Anda di halaman 1dari 22

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

www.elsevier.com/locate/scitotenv

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-


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@uregina.ca (T. Viraraghavan). 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 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
fibers.
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
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 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
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. 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 6.2.1.1. 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% 6.2.1.3. 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
6.2.1.2. 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
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. 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)
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- 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
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 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.
(ii) The anaerobic treatment of high strength Bajpai P. Treatment of pulp and paper mill effluents with anaerobic
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
advantages of both the treatment processes. Technol 1999;40(1):281 – 8.
(iv) Color is removed efficiently by fungal treat- Baruah BK. Effect of paper mill effluent on plankton population of
ment, coagulation, chemical oxidation, and wetland. Environ Ecol 1997;15(4):770 – 7.
ozonation. Berube PR, Hall ER. Fate and removal kinetics of contaminants
contained in the evaporator condensate during treatment for
(v) Chlorinated phenolic compounds and AOX can reuse using a high temperature membrane bioreactor. Proc.
be removed by adsorption, ozonation and 86th PAPTAC annual meeting, Montreal, Quebec. Canada: Pulp
membrane filtration. and Paper Technical Association of Canada; 2000. p. B67.
(vi) Combinations of two or more physicochemical Berube PR, Kahmark KA. Pulp and paper mill effluents. Water
processes produce a high removal of toxic Environ Res 2001;73(5):1 – 36.
Borch-Due A, Anderson R, Opheim B. Treatment of integrated
pollutants. newsprint mill wastewater in moving bed biofilm reactors. Wa-
(vii) Combinations of physicochemical and biolog- ter Sci Technol 1997;35(2 – 3):173 – 80.
ical treatment processes with optimization of Bryant CW, Avenell JJ, Barkley WA, Thut RN. The removal of
the process provide a long-term solution for chlorinated organics from conventional pulp and paper waste-
water treatment systems. Water Sci Technol 1992;26(1 – 2):
pulp and paper mill effluent treatment.
417 – 25.
(viii) More studies are needed on the removal of Bryant CW, Barkley WA, Garett RM, Gardner FD. Biological ni-
AOX and chlorinated phenolic compounds. trification of kraft wastewater. Water Sci Technol 1997;35(2 – 3):
147 – 53.
Carlson B-L, Ericsson T, Loyblad R, Persson S, Simon O. The
reconstruction of an aerated lagoon to a long-term aerated sludge
References (LAS) plant at Sodra cell, Monsteras kraft pulp mill. Tappi
International Environmental Conference and Exhibit, Denver,
Achoka JD. The efficiency of oxidation ponds at the kraft pulp CO, vol. 1. Norcross, GA 30092, USA: Technical Association
and paper mill at Webuye in Kenya. Water Res 2002;36: for Pulp and Paper Industry (TAPPI); 2000. p. 363 – 71.
1203 – 12. Chandra R. Microbial decolourisation of pulp mill effluent in pres-
Afonso MD, Pinho MN. Membrane separation processes in pulp ence of nitrogen and phosphorous by activated sludge process. J
and paper production. Filtr Sep 1991;28(1):42 – 4. Environ Biol 2001;22(1):23 – 7.
Andreasan K, Agertved J, Petersen JO, Skaarup H. Improvement Chen W, Horan NJ. The treatment of a high strength pulp and paper
of sludge settleability in activated sludge plants treating efflu- mill effluent for wastewater re-use (II) biological sulphate re-
ent from pulp and paper industries. Water Sci Technol 1999; moval from effluent with a low COD/sulphate ratio. Environ
40(11 – 12):215 – 21. Technol 1998;19:163 – 71.
Archibald F. The presence of coliform bacteria in Canadian pulp Chernoberezhskii YuM, Dyagileava AS, Barysheva IA. Coagula-
and paper mill water systems—a cause for concern? Water Qual tion treatment of wastewaters from paper and pulp plants. Russ J
Res J Can 2000;35(1):1 – 22. Appl Chem 1994;67(3):354 – 9.
Asselin C, Collin D, Graff S. Effluent treatment for chronic toxicity Chernysh A, Liss NS, Allen GD. A batch study of the aerobic and
removal with the suspended carrier biofilm reactor. Tappi Inter- anaerobic removal of chlorinated organic compounds in an aer-
national Environmental Conference and Exhibit. Denver CO, ated lagoon. Water Pollut Res J Can 1992;27(3):621 – 38.
vol. 2. Norcross, GA 30092, USA: Technical Association for Choudhury S, Sahoo N, Manthan M, Rohela RS. Fungal treatment
Pulp and Paper Industry (TAPPI); May 2000. p. 805 – 11. of pulp and paper mill effluents for pollution control. J Ind
Athanasopoulos NS. Use of various processes for pilot plant treat- Pollut Control 1998;14(1):1 – 13.
ment of wastewater from a wood processing factory. J Chem Dalentoft E, Thulin P. The use of the kaldnes suspended carrier
Technol Biotechnol 2001;76:246 – 50. process in treatment of wastewaters from the forest industry.
