This process involves steaming the raw materials
treatment measures in use. under pressure for a short period, prior to and during
refining. The thermo-mechanical process is further
modified using chemicals during the steaming stage,
2. Process description and the process is called chemi-thermomechanical
pulping (CTMP).
Pulping is the initial stage of the paper making
industry and provides the processed material. It is the 2.5. Papermaking
largest source of the pollution in the whole process of
papermaking. High amounts of wastewater are gene- The paper making operation consists of two parts;
rated at different stages of this process. one is stock preparation by treating the pulp to the
required degree of fitness and the other is paper
2.1. Mechanical pulping making where the treated pulp is passed through
continuous moulds/wires to form sheets.
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 3. Sources of pollution
Each pulping process utilizes large amounts of
2.2. Chemical pulping water, which reappear in the form of an effluent.
The most significant sources of pollution among
The wood chips are cooked with appropriate various process stages are wood preparation, pulping,
chemicals in an aqueous solution at an elevated pulp washing, screening, washing, bleaching, and
temperature and pressure to break chips into a fibrous paper machine and coating operations. Among the
mass. The yield of the pulp by this process is about processes, pulping generates a high-strength waste-
40 – 50% of the original wood material (Smook, water especially by chemical pulping. This wastewa-
1992). The chemical pulping is carried out in two ter contains wood debris and soluble wood materials.
media: alkaline and acidic. Pulp bleaching generates most toxic substances as it
utilizes chlorine for brightening the pulp. Pulp fibers
(a) Kraft process: The woodchips are cooked in a can be prepared from a vast majority of plants in
solution of sodium hydroxide (NaOH) and 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 making process. The pollutants at various stages of
of papermaking fiber. Wood consists of various com- the pulping and paper making process are presented in
pounds (lignin, carbohydrate, and extractives) which Fig. 1.
are hard to biodegrade, and these derivatives are It is clear that an individual pulping stage gene-
washed away from the fibers during the washing, rates different quantities, qualities and types of
dewatering, and screening processes. Depending upon pollutants. The wastewater pollution load from indi-
the type of the pulping process, various toxic chem- vidual pulping and papermaking process is given in
icals such as resin acids, unsaturated fatty acids, Table 1.
diterpene alcohols, juvaniones, chlorinated resin The amount of pollutants produced by an indivi-
acids, and others are generated in the pulp and paper 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
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
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
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 and paper mill wastewaters (Owens et al., 1994; Vass
pollution sources are given in Tables 5, 6 and 7. 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)
5. Fate and effects on the environment reported on serious concerns related to the surface
plankton population change in Elengabeel’s wetland
The pollutants discharged from the pulp and paper ecosystem in India due to untreated paper mill effluent
industry affect all aspects of the environment such as discharge into the system. Yen et al. (1996) reported on
water, air and land. Makris and Banerjee (2002) the possibility of the sub-lethal effects to the aquatic
studied the fate of the resin acid in the secondary organisms in the Dong Nai River in Vietnam due to the
treatment system. Various authors at different times effluents discharged from a pulp and paper mill.
reported the appearance of toxic effects on various fish However, there are also some contradictory reports
species due to exposure of pulp and paper mill efflu- by other authors. Kovacs et al. (2002) reported no
ents. Many authors reported the presence of toxic significant evidence of depressed plasma steroids nor
pollutants in fish or toxic effects on fish such as increase in mixed function oxygenase (MFO) activity
respiratory stress, mixed function oxygenase activity, in fish associated with pulp mill effluent. D’surney et
toxicity and mutagenicity, liver damage, or genotoxic al. (2002) and Felder et al. (1998) indicated no
effects, and lethal effects on the fishes exposed to pulp 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
(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)
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. wastewater. Mandal and Bandana (1996) reported on
Stepanova et al. (2000) reported no clear evidence of health impacts such as diarrhea, vomiting, headaches,
mutagens in most of aquatic animals studied in Lake nausea, and eye irritation on children and workers due
Baikal due to Baikalsk pulp and paper mill wastewater to the pulp and paper mill wastewater discharged to the
discharged to the lake. Wayland et al. (1998) reported environment. High carbon dioxide level in the pulp and
no effect on the tree shallow, which feed on the insects paper mill effluents as a potential source of distress and
downstream of the pulp mill. toxicity to rainbow trout was reported by O’connor et
Howe and Michael (1998) studied the effects of the al. (2000).
