Science of the Total Environment 333 (2004) 37 58 www.elsevier.

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Treatment of pulp and paper mill wastewatera 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 The rapid increase in population and the increased demand for industrial establishments to meet human requirements have created problems such as overexploitation of available resources, leading to pollution of the land, air and water environments. The pulp and paper industry is one of the most important industries of the North American economy and ranks as the fifth largest in the U.S. economy (Nemerow and Dasgupta, 1991). In Canada, the pulp and paper industry accounts for a major portion of the countrys economy in terms of value of production and total wages paid (Sinclair, 1990). The wood pulping and production of the paper products generate a considerable amount of
* Corresponding author. Tel.: +1-306-5854094; fax: +1-3065854855. E-mail address: t.viraraghavan@uregina.ca (T. Viraraghavan). 0048-9697/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.scitotenv.2004.05.017

pollutants characterized by biochemical oxygen demand (BOD), chemical oxygen demand (COD), suspended solids (SS), toxicity, and color when untreated or poorly treated effluents are discharged to receiving waters. The high water usage, between 20,000 and 60,000 gallons per ton of product, (Nemerow and Dasgupta, 1991) results in large amounts of wastewater generation. The pulp and paper industry is considered as the third largest polluter in the United States (US). It has been estimated that the pulp and paper industry is responsible for 50% of all wastes dumped into Canadas waters (Sinclair, 1990). The effluents from the industry cause slime growth, thermal impacts, scum formation, color problems, and loss of aesthetic beauty in the environment. They also increase the amount of toxic substances in the water, causing death to the zooplankton and fish, as well as profoundly affecting the terrestrial ecosystem.

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The growing public awareness of the fate of these pollutants and stringent regulations established by the various governmental authorities such as provincial and federal agencies are forcing the industry to treat effluents to the required compliance level before discharging them in to the environment. Many studies have been conducted so far on this sector regarding the impacts as well as the control of the pollutants. Berube and Kahmark (2001), Kahmark and Unwin (1996, 1998, 1999), and Srinivasan and Unwin (1995) have reviewed pollution control aspects of the pulp and paper industry. However, all these reviews have focused on the state of the art in integrated pollution management and lack a comparative evaluation of various treatment processes particular to the water pollution control. This review, therefore, would examine the pollution control systems and compare the performance of the effluent treatment measures in use.

sodium sulfide (NaS2). This process is widely used. (b) Sulfite process: The wood chips are cooked in a mixture of sulfurous acid (H2SO3) and bisulfide ions (HSO3 ) to dissolve lignin. 2.3. Chemo-mechanical pulping (CMP) The raw material is first treated chemically and then subjected to drastic mechanical treatment to separate the fibers. The efficiency of pulp obtained ranges from 85 90% and the strength of the pulp is relatively better than the pulp from the mechanical pulping alone. 2.4. Thermo-mechanical pulping (TMP) This process involves steaming the raw materials under pressure for a short period, prior to and during refining. The thermo-mechanical process is further modified using chemicals during the steaming stage, and the process is called chemi-thermomechanical pulping (CTMP). 2.5. Papermaking The paper making operation consists of two parts; one is stock preparation by treating the pulp to the required degree of fitness and the other is paper making where the treated pulp is passed through continuous moulds/wires to form sheets.

2. Process description Pulping is the initial stage of the paper making industry and provides the processed material. It is the largest source of the pollution in the whole process of papermaking. High amounts of wastewater are generated at different stages of this process. 2.1. Mechanical pulping The yield of the pulp by this process is as high as 90 95% (Smook, 1992) but the quality of the pulp is of low grade, highly colored, and contains short fibers. 2.2. Chemical pulping The wood chips are cooked with appropriate chemicals in an aqueous solution at an elevated temperature and pressure to break chips into a fibrous mass. The yield of the pulp by this process is about 40 50% of the original wood material (Smook, 1992). The chemical pulping is carried out in two media: alkaline and acidic. (a) Kraft process: The woodchips are cooked in a solution of sodium hydroxide (NaOH) and

3. Sources of pollution Each pulping process utilizes large amounts of water, which reappear in the form of an effluent. The most significant sources of pollution among various process stages are wood preparation, pulping, pulp washing, screening, washing, bleaching, and paper machine and coating operations. Among the processes, pulping generates a high-strength wastewater especially by chemical pulping. This wastewater contains wood debris and soluble wood materials. Pulp bleaching generates most toxic substances as it utilizes chlorine for brightening the pulp. Pulp fibers can be prepared from a vast majority of plants in nature such as woods, straws and grasses, bamboos,

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or canes and reeds. Wood is the most abundant source of papermaking fiber. Wood consists of various compounds (lignin, carbohydrate, and extractives) which are hard to biodegrade, and these derivatives are washed away from the fibers during the washing, dewatering, and screening processes. Depending upon the type of the pulping process, various toxic chemicals such as resin acids, unsaturated fatty acids, diterpene alcohols, juvaniones, chlorinated resin acids, and others are generated in the pulp and paper

making process. The pollutants at various stages of the pulping and paper making process are presented in Fig. 1. It is clear that an individual pulping stage generates different quantities, qualities and types of pollutants. The wastewater pollution load from individual pulping and papermaking process is given in Table 1. The amount of pollutants produced by an individual mill is an important indicator to evaluate the

Fig. 1. Pollutants from various sources of pulping and papermaking (US EPA, 1995).