Azevedo MAD, Drelich J, Miller JD. The effect of pH on pulping Water Sci Technol 1997;35(2 – 3):123 – 30.
and flotation of mixed office wastepaper. J Pulp Pap Sci 1999; Das KT, Jain AK. Pollution prevention advances in pulp and paper
25(9):317 – 30. processing. Environ Prog 2001;20(1):87 – 92.
54 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

Das CP, Patnaik LN. Removal of lignin by industrial solid wastes. aspects about paper mill effluent treatment with ozone. Environ
Pract Period Hazard, Toxic, Radioact Waste Manag 2000; Technol 2000;21:717 – 21.
4(4):156 – 61. Ganjidoust H, Tatsumi K, Yamagishi T, Gholian RN. Effect of syn-
Demirbas G, Gokcay CF, Dilek FB. Treatment of organic chlorine thetic and natural coagulant on lignin removal from pulp and
in pulping effluents by activated sludge. Water Sci Technol paper waste water. Water Sci Technol 1997;35(2 – 3):291 – 6.
1999;40(1):275 – 9. Ginkel GCV, Virtapohja J, Steyaert JAG, Alen R. Treatment of
De Pinho MN, Minhalma M, Rosa MJ, Taborda F. Integration of EDTA-containing pulp and paper will wastewaters in activated
flotation/ultrafiltration for treatment of bleached pulp effluent. sludge plants. Tappi J 1999;82(2):138 – 42.
Pulp Pap Can 2000;104(4):50 – 4. Gokcay FC, Dilek FB. Treatment of effluents from hemp-based
Dey A, Sarkar D, Sengupta B, Banerjee S. Wastewater treatment in pulp and paper industry (2) biological treatability of pulping
pulp and paper industry-trend and practices. Indian J Environ effluents. Water Sci Technol 1994;29(9):165 – 8.
Prot 1991;11(12):899 – 905. Graves JW, Joyce TW. A critical review of the ability of biological
Dilek FB, Gokcay CF. Treatment of effluents from hemp-based treatment systems to remove chlorinated organics discharged by
pulp and paper industry: waste characterization and physico- the paper industry. Water SA 1994;20(2):155 – 60.
chemical treatability. Water Sci Technol 1994;29(9):161 – 3. Gubelt G, Lumpe C, Joore L. Towards zero liquid effluents at
D’surney SJ, Eddy LP, Felder DP, Rodgers JH, Deardorff TL. Niederauer Muhle—the validation of two noval separation tech-
Assesment of the impact of a bleached kraft mill effluent on a nologies. Pap Technol (UK) 2000;41(8):41 – 8.
south-central USA river. Environ Toxicol 2002;15(1):28 – 39. Gune NV. Total water management in pulp and paper industry with
Dube M, McLean R, MacLatchy D, Savage P. Reverse osmosis focus on achieving ‘zero effluent discharge’ status. IPPTA J
treatment: effects on effluent quality. Pulp Pap Can 2000; 2000;12(4):137 – 42.
101(8):42 – 5. Gupta A. Pollution load of paper mill effluent and its impact on
Dufresne R, Caouette L, Norval GW, Kanters CJ. Treat- biological environment. J Ecotoxicol Environ Monit 1997;7(2):
ment of clean condensate using catalytically enhanced oxida- 101 – 12.
tion. Proc. 86th PAPTAC annual meeting, Montreal, Quebec. Gupta VK, Minocha AK, Jain N. Batch and continuous studied on
Canada: Pulp and Paper Technical Association of Canada; treatment of pulp mill wastewater by aeromonas formicans. J
2000. p. A257. Chem Technol Biotechnol 2001;76:547 – 52.
Dufresne R, Liard A, Blum SM. Anaerobic treatment of condensates: Hansen E, Zadura L, Frankowski S, Wachowicz M. Upgrading of an
at a kraft pulp and paper mill. Water Environ Res 2001;73(1): activated sludge plant with floating biofilm carriers at Frant-
103 – 9. schach Swiecie S.A. to meet the new demands of year 2000.
Duncan A, Thia B. Treatment of pulp and paper mill effluent. Aust Water Science and Technology 1999;40(11 – 12):207 – 14.