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 6. Wastewater treatment
mill effluent (treated) applied to a paddy field in
Assam, India. Gupta (1997) and Singh et al. (1996) Pollution from the pulp and paper industry can be
reported high loads of organic pollutants derived from minimized by various internal process changes and
the paper mill wastewater in Tamilnadu, and Punjab, management measures such as the Best Available
India, respectively. Singh et al. indicated high level of Technology (BAT). Dube et al. (2000) reported a
coliform bacteria in the effluent too. However, Archi- 60% reduction in effluent BOD due to an internal
bald (2000) indicated that the presence of coliform process change in Irving Pulp and Paper Limited,
bacteria in the pulp and paper effluent did not neces- Canada. The estimated data by Springer (2000)
sarily mean a health hazard to the environment unless showed that the water use in the US in 1959 was about
pathogens were observed. Skipperud et al. (1998) and 250 m3/adt whereas water use in 1995 was reduced to
Holmbom et al. (1994) reported the presence of various 50 m3/adt. However, the average water use for the pulp
trace metals in the pulp and paper mill effluents at low and paper mills in India was still 200 –259 m3/ton of
levels. King et al. (1999) reported elevated levels of Mn paper production (Gune, 2000). Several authors have
accumulation in the Crayfish exposed to the paper mill suggested internal process change as a measure to
D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 43

control pollution (Reilama and Ilomaki, 1999; Webb, treatment of foul condensate, defined by phenolic
1994; Dey et al., 1991). Raghuveer and Sastry (1990) compounds, and toxicity using microtox assay from
reported BOD, COD, and color reduction by internal kraft pulping by horseradish peroxide and H2O2 and
management measures. However, the treatment of the found a total phenol reduction below 1 mg/l and
wastewater by various external processes is essential. toxicity (microtox assay) reduction by 46%. Dilek
Since pulp and paper industry discharges varieties of and Gokcay (1994) reported 96% removal of COD
pollutants, the treatment methods also vary. from the paper machine, 50% from the pulping, and
20% for bleaching effluents by using alum as a
6.1. Physicochemical treatment coagulant. Rohella et al. (2001) stated polyelectrolytes
were better than the conventional coagulant alum to
Physicochemical treatment processes include re- remove turbidity, COD, and color. Sheela and Distidar
moval of suspended solids, colloidal particles, floating (1989) reported on black liquor treatment by precipi-
matters, colors, and toxic compounds by either sedi- tation with CaSO42H2O in the presence of CO2. The
mentation, flotation, screening, adsorption, coagula- removal of dissolved solids was reported to be 63%.
tion, oxidation, ozonation, electrolysis, reverse osmo- However, Wang and Pan (1999) reported that the use
sis, ultra-filtration, and nano-filtration technologies. of coagulants such as polyethylene oxide (PEO),
worsened the settlability and increased COD levels,
6.1.1. Sedimentation/flotation turbidity, and suspended solids of the treated effluent
Suspended matters present in the pulp and paper when the dose was between 25 and 250 ppm. Cher-
wastewater are comprised primarily of bark particles, noberezhskii et al. (1994) reported that coagulation
fiber, fiber debris, filler and coating materials. Thomp- with aluminum sulfate or modified adsorbents was the
son et al. (2001) stated that sedimentation was the best option for color removal from the sulfate and
preferred option within the paper mills in the UK, and sulfite wood pulp and paper industry.
contributed to more than 80% removal of the sus-
pended solids on an average. Rajvaidya and Markan- 6.1.3. Adsorption
dey (1998) stated that the design value of the primary Murthy et al. (1991) reported a high removal of
clarifier was 70 – 80% in average. Azevedo et al. color by activated charcoal, fuller’s earth, and coal ash.
(1999) reported on the effect of pH on pulp settal- Shawwa et al. (2001) reported 90% removal of color,
ability. Gubelt et al. (2000) reported 65 – 95% removal COD, DOC, and AOX from bleached wastewater by
of TSS by dissolved air flotation and it was an the adsorption process, using activated coke as an
unstable unit. However, Wenta and Hartmen (2002) adsorbent. Sullivan (1986) concluded that the waste-
mentioned that dissolved air flotation was able to water produced by the Union Camp Facility at Frank-
remove 95% of the TSS. lin, VA, can be treated by activated carbon and ion
exchange to reduce color and chloride to levels ac-
6.1.2. Coagulation and precipitation ceptable for reuse. Das and Patnaik (2000) investigated
Coagulation and flocculation is normally employed the lignin removal efficiency of the blast furnace dust
in the tertiary treatment in the case of pulp and paper (BFD) and slag by the adsorption mechanism. Their
mill wastewater treatment and not commonly adopted study showed 80.4% and 61% removal of lignin by
in the primary treatment. Tong et al. (1999) and BFD and slag, respectively. Narbaitz et al. (1997)
Ganjidoust et al. (1997) carried out a comparative reported that PACTk process was an effective process
study of horseradish peroxide (chitosan) and other to remove AOX from the kraft mill effluent to meet
coagulants such as (Al2(SO4)3), hexamethylene di- Ontario’s year 2000 regulation (AOX: 0.8 kg Cl/adt of
amine epichlorohydrin polycondensate (HE), poly- production).