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D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 Table 3 Comparison of actual emissions from pulp mills (TAPPI, 1990) Country Parameters SS BOD COD AOX N P (kg/adt) (kg/adt) (kg/adt) (kg/adt) (kg/adt) (kg/adt) Bleach kraft USA 5 Sweden 3.8 Bleached sulfite Sweden 6.8 5 12 68 2.2 2 0.23 0.09

Table 1 Typical wastewater generation and pollution load from pulp and paper industry (Rintala and Puhakka, 1994) Process Wastewater (m3/adt pulp or paper) 5 25 10 15 10 30 10 30 10 15 10 15 20 80 80 100 150 180 40 60 40 60 60 90 10 50 200 250 SS (kg/adt pulp) nr nr 10 40 10 40 20 50 20 50 3 10 20 50 20 60 10 40 10 20 10 40 nr 50 100 COD (kg/adt pulp) 5 20 15 32 40 60 50 120 70 120 100 180 30 120 nr 120 180 60 120 40 60 100 140 nr 1000 1100

Wet debarking Groundwood pulping TMP -unbleached TMP-bleached CTMP-unbleached CTMP-bleached NSSC Ca-sulfite (unbleached) Ca-sulfite (bleached) Mg-sulfite (unbleached) Kraft-unbleached Kraft-bleached Paper making Agrobased small paper mill

17.8

145

1.8

0.3

0.10

Sweden for selected process are presented in Table 3. The pollutant load discharge guidelines for the pulp and paper industry of some countries are presented in Table 4.

nrnot reported; adtair dry ton; NSSCneutral sulfite semichemicals.

4. Wastewater characteristics The characteristics of the wastewater generated from various processes of the pulp and paper industry depend upon the type of process, type of the wood materials, process technology applied, management practices, internal recirculation of the effluent for recovery, and the amount of water to be used in the particular process. As an example, Mohamed et al. (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 wood kraft mill. The general characteristics of the

performance of the system as well as a crosscheck whether the mills have followed the guidelines. Table 2 provides performance data of selected processes and mills. The environmental guidelines on discharge vary with countries. The emission data from USA and

Table 2 Typical pollution load per ton of production (kg/ton) Process Pollutants SS Deinking BOD 11 COD 54 Color Reference

Vlyssides and Economides (1997) Wood yard 3.75 1 2 Springer (2000) Pulping 13.5 5 1.5 Springer (2000) Bleaching 6 15.5 40 Springer (2000) Papermaking 30.8 10.8 1.5 Springer (2000) Riocell 0.4 0.5 0.2 0.3 5 5.5 19 20a Foelkel (1989) (Brazil) Large mill 31.2 13 82.4 Srivastava et al. (India) (1990) Small mill 140.3 152.26 639.4 Srivastava et al. (India) (1990) Sweden 0.7 0.2 7.6 Carlson et al. (2000)
a

Table 4 Discharge limits (monthly, semiannual, or annual verges) for bleached kraft pulp Country Parameters SS (kg/adt) Canada Finland Norway Sweden Belgium France USA 9.5 14.5 5 15 5 0.3 5.8 7 14.4 6.5 10 3.86 (8.47) BOD COD (kg/adt) (kg/adt) 5.5 30 6.8 34 7.5 17 2.3 5.4 3.3 30 2.41 (4.52) 90 90 39 107 22 63 48 95 Reserved AOX Reference (kg/adt) 1.4 1.5 1.4 6 1.5 2 1.5 0.272 (0.476) TAPPI, 1990 TAPPI, 1990 TAPPI, 1990 TAPPI, 1990 TAPPI, 1990 TAPPI, 1990 US EPA, 2000

Pt Co (kg/ton).

The U.S. EPA values are monthly average values for new bleached kraft mill. The values in the ( ) are daily maximum allowable.

D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 Table 5 Typical characteristics of wastewater (mg/l) at different processes (Bajpai, 2000) Process Parameters pH TMP (1) TMP (2) CTMP Kraft bleaching Kraft foul (1) Kraft foul (2) Kraft foul (3) Sulfite condensate (1) Sulfite condensate (2) NSSC Pulping: Spent liquor Chip wash Paper mill 4.2 10.1 8.0 10.2 9.5 10.5 2.5 2.8 5.9 SS 383 810 500 37 74 16 0 0 BOD5 2800 2800 3000 4000 128 184 568 10,700 5500 8500 2000 4000 COD Carbohydrate Acetic Methanol acid 235 1500 0 25 40 76 421 7500 8500 250 N 12 306 350 600 P 2.3 S

41

7210 2700 5600 1230 6000 9000 1000 1124 1738 1202 16,000 10,000 13,000 4000 8000

72 167 5.9 1 91 0.02 1.55 120 375 800 850 840 1270

3700 5110 9800 27,100

253 6095 800

13,300 12,000 1600

39,800 20,600 5020

6210 3210 610

3200 820 54

90 70 9

55 86 11

10 36 0.6

868 315 97

wastewater produced at various process stages and pollution sources are given in Tables 5, 6 and 7.

5. Fate and effects on the environment The pollutants discharged from the pulp and paper industry affect all aspects of the environment such as water, air and land. Makris and Banerjee (2002) studied the fate of the resin acid in the secondary treatment system. Various authors at different times reported the appearance of toxic effects on various fish species due to exposure of pulp and paper mill effluents. Many authors reported the presence of toxic pollutants in fish or toxic effects on fish such as respiratory stress, mixed function oxygenase activity, toxicity and mutagenicity, liver damage, or genotoxic effects, and lethal effects on the fishes exposed to pulp
Table 6 Characteristics of wastewater (mg/l) at various pulp and paper processes Process Parameters TS Wood preparation Drum debarking Bleach kraft mill Newsprint mill 1160 2017 3171 3750 SS 600 34 250 BOD5 250 480 987 23

and paper mill wastewaters (Owens et al., 1994; Vass et al., 1996; Schnell et al., 2000b; Lindstrom-Seppa et al., 1998; Leppanen and Oikari, 1999; Johnsen et al., 1998; Erisction and Larsson, 2000). Baruah (1997) reported on serious concerns related to the surface plankton population change in Elengabeels wetland ecosystem in India due to untreated paper mill effluent discharge into the system. Yen et al. (1996) reported on the possibility of the sub-lethal effects to the aquatic organisms in the Dong Nai River in Vietnam due to the effluents discharged from a pulp and paper mill. However, there are also some contradictory reports by other authors. Kovacs et al. (2002) reported no significant evidence of depressed plasma steroids nor increase in mixed function oxygenase (MFO) activity in fish associated with pulp mill effluent. Dsurney et al. (2002) and Felder et al. (1998) indicated no significant adverse effect in sediments, and river biota