Biotechnol 1992;2(4):235. Hassan MM, Hawkyard CJ. Decolourisation of aqueous dyes by
Duran N, Esposito E, Innicentini-Mei LH, Canhos PV. A new al- sequential oxidation treatment with ozone and Fenton’s
ternative process for kraft E1 effluent treatment. Biodegradation reagent. Journal of Chemical Technology and Biotechnology
1994;5:13 – 9. 2002;77:834 – 41.
Dutta SK. Study of the physicochemical properties of effluent of the Helble A, Schalyer W, Liechti PA, Jenny R, Christian MH. Ad-
paper mill that affected the paddy plants. J Environ Pollut vanced effluent treatment in the pulp and paper industry with a
1999;6(2 and 3):181 – 8. combined process of ozonation and fixed bed biofilm reactors.
Erisction G, Larsson A. DNA A dots in perch (Perca fluviatillis) in Water Sci Technol 1999;40(11 – 12):343 – 50.
coastal water pollution with bleachen in pulp mill effluents. Hinck ML, Ferguson J, Puhaakka J. Resistance of EDTA and DPTA
Ecotoxicol Environ Saf 2000;46:167 – 73. to aerobic biodegradation. Water Sci Technol 1997;35(2 – 3):
Falth F. Ultrafiltration of E1 stage effluent for partial closure of 25 – 31.
the bleach plant. Proc. 86th PAPTAC annual meeting, Mon- Holmbom B, Harju L, Lindholm J, Groning AL. Effect of a pulp
treal, Quebec. Canada: Pulp and Paper Technical Association and paper mill on metal concentration in the receiving lake
of Canada; 2000. p. B85. system. Aqua Fenn 1994;24(1):93 – 110.
Felder DP, D’surney SJ, Rodgers JH, Deardorff TL. A comprehen- Hostachy JC, Lenon G, Pisicchio JL, Coste S, Lgeay C. Reduction
sive environmental assessment of a receiving aquatic system of pulp and paper mill pollution by ozone treatment. Water Sci
near an unbleached kraft mill. Ecotoxicology 1998;7:313 – 24. Technol 1997;35(2 – 3):261 – 8.
Foelkel C. Advanced waste treatment. Pulp Pap 1989;63(4):173 – 4. Howe J, Michael RW. Effects of pulp mill effluent irrigation on the
Franta JR, Wilderer PA. Biological treatment of papermill waste- distribution of elements in the profile of an arid region soil.
water by sequencing batch reactor technology to reduce residual Environ Pollut 1998;105:129 – 35.
organics. Water Sci Technol 1997;35(1):129 – 36. Jackson-Moss CA, Maree JP, Wotton SC. Treatment of bleach plant
Franta J, Helmreich B, Pribyl M, Adamietz E, Wilderer PA. effluent with the biological granular activated carbon process.
Advanced biological treatment of papermill wastewaters; effects Water Sci Technol 1992;26(1 – 2):427 – 34.
of operating conditions on COD removal and production of sol- Jahren SJ, Oedegaard H. Treatment of thermomechanical pulping
uble organic compounds in activated sludge systems. Water Sci (TMP) whitewater in termophilic (55 (C) anaerobic – aerobic
Technol 1994;30(3):199 – 207. moving bed biofilm reactors. Water Sci Technol 1999;40(8):
Freire RS, Kunz A, Duran N. Some chemical and toxicological 81 – 90.
D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 55

Jahren SJ, Rintala JA, Odegaard H. Evaluation of internal thermo- fish in a river receiving pulp and paper mill effluents. Environ
philic biotreatment as a strategy in TMP mill closure. Tappi J Pollut 2002;118:123 – 40.
1999;82(8):141 – 9. Laari A, Korhonen S, Tuhkanen T, Verenich S, Kallas J. Ozonation
Jahren JS, Rintala JA, Odegaard H. Aerobic moving bed biofilm and wet oxidation in the treatment of thermomechanical pulp
reactor treating thermomechanical pulping whitewater under (TMP) circulation waters. Water Sci Technol 1999;40(11 – 12):
thermophilic conditions. Water Research 2002;36:1067 – 75. 51 – 8.
Jemaa N, Thompson R, Paleologou M, Berry RM. Non-process Laari A, Korhonen S, Kallas J, Tuhkanen T. Selective removal of
elements in the kraft recovery cycle, Part II: control and removal lipophilic wood extractives from paper mill water circulations
options. Pulp and Paper Canada 2000;101(2):41 – 6. by ozonation. Ozone: Sci Eng 2000;22:585 – 605.