ethyleneimine (PEI), to remove adsorbable organic
halides (AOX), total organic carbon (TOC), and color. 6.1.4. Chemical oxidation
The authors indicated that modified chitosan was far Balcioglu and Ferhan (1999) reported on photo-
more effective in removing these pollutants than other catalytic oxidation of kraft pulp bleaching wastewater
coagulants. Wagner and Nicell (2001) investigated the 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 6.1.6. Ozonation

level. Zamora et al. (1998) reported on the use of Yeber et al. (1999) reported that a substantial
horseradish peroxide to decolorize kraft effluent by removal of COD, TOC, and toxicity from pulp mill
50% within three hours of reaction time. The degra- effluent and increased biodegradability of the effluent
dation of phenolic and polyphenolic compounds pres- were achieved after treatment with ozone. Korhonen
ent in the bleaching effluent was studied using et al. (2000) reported a 90% removal of ethylenedia-
advanced oxidation systems such as photocatalysis minetetraacetic acid (EDTA) and a 65% removal of
with O2/ZnO/UV, O2/TiO2/UV, O3 and O3/UV. The COD by ozone treatment of the pulp mill effluent.
authors concluded that O2/ZnO/UV and O2/TiO2/UV Hinck et al. (1997) reported that neither EDTA nor
were the best systems to oxidize the effluent in a short diethylene triamine pentaacetic acid (DTPA) are bio-
period of time. Perez et al. (2002c) reported that the degraded in aerobic conditions. Oeller et al. (1997)
combination of Fenton and photo-fenton reactions reported high removal of COD and DOC from the
proved to be highly effective for the treatment of pulp effluent by ozone treatment. Freire et al. (2000)
bleaching kraft mill effluent. Verenich et al. (2000) reported a 12% reduction of total organic carbon, total
reported on the improvement in biodegradability of an phenols reduced to 70%, and effluent colors to 35% of
effluent from 30% to 70% by wet oxidation method. bleached pulp mill effluent after 60 min of ozonation.
Hassan and Hawkyard (2002) studied the removal of Several authors reported on toxic compounds, COD,
color by combined oxidation with ozone and Fenton’s and color removal by ozone treatment (Hostachy et
reagent and stated that 100% color removal was al., 1997; Zhou and Smith, 1997; Yamamoto, 2001).
achieved at a pH of 4 – 5 in the case of ferral (derived Roy-Arcand and Archibald (1996) reported that bio-
from natural clay sources, which contains 2% ferric treated kraft effluents yielded a substantial decrease in
sulfate and 6% aluminum sulfate) and ferric sulfate. the biologically recalcitrant residual adsorbable or-
Dufresne et al. (2000) reported on the oxidation of ganic halogens (AOX), converted COD to BOD and
total reduced sulfur (TRS) giving odor free products yielded large decrease in color. Laari et al. (2000)
by catalytically enhanced oxidation. investigated the removal of lipophilic wood extrac-
tives from TMP wastewater by ozonation. The authors
6.1.5. Membrane filtration indicated that a high dosage of ozone (100 –300 mg/
Jonsson et al. (1996) reported on the treatment of dm3) was required to remove 50% of lippphilic wood
paper coating color effluent treatment by membrane extractives. Korhonen and Tuhkanen (2000) reported
filtration suggesting that the composition of the color that ozone doses of 0.2 mgO3/initial mgCOD elimi-
had a significant influence on the performance. Mem- nated over 90% resin acid. Torrades et al. (2001)
brane separation techniques were reported to be reported high removals of TOC, COD, AOX, and
suitable for removing AOX, COD, and color from color from bleached kraft mill effluent (BKME1)
pulp and paper mills (Zaidi et al., 1992; Afonso and using heterogeneous photocatalysis and ozone treat-
Pinho, 1991, Falth, 2000). De Pinho et al. (2000) ment. Sevimli and Sarikaya (2002) reported a 95–
compared the efficiency of (1) ultrafiltration and (2) 97% color removal for high doses of ozone in 15 min
ultrafiltration plus dissolved air flotation. The results of ozonation. Kallas and Munter (1994) suggested
showed 54%, 88%, 100% removal of TOC, color, post treatment of bleached mill effluent by ozonation
and SS, respectively by ultrafiltration alone. Ultrafil- and adsorption.