References COD 3500 AOX 12.5 Resin (Ag/l) Color (Pt Co) 20 50 1000 Nemerow and Dasgupta (1991) Springer (2000) Wayland et al. (1998) Tardif and Hall (1997)

69 16

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Table 7 Characteristics of wastewater at various pulp and paper processes Process Parameters pH Large mills (India) Small mills (India) Digester house Combined effluent TMP whitewater TMP whitewater Kraft mill Pulping Kraft mill (unbleached) Bleached pulp mill Bleaching Pulp and paper News air and land paper deinking Paper making Paper mill Paper machine Paper machine
a

References SS (mg/l) 1233 4890 23,319 2023 91 105 3620 256 150 1133 216 1400 400 760 935 503 1032 BOD5 (mg/l) 983 2628 13,088 103 1090 1125 360 175 1566 140 1050 16 561 425 170 240 COD (mg/l) 2530 6145 38,588 675 2440 2475 4112 2572 4870 78 953 845 723 Color (Pt Co) black DB 16.6a 1.0a 4667.5 250 4033 DB Black DB 243 Srivastava et al. (1990) Srivastava et al. (1990) Singh et al. (1996) Singh et al. (1996) Jahren et al. (1999) Jahren et al. (2002) Rohella et al. (2001) Dilek and Gokcay (1994) Nemerow and Dasgupta (1991) Yen et al. (1996) Dilek and Gokcay (1994) Mandal and Bandana (1996) Vlyssides and Economides (1997) Gupta (1997) Dutta (1999) Yen et al. (1996) Dilek and Gokcay (1994)

TS (mg/l) 5250 15,120 51,589 3318 8260 1810 1200 2285 4200 450 1844 2415

11.0 12.3 11.6 7.6 4.7 4.7 8.2 10 8.2 7.5 2.5 7.8 8.3 7.8 8.7 4.5 8.3

Unit [Optical Density (O.D) at 465 nm]; DB means dark brown; LY means light yellow.

or on fish attributable to the treated mill effluent. Stepanova et al. (2000) reported no clear evidence of mutagens in most of aquatic animals studied in Lake Baikal due to Baikalsk pulp and paper mill wastewater discharged to the lake. Wayland et al. (1998) reported no effect on the tree shallow, which feed on the insects downstream of the pulp mill. Howe and Michael (1998) studied the effects of the treated pulp mill effluent on irrigated soil in northern Arizona, which showed serious soil chemistry change. Dutta (1999) investigated the toxic effect of the paper mill effluent (treated) applied to a paddy field in Assam, India. Gupta (1997) and Singh et al. (1996) reported high loads of organic pollutants derived from the paper mill wastewater in Tamilnadu, and Punjab, India, respectively. Singh et al. indicated high level of coliform bacteria in the effluent too. However, Archibald (2000) indicated that the presence of coliform bacteria in the pulp and paper effluent did not necessarily mean a health hazard to the environment unless pathogens were observed. Skipperud et al. (1998) and Holmbom et al. (1994) reported the presence of various trace metals in the pulp and paper mill effluents at low levels. King et al. (1999) reported elevated levels of Mn accumulation in the Crayfish exposed to the paper mill

wastewater. Mandal and Bandana (1996) reported on health impacts such as diarrhea, vomiting, headaches, nausea, and eye irritation on children and workers due to the pulp and paper mill wastewater discharged to the environment. High carbon dioxide level in the pulp and paper mill effluents as a potential source of distress and toxicity to rainbow trout was reported by Oconnor et al. (2000).

6. Wastewater treatment Pollution from the pulp and paper industry can be minimized by various internal process changes and management measures such as the Best Available Technology (BAT). Dube et al. (2000) reported a 60% reduction in effluent BOD due to an internal process change in Irving Pulp and Paper Limited, Canada. The estimated data by Springer (2000) showed that the water use in the US in 1959 was about 250 m3/adt whereas water use in 1995 was reduced to 50 m3/adt. However, the average water use for the pulp and paper mills in India was still 200 259 m3/ton of paper production (Gune, 2000). Several authors have suggested internal process change as a measure to

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control pollution (Reilama and Ilomaki, 1999; Webb, 1994; Dey et al., 1991). Raghuveer and Sastry (1990) reported BOD, COD, and color reduction by internal management measures. However, the treatment of the wastewater by various external processes is essential. Since pulp and paper industry discharges varieties of pollutants, the treatment methods also vary. 6.1. Physicochemical treatment Physicochemical treatment processes include removal of suspended solids, colloidal particles, floating matters, colors, and toxic compounds by either sedimentation, flotation, screening, adsorption, coagulation, oxidation, ozonation, electrolysis, reverse osmosis, ultra-filtration, and nano-filtration technologies. 6.1.1. Sedimentation/flotation Suspended matters present in the pulp and paper wastewater are comprised primarily of bark particles, fiber, fiber debris, filler and coating materials. Thompson et al. (2001) stated that sedimentation was the preferred option within the paper mills in the UK, and contributed to more than 80% removal of the suspended solids on an average. Rajvaidya and Markandey (1998) stated that the design value of the primary clarifier was 70 80% in average. Azevedo et al. (1999) reported on the effect of pH on pulp settalability. Gubelt et al. (2000) reported 65 95% removal of TSS by dissolved air flotation and it was an unstable unit. However, Wenta and Hartmen (2002) mentioned that dissolved air flotation was able to remove 95% of the TSS. 6.1.2. Coagulation and precipitation Coagulation and flocculation is normally employed in the tertiary treatment in the case of pulp and paper mill wastewater treatment and not commonly adopted in the primary treatment. Tong et al. (1999) and Ganjidoust et al. (1997) carried out a comparative study of horseradish peroxide (chitosan) and other coagulants such as (Al2(SO4)3), hexamethylene diamine epichlorohydrin polycondensate (HE), polyethyleneimine (PEI), to remove adsorbable organic halides (AOX), total organic carbon (TOC), and color. The authors indicated that modified chitosan was far more effective in removing these pollutants than other coagulants. Wagner and Nicell (2001) investigated the