Johnsen K, Tana J, Lehtinen K-J, Stuthridge T, Mattsson K, Hem- Larisch BC, Duff JB. Effect of H2 O2 and data on the character-
ming J, Carlberg GE. Experimental field exposure of brown istics and treatment of TCF (totally chlorine-free) and ECF
trout to river receiving effluent from an integrated news- (elementally chlorine-free) kraft pulping effluents. Water Sci
print mill. Ecotoxicology and Environmental Safety 1998;40: Technol 1997;35(2 – 3):163 – 71.
184 – 93. Larisch BC, Duff JB. Effect of DTPA and EDTA on activated
Jokela P, Keskitalo P. Plywood mill water system closure by dis- sludge reactors treating bleached kraft mill effluent. Tappi J
solved air floatation treatment. Water Science and Technology 2000;83(6):54.
1999;40(11 – 12):33 – 41. Leppanen H, Oikari A. Occurrence of retene and resin acids in
Jonsson AS, Jonsson C, Teppler M, Tomani P, Wannstrom S. Treat- sediments and fish bile from lake receiving pulp and a
ments of paper coating colour effluents by membrane filtration. paper mill effluents. Environ Toxicol Chem 1999;18(7):
Desalination 1996;105:263 – 76. 1498 – 505.
Junna J, Ruonala S. Trends and guidelines in water pollution con- Lescot JC, Jappinen H. Effluent treatment in pulp and paper mills:
trol in the Finnish pulp and paper industry. Tappi J 1991; present technology and development trends. Appita J 1994;
74(7):105 – 11. 47(4):330 – 2.
Kabdash I, Tunay O, Eldem N. Treatability of wastepaper pulping Lindstrom-Seppa P, Hunskonen S, Kotelevtsev S, Mikkelson P, Ran-
process wastewater. Proceedings of the Industrial Waste Confer- nen T, Stepanova L, et al. Toxicity and mutagenity of waste
ence, West Lefayette, USA, vol. 51. Chelsea, Michigan 68118, waters from Baikalsk pulp and paper mill: evaluation of pollutant
USA: Ann Arbor Press Inc.; 1996. p. 645 – 50. contamination in lake Baikal. Mar Environ Res 1998;46(1 – 5):
Kahmark KA, Unwin JP. Pulp and paper effluent management. 273 – 7.
Water Environ Res 1996;68(4):551. Magnus E, Carlberg GE, Norske HH. TMP wastewater treatment
Kahmark KA, Unwin JP. Pulp and paper effluent management. including a biological high-efficiency compact reactor. Nord
Water Environ Res 1998;70(4):667. Pulp Pap Res J 2000a;15(1):29 – 36.
Kahmark KA, Unwin JP. Pulp and paper effluent management. Magnus E, Carlberg GE, Norske HH. TMP wastewater treatment
Water Environ Res 1999;71(5):836. including a biological high-efficiency compact reactor. Nord
Kallas J, Munter R. Post-treatement of pulp and paper industry Pulp Pap Res J 2000b;5(1):37 – 45.
wastewaters using oxidation and adsorption processes. Water Magnus E, Hoel H, Carlberg GE. Treatment of an NSSC effluent in
Sci Technol 1994;29(5 – 6):259 – 71. a biological high-efficiency compact reactor. Tappi J 2000c;
Kantardjieff A, Jones JP. Practical experiences with aerobic biofil- 83(1):149 – 56.
ters in TMP sulfite and fine paper mills in Canada. Water Sci Makris SP, Banerjee S. Fate of resin acids in pulp mills secondary
Technol 1997;35(2 – 3):227 – 34. treatment systems. Water Res 2002;36:2878 – 82.
Kennedy KJ, Graham B, Droste RL, Fernandes L, Narbaitz R. Malmquist A, Ternstrom A, Welander T. In-mill biological treat-
Microtox and Ceriodaphnia dubia toxicity of BKME with ment for paper mill closure. Water Sci Technol 1999;40(11 – 12):
powdered activated carbon treatment. Water SA 2000;26(2): 43 – 50.
205 – 16. Mandal TN, Bandana TN. Studies on physicochemical and
King HM, Baldwin DS, Rees GN, Mcdonald S. Apparent bio- biological characteristics of pulp and paper mill effluents
accumulation of Mn derived from paper-mill effluent by the and its impact on human beings. J Freshw Biol
freshwater crayfish cherax destructor—the role of Mn oxidis- 1996;8(4):191 – 6.
ing bacteria. Sci Total Environ 1999;226:261 – 7. Mendonca R, Guerra A, Ferraz A. Delignification of Pinus teada
Knudsen L, Pedersen JA, Munck J. Advanced treatment of paper wood chips treated with ceriporiopsis sbvermispora for prepar-
mill effluents by a two-stage activated sludge process. Water Sci ing high-yield kraft pulp. J Chem Technol Biotechnol 2002;
Technol 1994;30(3):173 – 81. 77:411 – 8.