tration plus dissolved air flotation resulted in 65%,
90% and 100% removal of TOC, color, and SS, 6.2. Biological treatment
respectively. Dube et al. (2000) reported that 88%
and 89% removal of BOD, and COD, respectively 6.2.1. Aerobic treatment
was achieved by reverse osmosis (RO). Merrill et al.
(2001) stated that membrane filtration (MF), and Activated sludge process. The performance
granular membrane filtration (GMF) were suitable variation of the activated sludge due to the changes in
for removing heavy metals from the pulp and paper pH, temperature, and H2O2 and DTPA was reported
mill wastewaters. by Ginkel et al. (1999), Norris et al. (2000), and
D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 45

Larisch and Duff (1997, 2000), respectively. Knudsen monia from black liquor spill at temperatures of 22 –
et al. (1994) reported a high reduction of BOD and 35 jC, pH near 7.3 in an aerated lagoon. Chernysh
soluble COD by a two-stage activated sludge process. et al. (1992) reported large variations in AOX and
Shere and Daly (1982) claimed that TMP wastewater TOC removal in a controlled batch study of bleached
was readily degradable by the activated sludge pro- kraft effluent in an operating lagoon under both
cess. Hansen et al. (1999) suggested upgrading the aerobic and anaerobic conditions. Welander et al.
activated sludge plant by the addition of Floobeds (1997) reported COD removal of 30– 40% in a full-
(floating biological bed) in series that increased COD scale lagoon and 60 – 70% in a pilot-scale plant.
and BOD removal from 51% to 90% and 70% to Stuthridge et al. (1991) reported 65% removal of
93%, respectively. Chandra (2001) reported efficient AOX from bleached kraft pulp and paper mill
removal of color, BOD, COD, phenolics, and sulfide effluent. Junna and Ruonala (1991) reported removal
by microorganisms such as Pseudomonas putida, of BOD7 ranging between 50% and 75% and chlo-
Citrobacter sp., and Enterobacter sp. in the activated rinated phenolics 10 – 50% by an aerated lagoon.
sludge process. Mohamed et al. (1989) reported Achoka (2002) reported that an oxidation pond
removal of chlorinated phenols, 1,1-dichlorodimethyl removed chemical compounds greater than 50%.
sulfone (DDS), and chlorinated acetic acids in an Schnell et al. (2000a) reported removals of BOD,
oxygen activated sludge effluent treatment plant. AOX, chlorinated phenolics, and polychlorinated
Demirbas et al. (1999) reported AOX removal by phenolics respectively from an aerated lagoon.
the activated sludge process. Junna and Ruonala
(1991) reported 90% BOD7, 70% COD, 40 – 60% Aerobic biological reactors. Many authors
AOX, and 60 – 95% chlorinated phenols removal by have reported high removals of organic pollutants of
the activated sludge process. Bryant et al. (1992) kraft mill wastewater by sequencing batch reactor
reported AOX removal of 46% on average from (SBR) treatment (Franta et al., 1994; Franta and
two activated sludge systems studied. Andreasan et Wilderer, 1997; Milet and Duff, 1998). Reid and
al. (1999) suggested the addition of an anoxic selector Simon (2000) reported 100% removal of methanol
before the activated sludge plant to improve the and 90% removal of CODsol by SBR. Substantial
sludge settlability problem. Raghuveer and Sastry removal of COD, TOC, BOD (Magnus et al.,
(1991) reported that a minimum of mixed liquor 2000a), lignin and resin acids (Magnus et al.,
suspended solids (MLSS) of 2000 –2500 mg/l and 2000b) of TMP wastewater using high rate compact
an aeration time of 6– 8 h were required to remove reactors (HCRs) at a retention time of 1.5 h had
83 – 88% of BOD. High removals of BOD, COD, been reported. Removal of COD by a moving bed
AOX, and chlorinated phenolics have been achieved bifilm reactor (MBBR) had been demonstrated (Jah-
in the activated sludge process (Saunamaki, 1997; ren et al., 2002; Borch-Due et al., 1997). Magnus et
Schnell et al., 2000a). Kennedy et al. (2000) reported al. (2000c) reported 93% and 65% removal of BOD
that the activated sludge was successful in removing and COD, respectively by a biological compact
nearly all detectable Microtoxk toxicity from reactor. Berube and Hall (2000) showed that approx-
bleached kraft pulp mills at low level whereas the imately 93% removal of TOC could be achieved by
PACTk was slightly better in removing highly toxic a membrane bioreactor. Asselin et al. (2000) con-
concentrated effluents. cluded that suspended carrier biofilm reactor (SCBR)
was highly efficient in removing chronic toxicity Aerated lagoons. Stuthridge and Mcfarlane from the effluent. Rovel et al. (1994) achieved
(1994) stated that 70% removal of the AOX from the 76%, 62%, 81%, and 48% removal of BOD,
aerated lagoon was attributed to a short residence COD, SS, and AOX, respectively, using a biofilter.