treatment of foul condensate, defined by phenolic compounds, and toxicity using microtox assay from kraft pulping by horseradish peroxide and H2O2 and found a total phenol reduction below 1 mg/l and toxicity (microtox assay) reduction by 46%. Dilek and Gokcay (1994) reported 96% removal of COD from the paper machine, 50% from the pulping, and 20% for bleaching effluents by using alum as a coagulant. Rohella et al. (2001) stated polyelectrolytes were better than the conventional coagulant alum to remove turbidity, COD, and color. Sheela and Distidar (1989) reported on black liquor treatment by precipitation with CaSO42H2O in the presence of CO2. The removal of dissolved solids was reported to be 63%. However, Wang and Pan (1999) reported that the use of coagulants such as polyethylene oxide (PEO), worsened the settlability and increased COD levels, turbidity, and suspended solids of the treated effluent when the dose was between 25 and 250 ppm. Chernoberezhskii et al. (1994) reported that coagulation with aluminum sulfate or modified adsorbents was the best option for color removal from the sulfate and sulfite wood pulp and paper industry. 6.1.3. Adsorption Murthy et al. (1991) reported a high removal of color by activated charcoal, fullers earth, and coal ash. Shawwa et al. (2001) reported 90% removal of color, COD, DOC, and AOX from bleached wastewater by the adsorption process, using activated coke as an adsorbent. Sullivan (1986) concluded that the wastewater produced by the Union Camp Facility at Franklin, VA, can be treated by activated carbon and ion exchange to reduce color and chloride to levels acceptable for reuse. Das and Patnaik (2000) investigated the lignin removal efficiency of the blast furnace dust (BFD) and slag by the adsorption mechanism. Their study showed 80.4% and 61% removal of lignin by BFD and slag, respectively. Narbaitz et al. (1997) reported that PACTk process was an effective process to remove AOX from the kraft mill effluent to meet Ontarios year 2000 regulation (AOX: 0.8 kg Cl/adt of production). 6.1.4. Chemical oxidation Balcioglu and Ferhan (1999) reported on photocatalytic oxidation of kraft pulp bleaching wastewater showing that the removal largely depended on the

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concentration of COD and chloride below a certain level. Zamora et al. (1998) reported on the use of horseradish peroxide to decolorize kraft effluent by 50% within three hours of reaction time. The degradation of phenolic and polyphenolic compounds present in the bleaching effluent was studied using advanced oxidation systems such as photocatalysis with O2/ZnO/UV, O2/TiO2/UV, O3 and O3/UV. The authors concluded that O2/ZnO/UV and O2/TiO2/UV were the best systems to oxidize the effluent in a short period of time. Perez et al. (2002c) reported that the combination of Fenton and photo-fenton reactions proved to be highly effective for the treatment of bleaching kraft mill effluent. Verenich et al. (2000) reported on the improvement in biodegradability of an effluent from 30% to 70% by wet oxidation method. Hassan and Hawkyard (2002) studied the removal of color by combined oxidation with ozone and Fentons reagent and stated that 100% color removal was achieved at a pH of 4 5 in the case of ferral (derived from natural clay sources, which contains 2% ferric sulfate and 6% aluminum sulfate) and ferric sulfate. Dufresne et al. (2000) reported on the oxidation of total reduced sulfur (TRS) giving odor free products by catalytically enhanced oxidation. 6.1.5. Membrane filtration Jonsson et al. (1996) reported on the treatment of paper coating color effluent treatment by membrane filtration suggesting that the composition of the color had a significant influence on the performance. Membrane separation techniques were reported to be suitable for removing AOX, COD, and color from pulp and paper mills (Zaidi et al., 1992; Afonso and Pinho, 1991, Falth, 2000). De Pinho et al. (2000) compared the efficiency of (1) ultrafiltration and (2) ultrafiltration plus dissolved air flotation. The results showed 54%, 88%, 100% removal of TOC, color, and SS, respectively by ultrafiltration alone. Ultrafiltration plus dissolved air flotation resulted in 65%, 90% and 100% removal of TOC, color, and SS, respectively. Dube et al. (2000) reported that 88% and 89% removal of BOD, and COD, respectively was achieved by reverse osmosis (RO). Merrill et al. (2001) stated that membrane filtration (MF), and granular membrane filtration (GMF) were suitable for removing heavy metals from the pulp and paper mill wastewaters.

6.1.6. Ozonation Yeber et al. (1999) reported that a substantial removal of COD, TOC, and toxicity from pulp mill effluent and increased biodegradability of the effluent were achieved after treatment with ozone. Korhonen et al. (2000) reported a 90% removal of ethylenediaminetetraacetic acid (EDTA) and a 65% removal of COD by ozone treatment of the pulp mill effluent. Hinck et al. (1997) reported that neither EDTA nor diethylene triamine pentaacetic acid (DTPA) are biodegraded in aerobic conditions. Oeller et al. (1997) reported high removal of COD and DOC from the pulp effluent by ozone treatment. Freire et al. (2000) reported a 12% reduction of total organic carbon, total phenols reduced to 70%, and effluent colors to 35% of bleached pulp mill effluent after 60 min of ozonation. Several authors reported on toxic compounds, COD, and color removal by ozone treatment (Hostachy et al., 1997; Zhou and Smith, 1997; Yamamoto, 2001). Roy-Arcand and Archibald (1996) reported that biotreated kraft effluents yielded a substantial decrease in the biologically recalcitrant residual adsorbable organic halogens (AOX), converted COD to BOD and yielded large decrease in color. Laari et al. (2000) investigated the removal of lipophilic wood extractives from TMP wastewater by ozonation. The authors indicated that a high dosage of ozone (100 300 mg/ dm3) was required to remove 50% of lippphilic wood extractives. Korhonen and Tuhkanen (2000) reported that ozone doses of 0.2 mgO3/initial mgCOD eliminated over 90% resin acid. Torrades et al. (2001) reported high removals of TOC, COD, AOX, and color from bleached kraft mill effluent (BKME1) using heterogeneous photocatalysis and ozone treatment. Sevimli and Sarikaya (2002) reported a 95 97% color removal for high doses of ozone in 15 min of ozonation. Kallas and Munter (1994) suggested post treatment of bleached mill effluent by ozonation and adsorption. 6.2. Biological treatment 6.2.1. Aerobic treatment 6.2.1.1. Activated sludge process. The performance variation of the activated sludge due to the changes in pH, temperature, and H2O2 and DTPA was reported by Ginkel et al. (1999), Norris et al. (2000), and