Korhonen S, Tuhkanen T. Effects of ozone on resin acids in ther- Merrill DT, Maltby CV, Kahmark K, Gerhardt M, Melecer H. Eval-
momechanical pulp and paper mill circulation waters. Ozone: uating treatment process to reduce metals concentrations in pulp
Sci Eng 2000;22(6):575 – 84. and paper mill wastewaters to extremely low values. Tappi J
Korhonen SM, Metsarinne SE, Tuhakanen TA. Removal of eth- 2001;84(4):52.
ylenediaminenetraacetic acid (EDTA) from pulp mill effluents Milet GM, Duff SJB. Treatment of kraft condensates in a feedback -
by ozonation. Ozone: Sci Eng 2000;22:279 – 86. controlled sequencing batch reactor. Water Sci Technol 1998;
Kovacs TG, Martel PH, Voss RH. Assessing the biological status of 38(4 – 5):263 – 71.
56 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

Mobius CH, Cordes-Tolle M. Advanced treatment of paper mill effluent by two White-rot fungi. Indian J Environ Health 1997;
wastewaters. Water Sci Technol 1994;29(5 – 6):273 – 82. 39(2):89 – 96.
Mohamed M, Matayun M, Lim TS. Chlorinated organics in tropical Raghuveer S, Sastry CA. Effect of simple in-plant control measures
hardwood kraft pulp and paper mill effluents and their elimina- on the characteristics of wastewater from a pulp and paper mill.
tion in an activated sludge treatment system. Pertanika 1989; Indian J Environ Prot 1990;10(10):739 – 46.
2(3):387 – 94. Raghuveer S, Sastry CA. Biological treatment of pulp mill waste-
Murthy BSA, Sihorwala TA, Tilwankar HV, Killedar DJ. Remov- water and study of biokinetic constants. Indian J Environ Prot
al of colour from pulp and paper mill effluents by sorption 1991;11(8):614 – 21.
t e c h n i q u e — a c a s e s t u d y. I n d i a n J E n v i r o n P r o t Rajeshwari KV, Balakrishnan M, Kansal A, Lata K, Kishore VVN.
1991;11(5):360. State of the art of anaerobic digestion technology for industrial
Nakamura Y, Sawada T, Kobayshi F, Godliving M. Microbial treat- wastewater treatment. Renew Sustain Energy Rev 2000;4(2):
ment of kraft pulp wastewater pretreated with ozone. Water Sci 135 – 56.
Technol 1997;35(2 – 3):277 – 82. Rajvaidya N, Markandey DK. Advances in environmental science
Narbaitz RM, Droste RL, Fernandes L, Kennedy KJ, Ball D. and technology: treatment of pulp and paper industrial effluent.
PACTk process for treatment of kraft mill effluent. Water Sci Ansari Road, New Delhi, India: A.P.H. Publishing; 1998.
Technol 1997;35(2 – 3):283 – 90. Reid TK, Simon A. Feasibility study of sequencing batch reactor
Nemerow NL, Dasgupta A. Industrial and hazardous waste man- technology treating high strength foul condensate for methanol
agement. New York: Van Nostrand Reinhold; 1991. reduction. Tappi International Environmental Conference and
Norris P, Marshall R, Richard M. High temperature on activated Exhibit, Denver, CO 2000;1:185 – 91.
sludge treatment performance and sludge quality in a recycle Reilama I, Ilomaki N. Respect for the environment is part of com-
mill. Tappi International Environmental Conference and Ex- petitiveness-best available technology applied to an old pulp
hibit, Denver, CO, vol. 1. Norcross, GA, 30092, USA: Tech- mill at Kastinen. Water Sci Technol 1999;40(11 – 12):201 – 6.
nical Association for Pulp and Paper Industry (TAPPI); 2000. Rintala JA, Puhakka JA. Anaerobic treatment in pulp and paper mill
p. 383 – 7. waste management: a review. Bioresour Technol 1994;47:1 – 18.