time section of the treatment system where the Rudolfs and Amberg (1953) demonstrated that aer-
chlorinated stage effluents were mixed with general obic treatment of whitewater (high strength) was
mill wastewaters. The effect of simple mixing was able to achieve 70 –80% removal of BOD. Typical
reported to be responsible for 15 – 46% removal. efficiencies of aerobic systems are presented in
Bryant et al. (1997) reported 67% removal of am- Table 8.
46 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

Table 8 activated carbon. Dufresne et al. (2001) observed that

Typical efficiencies of aerobic systems (Springer, 2000; *Kantar- undiluted foul condensates at Windsor mill were toxic
djieff and Jones, 1997)
to anaerobic biomass. Chen and Horan (1998) stated
System Aeration Organic loading Efficiency
that COD, and sulfate removals of 66% and 73%,
time (day) (lb BOD/1000 ft3) (%)
respectively, were obtained using a UASB reactor
Aerobic biofilters – 3.4 kg/m3/day 74 – 92
with a hydraulic retention time of 6 h. Peerbhoi
(sulfite mill)*
Aerobic biofilters – – 74 – 90 (2000) investigated anaerobic treatability of black
(TMP)* liquor by a UASB reactor in her study at the Univer-
Aerobic stabiliztion 5 – 10 50 80 – 90 sity of Roorkee, India. The author concluded that
basin anaerobic biological treatment of black liquor was
Activated sludge 3–8 h 50 80 – 85
not feasible, as the pollutants were not readily de-
gradable. Perez et al. (1998) evaluated two anaerobic
6.2.2. Anaerobic treatment systems (anaerobic filters and fluidized bed) in labo-
An anaerobic process is considered more suitable ratory-scale reactors and reported that 81.5% organic
to treat high strength organic effluents. Before 1980s, removal efficiency was obtained in the case of fluid-
the treatment of pulp mill effluents by anaerobic ized bed with porous packing and 50% removal was
means was limited, as most of the pulp mill effluents obtained in the case of anaerobic filters on corrugated
at that time were less concentrated (300 – 2000 mg/ plastic tubes. Rajeswori et al. (2000) reported a 50%
l BOD) (Bajpai, 2000) and were not suitable for reduction of BOD of debarking wastewater by a
anaerobic treatment. Anaerobic filter, upflow sludge fluidized bed reactor. Thompson et al. (2001) reported
blanket (UASB), fluidized bed, anaerobic lagoon, and that COD removal efficiency of 80% was constantly
anaerobic contact reactors are anaerobic processes, achievable but the residual COD was around 800 mg/
that are commonly used to treat pulp and paper mill l meaning that additional treatment was essential.
effluents. Pretreatment of the kraft mill black liquor Schnell et al. (1992) concluded that anaerobic treat-
was investigated by Poggi-Varaldo et al. (1996) and ment systems were less suitable for treatment of
they reported that continuous anaerobic treatment of sulfite-spent liquor compared to an aerobic system.
wastewater contaminated with black liquor was fea- The anaerobic treatability of different processes are
sible at low to medium loading rates, with a total COD given in Table 9.
removal of 48– 80% and biodegradable COD reduc-
tion of 87 – 96%. Jahren et al. (1999) compared 6.3. Fungal treatment
anaerobic and aerobic treatment for TMP mill effluent
and found that 84% and 86% removal of COD from Taseli and Gokcay (1999) isolated fungal specie
anaerobic and aerobic treatment systems, respectively, (Pencillium sp.) which was able to remove 50% of the
was achieved. Rajeshwari et al. (2000) reported that AOX, and color from the soft-wood bleachery efflu-
chlorine bleaching effluents were not suitable for ents in a contact time of 2 days. Several authors
anaerobic treatment due to their low biodegradability reported on the capacity of different fungal species
and presence of toxic substances that affects metha- to remove color from kraft mill effluent (Gokcay and
nogens. Sandquist and Sandstrom (2000) developed a Dilek, 1994; Duran et al., 1994; Sakurai et al., 2001).