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Larisch and Duff (1997, 2000), respectively. Knudsen et al. (1994) reported a high reduction of BOD and soluble COD by a two-stage activated sludge process. Shere and Daly (1982) claimed that TMP wastewater was readily degradable by the activated sludge process. Hansen et al. (1999) suggested upgrading the activated sludge plant by the addition of Floobeds (floating biological bed) in series that increased COD and BOD removal from 51% to 90% and 70% to 93%, respectively. Chandra (2001) reported efficient removal of color, BOD, COD, phenolics, and sulfide by microorganisms such as Pseudomonas putida, Citrobacter sp., and Enterobacter sp. in the activated sludge process. Mohamed et al. (1989) reported removal of chlorinated phenols, 1,1-dichlorodimethyl sulfone (DDS), and chlorinated acetic acids in an oxygen activated sludge effluent treatment plant. Demirbas et al. (1999) reported AOX removal by the activated sludge process. Junna and Ruonala (1991) reported 90% BOD7, 70% COD, 40 60% AOX, and 60 95% chlorinated phenols removal by the activated sludge process. Bryant et al. (1992) reported AOX removal of 46% on average from two activated sludge systems studied. Andreasan et al. (1999) suggested the addition of an anoxic selector before the activated sludge plant to improve the sludge settlability problem. Raghuveer and Sastry (1991) reported that a minimum of mixed liquor suspended solids (MLSS) of 2000 2500 mg/l and an aeration time of 6 8 h were required to remove 83 88% of BOD. High removals of BOD, COD, AOX, and chlorinated phenolics have been achieved in the activated sludge process (Saunamaki, 1997; Schnell et al., 2000a). Kennedy et al. (2000) reported that the activated sludge was successful in removing nearly all detectable Microtox k toxicity from bleached kraft pulp mills at low level whereas the PACTk was slightly better in removing highly toxic concentrated effluents. 6.2.1.2. Aerated lagoons. Stuthridge and Mcfarlane (1994) stated that 70% removal of the AOX from the aerated lagoon was attributed to a short residence time section of the treatment system where the chlorinated stage effluents were mixed with general mill wastewaters. The effect of simple mixing was reported to be responsible for 15 46% removal. Bryant et al. (1997) reported 67% removal of am-

monia from black liquor spill at temperatures of 22 35 jC, pH near 7.3 in an aerated lagoon. Chernysh et al. (1992) reported large variations in AOX and TOC removal in a controlled batch study of bleached kraft effluent in an operating lagoon under both aerobic and anaerobic conditions. Welander et al. (1997) reported COD removal of 30 40% in a fullscale lagoon and 60 70% in a pilot-scale plant. Stuthridge et al. (1991) reported 65% removal of AOX from bleached kraft pulp and paper mill effluent. Junna and Ruonala (1991) reported removal of BOD7 ranging between 50% and 75% and chlorinated phenolics 10 50% by an aerated lagoon. Achoka (2002) reported that an oxidation pond removed chemical compounds greater than 50%. Schnell et al. (2000a) reported removals of BOD, AOX, chlorinated phenolics, and polychlorinated phenolics respectively from an aerated lagoon. 6.2.1.3. Aerobic biological reactors. Many authors have reported high removals of organic pollutants of kraft mill wastewater by sequencing batch reactor (SBR) treatment (Franta et al., 1994; Franta and Wilderer, 1997; Milet and Duff, 1998). Reid and Simon (2000) reported 100% removal of methanol and 90% removal of CODsol by SBR. Substantial removal of COD, TOC, BOD (Magnus et al., 2000a), lignin and resin acids (Magnus et al., 2000b) of TMP wastewater using high rate compact reactors (HCRs) at a retention time of 1.5 h had been reported. Removal of COD by a moving bed bifilm reactor (MBBR) had been demonstrated (Jahren et al., 2002; Borch-Due et al., 1997). Magnus et al. (2000c) reported 93% and 65% removal of BOD and COD, respectively by a biological compact reactor. Berube and Hall (2000) showed that approximately 93% removal of TOC could be achieved by a membrane bioreactor. Asselin et al. (2000) concluded that suspended carrier biofilm reactor (SCBR) was highly efficient in removing chronic toxicity from the effluent. Rovel et al. (1994) achieved 76%, 62%, 81%, and 48% removal of BOD, COD, SS, and AOX, respectively, using a biofilter. Rudolfs and Amberg (1953) demonstrated that aerobic treatment of whitewater (high strength) was able to achieve 70 80% removal of BOD. Typical efficiencies of aerobic systems are presented in Table 8.