O’connor B, Kovacs T, Gibbons S, Strang AL. Carbon dioxide in Rohella RS, Choudhury S, Manthan M, Murthy JS. Removal of
pulp and paper mill effluents from oxygen -activated sludge colour and turbidity in pulp and paper mill effluents using poly-
treatment plants as a potential source of distress and toxicity electrolytes. Indian J Environ Health 2001;43(4):159 – 63.
to fish. Water Qual Res J Can 2000;35(2):189 – 200. Rovel JM, Trudel JP, Lavalle P, Schroeter I. Paper mill efflu-
Oeller HJ, Daniel I, Weinberger G. Reduction in residual COD in ent treatment using biofliltration. Water Sci Technol 1994;
biologically treated paper mill effluents by means of combined 29(10 – 11):217 – 22.
Ozone and Ozone/UV reactor stages. Water Sci Technol 1997; Roy-Arcand L, Archibald FS. Ozonation as a treatment for mechan-
35(2 – 3):269 – 76. ical and chemical pulp mill effluents. Ozone: Sci Eng
Owens JW, Swanson SM, Birkholz DA. Environmental monitoring 1996;18:363 – 84.
of bleached kraft pulp mill chlorophenolic compounds in a Rudolfs W, Amberg HR. White water treatment: V. Areation with
Northern Canadian River system. Chemosphere 1994;29(1): nonflocclent growths. Sew Ind Wastes 1953;25(1):70 – 8.
89 – 109. Rusten B, Mattsson E, Due BA, Westren T. Treatment of pulp and
Peerbhoi Z. Treatability studies of black liquor by UASBR-PhD paper industry wastewaters in novel moving bed biofilm reac-
thesis 2000. University of Roorkee, India. tors. Water Sci Technol 1994;30(3):161 – 71.
Perez M, Romero LI, Sales D. Comparative performance of high Sakurai A, Yamomoto T, Makabe A, Kinoshita S, Sakakibara M.
rate anaerobic thermophilic technologies treating industrial Removal of lignin in a liquid system by an isolated fungus. J
wastewater. Water Res 1998;2(3):559 – 64. Chem Technol Biotechnol 2001;77:9 – 14.
Perez M, Torrades F, Domenech X, Peral J. Removal of organic Sandquist KK, Sandstrom E. A novel technology to treat foul con-
contaminants in pulp effluents by AOPs: an economic study. densate and NCG gases in a closed loop. TAPPI International
J Chem Technol Biotechnol 2002a;77:525 – 32. Environmental Conference and Exhibit, Denver, CO, vol. 1.
Perez M, Torrades F, Garcia-Hortal JA, Domenech X, Peral J. Re- Norcross, GA, 30092, USA: Technical Association for Pulp
moval of organic contaminants in paper pulp treatment effluents and Paper Industry (TAPPI); 2000. p. 147 – 55.
under fenton and photo-fenton conditions. Appl Catal 2002b; Saunamaki R. Activated sludge plants in Finland. Water Sci Tech-
36(1):63 – 74. nol 1997;35(2 – 3):235 – 43.
Perez M, Torrades F, Domenech X, Peral J. Treatment of bleach- Saxena N, Gupta RK. Decolourization and delignification of pulp
ing Kraft mill effluents and polychlorinated phenolic com- and paper mill effluent by white rot fungi. Indian J Exp Biol
pounds with ozonation. J Chem Technol Biotechnol 2002c;77: 1998;36:1049 – 51.
891 – 7. Schmidt T, Lange S. Treatment of paper mill effluent by the
Poggi-Varaldo HM, Estrada-Vazquez C, Fernandez-Villagomez G, use of ozone and biological systems: large scale application
Esparza-Garcia F. Pretreatment of black liquor spills effluent. at lang paper, Ettringen (Germany). Tappi International Envi-
Proceedings of the Industrial Waste Conference, West Lafayette, ronmental Conference and Exhibit, Denver, CO, vol. 2. Nor-
USA 1996;51:651 – 61. cross, GA, 30092, USA: Technical Association for Pulp and
Prasad GK, Gupta RK. Decolourization of pulp and paper mill Paper Industry (TAPPI); 2000. p. 765 – 75.
D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58 57

Schnell A, Hall ER, Skog S. Anaerobic and aerobic treatability of Sullivan, E.C., 1986. The use of advanced treatment methods for
high-yield sulphate spent liquor. Water Pollut Res J Can removal of color and dissolved solids from pulp and paper
1992;27(3):601 – 20. wastewater-Master’s thesis. Virginia Polytechnic Institute and
Schnell A, Sabourin MJ, Skog S, Garvie M. Chemical character- State University.
ization and biotreability of effluents from an integrated alkaline- TAPPI. Environmental issues: a TAPPI press anthology of pub-
peroxide mechanical pulping/machine finish coated paper mill. lished papers. Atlanta, GA: TAPPI Press; 1990.