new treatment technology [the process consists of Prasad and Gupta (1997) reported on a substantial
three steps: (1) stripping of sulfides and other volatile reduction of color and COD by the use of white rot
components from condensate; (2) regenerative ther- fungi T. versicolor and P. chrysosporium. Saxena and
mal oxidation of stripper off gases; (3) adsorption of Gupta (1998) showed that white-rot fungi P. chrys-
sulfur oxide] to treat foul condensate (sulfide) from osporium in combination with other white-rot fungi
the black liquor. Removal efficiency for foul conden- (P. sanguineus, P. ostreatus and H. annosum) and with
sate was reported to be more than 99% at a pH of 4 the use of the surfactants were able to remove color,
and removal of methanol was 90% at a low liquid/gas COD, and lignin content. Choudhury et al. (1998)
ratio. Jackson-Moss et al. (1992) found 50% removal found that lignin, BOD, COD and color removal were
of COD and color by anaerobic biological granular 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
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. 83% of color and 75% of lignin (Verenich and Kallas,
Zhang et al. (2000a) examined the removal of most of 2001). A combination of ozone and biofilm reactor
the detrimental organics from whitewater by com- removed 80% COD (Helble et al., 1999). A combi-
bined enzyme and fungal treatment. The removal of nation of chemical oxidation with ozone removed
lignin was >90% whereas resin and fatty acids were 90% of wood extractives and 50% of the COD from
reduced by 20%. Zhang et al. (2000b) showed that TMP wastewater at 150 jC (Laari et al., 1999).
fungus such as T. versicolor and fungal culture filtrate Athanasopoulos (2001) suggested post treatment
(FCF) obtained from these organisms were able to methods such as electrolysis or ozonation to reduce
efficiently degrade the dissolved and colloidal sub- COD, and NH4+ – N concentration to the permitted
stances. Mendonca et al. (2002) suggested fungal level. Nakamura et al. (1997) reported on efficient
pretreatment of P. taeda wood chips by C. subvermis- degradation of lignin using a combined treatment of
pora. The performance of fungal treatment is summa- ozone and activated sludge process. Jokela and Keski-
rized in Table 10. talo (1999) reported that a combination of dissolved
air flotation and chemical precipitation removed 93%
6.4. Integrated treatment processes SS, 50% BOD7, 57% COD, 92% phosphorus, and
52% nitrogen.
An integrated or hybrid system is designed to take A combination of activated sludge and with
advantage of unique features of two or more process- ozonation (as tertiary treatment) removed 87 –97%
es. A combination of coagulation and wet oxidation COD, and 97% BOD (Schmidt and Lange, 2000).
removed 51% of COD (Verenich et al., 2001); and 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)
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
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)
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)
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)
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.
Pulp and – – – 96.63 – 96.8 – – – 96.92 Chandra (2001)
paper mill
Paper mill – – 1000 99 1533a 85 – – – – Knudsen et al.

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.

Kraft mill – – – – 20 – 65 – 17 – 70 – – Chernysh et al.
(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.
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)
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)
Unit in g/d.
50 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

whitewater. A combined anaerobic – aerobic treat- basin at Monsteras mill. The system comprised of
ment system was suggested to treat bleached kraft an anoxic selector, an aerated basin, and a secondary
pulp and paper mill effluents (Duncan and Thia, clarifier in series. The removals of extractives, resin
1992; Wang et al., 1997). Lescot and Jappinen and fatty acids were 96% and 98%, respectively,
(1994) showed that a combination of an aerated whereas the system reduced Microtoxk by 99%.