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Table 8 Typical efficiencies of aerobic systems (Springer, 2000; *Kantardjieff and Jones, 1997) System Aerobic biofilters (sulfite mill)* Aerobic biofilters (TMP)* Aerobic stabiliztion basin Activated sludge Aeration time (day) 5 10 38 h Organic loading (lb BOD/1000 ft3) 3.4 kg/m3/day 50 50 Efficiency (%) 74 92 74 90 80 90 80 85

6.2.2. Anaerobic treatment An anaerobic process is considered more suitable to treat high strength organic effluents. Before 1980s, the treatment of pulp mill effluents by anaerobic means was limited, as most of the pulp mill effluents at that time were less concentrated (300 2000 mg/ l BOD) (Bajpai, 2000) and were not suitable for anaerobic treatment. Anaerobic filter, upflow sludge blanket (UASB), fluidized bed, anaerobic lagoon, and anaerobic contact reactors are anaerobic processes, that are commonly used to treat pulp and paper mill effluents. Pretreatment of the kraft mill black liquor was investigated by Poggi-Varaldo et al. (1996) and they reported that continuous anaerobic treatment of wastewater contaminated with black liquor was feasible at low to medium loading rates, with a total COD removal of 48 80% and biodegradable COD reduction of 87 96%. Jahren et al. (1999) compared anaerobic and aerobic treatment for TMP mill effluent and found that 84% and 86% removal of COD from anaerobic and aerobic treatment systems, respectively, was achieved. Rajeshwari et al. (2000) reported that chlorine bleaching effluents were not suitable for anaerobic treatment due to their low biodegradability and presence of toxic substances that affects methanogens. Sandquist and Sandstrom (2000) developed a new treatment technology [the process consists of three steps: (1) stripping of sulfides and other volatile components from condensate; (2) regenerative thermal oxidation of stripper off gases; (3) adsorption of sulfur oxide] to treat foul condensate (sulfide) from the black liquor. Removal efficiency for foul condensate was reported to be more than 99% at a pH of 4 and removal of methanol was 90% at a low liquid/gas ratio. Jackson-Moss et al. (1992) found 50% removal of COD and color by anaerobic biological granular

activated carbon. Dufresne et al. (2001) observed that undiluted foul condensates at Windsor mill were toxic to anaerobic biomass. Chen and Horan (1998) stated that COD, and sulfate removals of 66% and 73%, respectively, were obtained using a UASB reactor with a hydraulic retention time of 6 h. Peerbhoi (2000) investigated anaerobic treatability of black liquor by a UASB reactor in her study at the University of Roorkee, India. The author concluded that anaerobic biological treatment of black liquor was not feasible, as the pollutants were not readily degradable. Perez et al. (1998) evaluated two anaerobic systems (anaerobic filters and fluidized bed) in laboratory-scale reactors and reported that 81.5% organic removal efficiency was obtained in the case of fluidized bed with porous packing and 50% removal was obtained in the case of anaerobic filters on corrugated plastic tubes. Rajeswori et al. (2000) reported a 50% reduction of BOD of debarking wastewater by a fluidized bed reactor. Thompson et al. (2001) reported that COD removal efficiency of 80% was constantly achievable but the residual COD was around 800 mg/ l meaning that additional treatment was essential. Schnell et al. (1992) concluded that anaerobic treatment systems were less suitable for treatment of sulfite-spent liquor compared to an aerobic system. The anaerobic treatability of different processes are given in Table 9. 6.3. Fungal treatment Taseli and Gokcay (1999) isolated fungal specie (Pencillium sp.) which was able to remove 50% of the AOX, and color from the soft-wood bleachery effluents in a contact time of 2 days. Several authors reported on the capacity of different fungal species to remove color from kraft mill effluent (Gokcay and Dilek, 1994; Duran et al., 1994; Sakurai et al., 2001). Prasad and Gupta (1997) reported on a substantial reduction of color and COD by the use of white rot fungi T. versicolor and P. chrysosporium. Saxena and Gupta (1998) showed that white-rot fungi P. chrysosporium in combination with other white-rot fungi (P. sanguineus, P. ostreatus and H. annosum) and with the use of the surfactants were able to remove color, COD, and lignin content. Choudhury et al. (1998) found that lignin, BOD, COD and color removal were achieved to the extent of 77%, 76.8%, 60%, and 80%,

D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 Table 9 Anaerobic degradability of pulp and paper mill effluent (Rintala and Puhakka, 1994) Wastewater from Wet debarking Thermomechanical pulping Chemothermomechanical pulping NSSC-spent liquor NSSC-condensate Kraft condensate Spent condensate Chlorine bleaching Sulfite spent liquor COD (mg/l) 1300 4100 1000 5600 2500 13,000 40,000 7000 1000 33,600 7500 50,000 900 2000 120,000 220,000 Anaerobic degrad. (%) 44 78 60 87 40 60 nr nr 83 92 50 90 30 50 nr Inhibitors Resin acids Resin acids

47

Resin acids, fatty acids, sulfur, DTPA Tannins Sulfur, ammonia Sulfur, resin acids, fatty acids, terpenes Sulfur, organic sulfur Chlorinated phenols, resin acids nr

respectively, by the fungal specie Pleurotus ostreatus. Zhang et al. (2000a) examined the removal of most of the detrimental organics from whitewater by combined enzyme and fungal treatment. The removal of lignin was >90% whereas resin and fatty acids were reduced by 20%. Zhang et al. (2000b) showed that fungus such as T. versicolor and fungal culture filtrate (FCF) obtained from these organisms were able to efficiently degrade the dissolved and colloidal substances. Mendonca et al. (2002) suggested fungal pretreatment of P. taeda wood chips by C. subvermispora. The performance of fungal treatment is summarized in Table 10. 6.4. Integrated treatment processes An integrated or hybrid system is designed to take advantage of unique features of two or more processes. A combination of coagulation and wet oxidation removed 51% of COD (Verenich et al., 2001); and
Table 10 Performance of fungal treatment Treatment process Parameters COD Influent (mg/l) White White White White rot fungi rot + surfactants rot (T. versicolor) rot (P. chrysosporium) 39,012 39,012 % Removal 40.74 75.35 77.7 79.4 Lignin Influent (mg/l) 2870 2870