Water Sci Technol 1997;35(2 – 3):7 – 14. Tardif O, Hall ER. Alternatives for treating recirculated newsprint
Schnell A, Steel P, Melcer H, Hodson PV, Carey JH. Enhanced whitewater at high temperatures. Water Sci Technol 1997;
biological treatment of bleached kraft mill effluents: I. Removal 35(2 – 3):57 – 65.
of chlorinated organic compounds and toxicity. Water Res Taseli B, Gokcay CF. Biological treatment of paper pulping efflu-
2000a;34(2):493 – 500. ents by using a fungal reactor. Water Sci Technol 1999;
Schnell A, Steel P, Melcer H, Hodson PV, Carey JH. Enhanced 40(11 – 12):93 – 9.
biological treatment of bleached kraft mill effluents: II. Reduc- Thompson G, Swain J, Kay M, Forster CF. The treatment of pulp
tion of mixed function oxygenase (MFO) induction in fish. and paper mill effluent: a review. Bioresour Technol 2001;
Water Res 2000b;34(2):501 – 9. 77(3):275 – 86.
Sevimli MF, Sarikaya HZ. Ozone treatment of textile effluents and Tong Z, Wada S, Takao Y, Yamagishi T, Hiroyasu I, Tamatsu K, et
dyes: effect of applied ozone dose, pH and dye concentration. J al. Treatment of bleaching wastewater from pulp-paper plants in
Chem Technol Biotechnol 2002;77:842 – 50. China using enzymes and coagulants. J Environ Sci 1999;
Shaw CB, Carliell CM, Wheatley AD. Anaerobic/aerobic treatment 11(4):480 – 4.
of coloured textile effluents using sequencing batch reactors. Torrades F, Peral J, Perez M, Domenech X, Hortal JAG, Riva MC.
Water Res 2002;36:1993 – 2001. Removal of organic contaminants in bleached kraft effluents
Shawwa AR, Smith DW, Sego DC. Color and chlorinated organics using heterogeneous photocatalysis and ozone. Tappi J 2001;
removal from pulp wastewater using activated petroleum coke. 84(6):63.
Water Res 2001;35(3):745 – 9. Trotter PC. Biotechnology in the pulp and paper industry: a review-
Sheela V, Distidar MG. Treatment of black liquor wastes from small vol. (II). Tappi J 1990a;73(5):201 – 5.
paper mills. Indian J Environ Prot 1989;9(9):661 – 6. Trotter PC. Biotechnology in the pulp and paper industry: a review-
Shere SM, Daly PG. High rate biological treatment of TMP efflu- vol (I). Tappi J 1990b;73(4):198 – 204.
ent. Pulp Pap Can 1982;83n:61 – 6. US EPA. EPA office of compliance sector notebook project: profile
Sinclair WF. Controlling pollution from Canadian pulp and paper of pulp and paper industry. Washington, DC 20460, USA: EPA/
manufactures: a federal perspective. Ottawa: Canadian Govern- 310-R-95-015; 1995.
ment Publishing Centre; 1990. US EPA. Permit guidance document: pulp, paper and paperboard
Singh RS, Marwaha S.S, Khanna PK. Characteristics of pulp and manufacturing point source category. EPA-821-B-00-003; 2000.
paper mill effluents. J Ind Pollut Control 1996;12(2):163 – 72. Vass KK, Mukopadhyay MK, Mistra K, Joshi HC. Respiratory
Skipperud L, Salbu B, Hagebo E. Speciation of trace elements in stresses in fishes exposed to paper and pulp wastewater. Environ
discharges from the pulp industry. Sci Total Environ 1998; Ecol 1996;14(4):895 – 7.
217:251 – 6. Verenich S, Kallas J. Coagulation as a post-treatment for wet oxi-
Smook GA. Handbook for pulp and paper technologist. Vancouver, dation of pulp and paper mill circulation waters. Chem Eng
Bellingham: Angus Wilde Publications; 1992. Technol 2001;24(11):1183 – 8.
Springer AM. Industrial environmental control: pulp and paper Verenich S, Laari A, Kallas J. Wet oxidation of concentrated waste-
industry. Atlanta, Georgia: TAPPI Press; 2000. water of paper mills for water cycle closing. Waste Manage
Srinivasan D, Unwin JP. Pulp and paper effluent management. (N.Y.) 2000;20(4):287 – 93.