lagoon and a secondary clarifier was able to treat Welander et al. (2000) reported on the performance
bleached kraft mill effluent in Finland resulting in of an aerobic biological process called LSP (low
87%, 96%, 65%, 53%, and 22% removal of SS, sludge production) to lower the biological sludge by
BOD7, COD, AOX, and color, respectively. Carlson 80 – 90%. The system configuration was primary
et al. (2000) reported that 77%, 98 –99%, 72%, and clarifier, aeration basin, and secondary clarifier. A
81% removal of COD, BOD, TN, and TP, respec- combination of physicochemical, biological, and ef-
tively, was achieved after upgrading the aerated 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
McMillan Bloedel, NSSC/CTMP 15 7000 17,500 – 80 55
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 51

99% BOD, 91% COD, 97% SS, and 90% color of a when the production has been increased. Trotter
pulp and paper mill in Brazil (Foelkel, 1989). Rusten (1990a,b) evaluated biotechnological applications
et al. (1994) reported that a combination of a biofilm such as genetic modification of plant, biopulping,
reactor followed by one anaerobic and two aerobic and biobleaching to reduce chlorinated organic com-
reactors was found to remove 50% COD, 80– 90% pounds as an emerging technology for internal pollu-
BOD7, 50% AOX, 90% ClO3. Shaw et al. (2002) tion control. Enzyme treatment for pulp dissolving,
showed that a combination of aerobic reactor fol- improving tensile properties by treating mechanical
lowed by anaerobic reactor removed 94% color, and pulp with white rot organisms and enzymatic beating
66% TOC. Schnell et al. (1997) found that 87– 95%, of chemical pulps, hemicellulose, and decolorization
70 –77%, and 80 –94% removal of BOD, COD, and by white rot fungi were given as possible biotechno-
resin and fatty acids was provided by biological logical options.
treatment. Tardif and Hall (1997) reported 100%, Among the various treatment processes currently
96%, 76%, and 34% removal of resin acid (RA), used for pulp and paper effluent treatment, only a few
fatty acid (FA), dissolved chemical oxygen demand are commonly adopted by pulp and paper industry
(DCOD), and total dissolved solids (TDS), respec- especially for tertiary treatment. Some of the treatment
tively at temperatures 20– 40 jC by an SBR. An processes such as ozonation, fenton’s reagent, adsorp-
MBR removed 100% RA and FA, 84% DCOD, and tion, and membrane technology are efficient but are
37% TDS at 40 – 50 jC. Malmquist et al. (1999) more expensive. Sedimentation is the most commonly
reported a COD removal of 70 –90% of whitewater adopted process by the pulp and paper industry to
by biological treatment. Badar (1996) suggested a remove suspended solids. The performance data given
number of methods to improve the integrated paper by Springer (2000) showed 80 – 90% removal of
mill wastewater effluent treatment: (1) increasing the initial suspended solids from most of the mills except
capacity of the aeration basin; (2) installing an extra a deinking mill. Flotation is also commonly used in
dissolved air flotation clarifier; (3) adding chlorine the pulp and paper industry but most of the time as a
gas to improve bulking of sludge problem and (4) tertiary treatment. Coagulants are a preferred option
injecting oxygen to treat BOD during heavy rain and for removing turbidity and color from the wastewater.
flooded conditions. Graves and Joyce (1994) Reported results have shown that they are also capable
reviewed the ability of biological treatment systems in reducing COD, TOC, and AOX to some extent.
to remove chlorinated organic compounds discharged Among the coagulants, modified chitosan showed the
from pulp and paper industry. AOX removal of 32% highest performance for color and TOC removal.
(aerated lagoon) and 10 –65% by activated sludge Polyelectrolytes are better than alum and they produce
plant was reported. Gupta et al. (2001) isolated less sludge and pose less problems with sludge
bacterial specie Aeromonas formicans suitable to dewaterability than alum. Adsorption processes are
treat black liquor from kraft pulp and paper mills. useful to remove color, COD, and AOX. They are
Performances of various treatment processes are rather expensive and it is not known whether the pulp
summarized in Tables 11 –14. and paper industry are employing them widely. How-
ever, laboratory-scale experiments are usually
reported. Activated charcoal, fuller’s earth, and coal
7. Discussion ash showed better results for color removal. Activated
coke alone was able to remove 90% of the COD,
The literature review showed that an internal AOX, DOC, and color.
process change is one of the options to be adopted Chemical oxidants such as ozone + photocatalysis,
by the pulp and paper industry to reduce the pollution and ozone + UV are reported to be efficient in
at the source. A recent comprehensive study carried removing COD and TOC and color. However, the
out in a large number of pulp and paper mills in the efficiency largely depends upon the concentration of
US found that the effluent discharge has been reduced the COD. Ozone alone is able to remove 90% of
by 30%; TSS and BOD have been reduced by 45% EDTA and AOX, and over 80% of COD. However,
and 75%, respectively (Das and Jain, 2001) even 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 processes or combination of physicochemical and
in Europe but it is emerging in North America. biological processes. The confirmation of the reported
Membrane processes are efficient in reducing over results, their applicability in the real field, and eco-
90% of color, TSS, and AOX in most of the cases. nomic evaluations are very important in adopting the
Fouling of membranes is a problem in the case of process. For example, the anaerobic treatment process
soft wood effluent treated by membrane filtration. In for pulp and paper mill effluents is still in an initial
secondary treatment processes, activated sludge is application phase.