83% of color and 75% of lignin (Verenich and Kallas, 2001). A combination of ozone and biofilm reactor removed 80% COD (Helble et al., 1999). A combination of chemical oxidation with ozone removed 90% of wood extractives and 50% of the COD from TMP wastewater at 150 jC (Laari et al., 1999). Athanasopoulos (2001) suggested post treatment methods such as electrolysis or ozonation to reduce + COD, and NH4 N concentration to the permitted level. Nakamura et al. (1997) reported on efficient degradation of lignin using a combined treatment of ozone and activated sludge process. Jokela and Keskitalo (1999) reported that a combination of dissolved air flotation and chemical precipitation removed 93% SS, 50% BOD7, 57% COD, 92% phosphorus, and 52% nitrogen. A combination of activated sludge and with ozonation (as tertiary treatment) removed 87 97% COD, and 97% BOD (Schmidt and Lange, 2000). Kabdash et al. (1996) showed that a combination of

Reference Color % Removal 16.38 65.84 Influent (mg/l) 34,940 34,940 1875 1875 % Removal 34.49 81.29 93.8 83.5 Saxena and Gupta (1998) Saxena and Gupta (1998) Prasad and Gupta (1997) Prasad and Gupta (1997)

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Table 11 Performance of physicochemical treatment processes Treatment process Parameters TSS COD TOC % Influent Removal (mg/l) 55.65 >90 80 AOX Color Lignin/Resin* or Fatty# acid Influent % (mg/l) Removal 480 98.91 Rohella et al. Ganjidoust et Ganjidoust et Ganjidoust et (2001) al. (1997) al. (1997) al. (1997) Reference D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758

Influent % Influent (mg/l) Removal (mg/l) Coagulation: Polyelectrolyte Chitosan PE/PEI Alum Adsorption: Charcoal #1 Coal ash #2 Fuller earth #3 Activated coke #4 Oxidation: (Wet oxidation) (Ozone + Fenton) Ozonation: Ozone + UV Photocat. + ozone Photocat. + ozone Membrane: Ultrafiltrtion Nanofiltration Dissolved air + UF Microfiltration + UF 3620 100 4112 2126 10,000~19,000

% Influent % Influent % Removal (mg/l) Removal (Pt Co) Removal 70 30 40 80.2 >90 4667.5 3.9 mg/l 3.9 mg/l 3.9 mg/l 2300 82.58 90 80 80 98.13 98.5 99.21 >90 ~100

3500~4100 80

Murthy et al. (1991) Murthy et al. (1991) Murthy et al. (1991) Shawwa et al. (2001) Verenich et al. (2000) Hassan and Hawkyard (2002) Oeller et al. (1997) Torrades et al. (2001) Torrades et al. (2001) Zaidi et al. (1992) Zaidi et al. (1992) De Pinho et al. (2000) De Pinho et al. (2000)

397 397

100 100

~550 515 3700

82 85 57.5 85 90

306 1380 828 828

88 38 65 54

27.7 69.8

92.5 50 85 91 93 96

250 7030

100 65 93 98 99.2 99.9 90 88

1747 1747

(#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) 3758 Table 12 Performance of aerobic biological treatment processes Treatment process Parameters TSS BOD COD AOX Chlorinated phenolics % Removal 74 83 96.92 Reference

49

Influent % Influent % Influent % Influent % Influent (mg/l) Removal (mg/l) Removal (mg/l) Removal (mg/l) Removal (mg/l) Activated sludge Paper mill Pulp mill Kraft mill (period 1) (period 2) Pulp and paper mill Paper mill 1435 738 90.6 76.4 512 336 270 270 1000 94.2 93.8* >95* >98 96.63 99 1210 82.4 1192 57.1 660 (F) 60 660 (F) 70 1533a 96.8 85 11.7 22.5 22.5 55 36 40 0.255 0.255

Saunamaki (1997) Saunamaki (1997) Schnell et al. (2000a) Schnell et al. (2000a) Chandra (2001) Knudsen et al. (1994)

Aerobic stabilization basin Kraft mill (period 1) (period 2) Kraft mill (1) (2) (3) (4) (5)

270 270

>95 >98

660 (F) 62 660 (F) 73

22.5 22.5

53 55 17 70

0.255 0.255

85 86

20 65

Schnell et al. (2000a) Schnell et al. (2000a) Chernysh et al. (1992)

F means fraction of COD or soluble COD. Period 1: operating conditions for activated sludge-HRT 2 days, SRT 25 days, Temp. 30 jC, VSS 1800 mg/l. Period 1: operating conditions for aerated stabilization basin-HRT 15 days, SRT 15 days, Temp. 30 jC, VSS 60 mg/l. Period 2: operating conditions for activated sludge-HRT 1 day, SRT 25 days, Temp. 30 jC, VSS 2800 mg/l. 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 in 40 50% additional removal of COD compared to the activated sludge system. Jahren and Oedegaard
Table 13 Performance of biological treatment processes Treatment process Parameters BOD Influent (mg/l) Biological reactors HRC (TMP Mill) Total plant efficiency MBBR (HRT 4.5 hrs) SBR Anaerobic (GAC) Kraft mill Windsor
a

(1999) found that Kaldnes (anaerobic followed by aerobic) moving bed biofilm reactor at 55 jC removed about 60% of soluble COD from TMP

Reference COD % Removal 98 99 65 75 98 69 Influent (mg/l) 3340 5000 1400 2036a % Removal 79 86 85 95 85 93 50 59 Methanol Influent (mg/l) 1095a % Removal 84 Color Influent (mg/l) 1300 % Removal 50 Magnus et al. (2000a) Magnus et al. (2000a) Borch-Due et al. (1997) Franta and Wilderer (1997) Jackson-Moss et al. (1992) Dufresne et al. (2001)

1150 1490 1429a

Unit in g/d.