Water Environ Res 1995;67(4):531. Verenich S, Laari A, Kallas J. Combination of coagulation and
Srivastava SK, Bembi R, Singh AK, Sharma A. Physicochemical catalytic wet oxidation for the treatment of pulp and paper mill
studies on the characteristics and disposal problems of small and effluents. Water Sci Technol 2001;44(5):145 – 52.
large pulp and paper mill effluents. Indian J Environ Prot 1990; Vlyssides AG, Economides DG. Characterization of wastes from a
10(6):438 – 42. newspaper wash deinking process. Fresenius Environ Bull 1997;
Stepanova L, Lindstrom-Seppa P, Hanninen OOP, Kotelevtsev SV, 6:734 – 9.
Glaser VM, Novikow CN, et al. Lake Baikal: biomonitoring of Wagner M, Nicell JA. Treatment of a foul condensate from kraft
pulp and paper mill wastewater. Aquat Ecosyst Health Manag pulping with horseradish peroxidase and hydrogen peroxide.
2000;3:259 – 69. Water Sci Technol 2001;35(2):485 – 95.
Stuthridge TR, Mcfarlane PN. Adsorbable organic halide removal Wang I-C, Pan T-T. Interference of some papermaking chemical
mechanisms in a pulp and paper mill aerated lagoon treatment additives in the coagulation of wastewater. Taiwan J For Sci
system. Water Sci Technol 1994;29(5 – 6):195 – 208. 1999;14(4):367 – 84.
Stuthridge TR, Campin DN, Langdon AG, Mackie KL, Mcfarlange Wang X, Mize TH, Saunders FM, Baker SA. Biotreatability test of
PN, Wikins AL. Treatability of bleached kraft pulp and paper bleach wastewaters from pulp and paper mills. Water Sci Tech-
mill wastewaters in a New Zealand aerated lagoon treatment nol 1997;35(2 – 3):101 – 8.
system. Water Sci Technol 1991;24(3/4):309 – 17. Wayland M, Trudeau S, Marchant T, Parker D, Hobson KA. The
58 D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 37–58

effect of pulp and paper mill effluent on an insectivorous bird, Zaidi A, Buisson H, Sourirajan S, Wood H. Ultra-and nano-filtra-
the tree Swallow. Ecotoxicology 1998;7:237 – 51. tion in advanced effluent treatment schemes for pollution con-
Webb LJ. Integrated pollution control of emissions from the pulp trol in the pulp and paper industry. Water Sci Technol 1992;
and paper industry. Water Sci Technol 1994;29(5 – 6):123 – 30. 25(10):263 – 76.
Welander T, Lofqvist A, Selmer A. Upgrading aerated lagoons Zamora PP, Esposito E, Pelegrini R, Groto R, Duran N. Effluent
at pulp and paper mills. Water Sci Technol 1997;35(2 – 3): treatment of pulp and paper, and textile industries using
117 – 22. immobilised horseradish peroxidase. Environ Technol 1998;
Welander T, Ericsson T, Gunnarsson L, Storlie A. Reduction sludge 19:55 – 63.
production in biological effluent treatment by applying the LSP Zhang X, Stebbing D, Soong J, Saddler JN. The Removal of det-
process. Tappi International Environmental Conference and Ex- rimental dissolved and colloidal substances by a combined fun-
hibit, vol. 2. 2000. p. 757 – 63. gal and enzyme treatment system. 86th Annual Meeting,
Wenta B, Hartmen B. Dissolved air flotation system improves Montreal, Quebec, Canada; Pulp and Paper Technical Associa-
wastewater treatment at Glatfelter. Pulp Pap 2002;76(3):43 – 7. tion of Canada; 2000a. p. B99 – B102.
Yamamoto S. Ozone treatment of bleached kraft pulp and waste Zhang X, Stebbing DW, Saddler JN. Enzyme treatment of the dis-
paper. Japan Tappi J 2001;55(4):90 – 7. solved and colloidal substances present in mill white water and
Yeber MC, Rodriquez J, Freer J, Baeza J, Duran N, Mansilla HD. the effects of the resulting paper properties. J Wood Chem
Advanced oxidation of a pulp mill bleaching wastewater. Che- Technol 2000b;20(3):321 – 35.
mosphere 1999;39(10):1679 – 88. Zhou H, Smith DW. Process parameter development for ozonation
Yen NT, Oanh NTK, Reutergard LB, Wise DL, Lan LTT. An inte- of kraft pulp mill effluents. Water Sci Technol 1997;35(2 – 3):
grated waste survey and environmental effects of COGIDO, a 251 – 9.
bleached pulp and paper mill in Vietnam on the receiving water
body. Global Environ Biotechnol 1996;66:349 – 64.