the most commonly used. UASB and fluidized beds However, comprehensive evaluations made by var-
are also gaining in use recently. The problem with ious authors lead to a better understanding of the
activated sludge is sludge bulking. Reported results various treatment processes and their adaptability.
have shown that activated sludge can remove all For example, Jemaa et al. (2000) stated that chemical
types of the pollutants pertaining to the pulp and precipitation, evaporation, membrane technology, and
paper industry. However, the removal of AOX is ion exchange were the established options for the
below 50%, BOD around 95% in most of the mills, removal of colloids and metal ions. Perez et al.
and COD removal averages around 70%. This sys- (2002a) conducted an economic evaluation of various
tem is also efficient in removing chlorinated phenolic advanced oxidation processes to remove organic con-
compounds (over 75%) most of the time. Dalentoft taminants. Ozonation was stated to be effective but
and Thulin (1997) reported that Kaldnes (anaero- rather an expensive process. Rintala and Puhakka
bic + aerobic) process in series with an activated (1994) stated that operation costs of the activated
sludge, could be an efficient, stable, and a compet- sludge was about three times greater than that of
itive combination process, considering both invest- anaerobic systems. Bajpai (2000) presented compara-
ment and operating costs. Aerated lagoons are tive costs of the anaerobic and activated sludge treat-
efficient in removing BOD over 95% in most of ment, which showed that activated sludge was almost
the reported results. COD removals are moderate twice as expensive as anaerobic reactors. The recent
between 60% and 70%, AOX around 50%, and a paper by Perez et al. (2002b) reported a high efficiency
high removal (85%) for chlorinated phenolics. An- of COD and TOC removal when iron ion was used
aerobic contact reactors are efficient in removing with ozone/UV treatment system. The authors showed
biodegradable organic compounds such as BOD, that the presence of iron ion in the ozone/UV treatment
and COD. The performance data from various mills brought a complete removal of COD in 90 min while
showed that anaerobic contact reactors were able to TOC removal was higher than 90%. The report stated
remove over 90% of BOD and 65% of COD in most that the overall cost was reduced by 50%, which is
of the cases. Anaerobic filters and fluidized bed encouraging news for the industry. Mobius and
reactors are suitable in reducing organic pollutants Cordes-Tolle (1994) suggested that sand filters, bio-
only. Both the reactors achieve almost same efficien- filters, low capacity trickling filters, flocculation and
cy in terms of BOD (>80%), and COD (>70%) precipitation with inorganic salts in combination with
removal (refer to Table 14 for details). UASBs are filtration or flotation are the emerging systems for
able to remove over 80% of BOD and 50 – 80% of adoption by pulp and paper mills.
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. 8. Conclusions
Removal of color using white rot fungi was above
80% in most of the reported cases and COD removal Based on the above literature review, the following
was above 75%. White rot fungi particularly P. conclusions are drawn:
chrysosporium and C. versicolor are suitable for
efficient degradation of the refractory material (Baj- (i) Both aerobic and anaerobic treatment systems
pai and Bajpai, 1994). The reported results have are feasible to treat wastewater from all types
shown that high removals are achieved in the case of pulp and paper mills except that bleaching
of the combination of two or more physicochemical kraft effluents are less suitable for treatment by
D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 53

anaerobic means, as they are more toxic to Badar TA. Wastewater treatment at pulp and paper mills effluent
anaerobic bacteria. compliance improvements at a newsprint facility. Asia Pac Tech
Monit 1996;13(6):8 – 13.
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wastewater requires further treatment as it technology. Randalls Road, Leatherhead, UK: Pira International;
contains high residual COD. 2000.
(iii) A combination using an anaerobic process Bajpai P, Bajpai PK. Biological colour removal of pulp and paper
mill wastewaters. J Biotechnol 1994;33:211 – 20.
followed by an aerobic treatment system is a
Balcioglu AI, Ferhan C. Treatability of kraft pulp bleaching waste-
better option, as it can make use of the water by biochemical and photocatalytic oxidation. Water Sci
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