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whitewater. A combined anaerobic aerobic treatment system was suggested to treat bleached kraft pulp and paper mill effluents (Duncan and Thia, 1992; Wang et al., 1997). Lescot and Jappinen (1994) showed that a combination of an aerated lagoon and a secondary clarifier was able to treat bleached kraft mill effluent in Finland resulting in 87%, 96%, 65%, 53%, and 22% removal of SS, BOD7, COD, AOX, and color, respectively. Carlson et al. (2000) reported that 77%, 98 99%, 72%, and 81% removal of COD, BOD, TN, and TP, respectively, was achieved after upgrading the aerated

basin at Monsteras mill. The system comprised of an anoxic selector, an aerated basin, and a secondary clarifier in series. The removals of extractives, resin and fatty acids were 96% and 98%, respectively, whereas the system reduced Microtoxk by 99%. Welander et al. (2000) reported on the performance of an aerobic biological process called LSP (low sludge production) to lower the biological sludge by 80 90%. The system configuration was primary clarifier, aeration basin, and secondary clarifier. A combination of physicochemical, biological, and effluent polishing in the aerated lagoon removed 98

Table 14 Selected anaerobic process performance (Bajpai, 2000) Mill location Anaerobic contact reactor Hylte Bruk AB, Sweden SAICA, Zaragoza, Spain Hannover paper, Alfred, Germany Niagara of Wisconsin of USA SCA Ostrand, Ostrand, Sweden Alaska Pulp Corporation, Sitka Wastewater source Loading rate (kg COD/m3/d) 2.5 4.8 4.2 2.7 6 3 BOD5 (mg/l) 1300 COD (mg/l) 3500 TSS BOD5 COD (mg/l) Removal% Removal% 520 71 94 97 96 50 85 67 66 85 77 40 49

TMP, groundwood, deink Waste paper alkaline cooked straw Sulfite effluent condensate CTMP CTMP Sulfite condensate, bleach caustic and pulp whitewater

10,000 30,000 3000 2500 3700 6000

4800 3300 7900

3500 10,000

Upflow anaerobic sludge blanket Celtona, Holland Southern paper converter, Australia Davidson, United Kingdom Chimicadel, Friulli, Italy Quesnel River Pulp, Canada Lake Utopia Paper, Canada EnsoGutzeit, Finland McMillan Bloedel, Canada Anaerobic filter: Lanaken, Belgium Anaerobic fluidized bed: D Aubigne, France

Tissue Wastepaper Linerboard Sulfite condensate TMP/CTMP NSSC Bleached TMP/CTMP NSSC/CTMP CTMP Paperboard

3 10 9 12.5 18 20 13.5 15 12.7 35

600 1200 10,000 1440 2880

75 > 80 90 90 60 80 75 80 85 83.3

60 > 80 75 80 50 55 60 55 70 72.2

12,000 15,600 3000 7800

6000 16,000 1800 4000

7000 17,500 4000 1500 7900 3000

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99% BOD, 91% COD, 97% SS, and 90% color of a pulp and paper mill in Brazil (Foelkel, 1989). Rusten et al. (1994) reported that a combination of a biofilm reactor followed by one anaerobic and two aerobic reactors was found to remove 50% COD, 80 90% BOD7, 50% AOX, 90% ClO3. Shaw et al. (2002) showed that a combination of aerobic reactor followed by anaerobic reactor removed 94% color, and 66% TOC. Schnell et al. (1997) found that 87 95%, 70 77%, and 80 94% removal of BOD, COD, and resin and fatty acids was provided by biological treatment. Tardif and Hall (1997) reported 100%, 96%, 76%, and 34% removal of resin acid (RA), fatty acid (FA), dissolved chemical oxygen demand (DCOD), and total dissolved solids (TDS), respectively at temperatures 20 40 jC by an SBR. An MBR removed 100% RA and FA, 84% DCOD, and 37% TDS at 40 50 jC. Malmquist et al. (1999) reported a COD removal of 70 90% of whitewater by biological treatment. Badar (1996) suggested a number of methods to improve the integrated paper mill wastewater effluent treatment: (1) increasing the capacity of the aeration basin; (2) installing an extra dissolved air flotation clarifier; (3) adding chlorine gas to improve bulking of sludge problem and (4) injecting oxygen to treat BOD during heavy rain and flooded conditions. Graves and Joyce (1994) reviewed the ability of biological treatment systems to remove chlorinated organic compounds discharged from pulp and paper industry. AOX removal of 32% (aerated lagoon) and 10 65% by activated sludge plant was reported. Gupta et al. (2001) isolated bacterial specie Aeromonas formicans suitable to treat black liquor from kraft pulp and paper mills. Performances of various treatment processes are summarized in Tables 11 14.

7. Discussion The literature review showed that an internal process change is one of the options to be adopted by the pulp and paper industry to reduce the pollution at the source. A recent comprehensive study carried out in a large number of pulp and paper mills in the US found that the effluent discharge has been reduced by 30%; TSS and BOD have been reduced by 45% and 75%, respectively (Das and Jain, 2001) even

when the production has been increased. Trotter (1990a,b) evaluated biotechnological applications such as genetic modification of plant, biopulping, and biobleaching to reduce chlorinated organic compounds as an emerging technology for internal pollution control. Enzyme treatment for pulp dissolving, improving tensile properties by treating mechanical pulp with white rot organisms and enzymatic beating of chemical pulps, hemicellulose, and decolorization by white rot fungi were given as possible biotechnological options. Among the various treatment processes currently used for pulp and paper effluent treatment, only a few are commonly adopted by pulp and paper industry especially for tertiary treatment. Some of the treatment processes such as ozonation, fentons reagent, adsorption, and membrane technology are efficient but are more expensive. Sedimentation is the most commonly adopted process by the pulp and paper industry to remove suspended solids. The performance data given by Springer (2000) showed 80 90% removal of initial suspended solids from most of the mills except a deinking mill. Flotation is also commonly used in the pulp and paper industry but most of the time as a tertiary treatment. Coagulants are a preferred option for removing turbidity and color from the wastewater. Reported results have shown that they are also capable in reducing COD, TOC, and AOX to some extent. Among the coagulants, modified chitosan showed the highest performance for color and TOC removal. Polyelectrolytes are better than alum and they produce less sludge and pose less problems with sludge dewaterability than alum. Adsorption processes are useful to remove color, COD, and AOX. They are rather expensive and it is not known whether the pulp and paper industry are employing them widely. However, laboratory-scale experiments are usually reported. Activated charcoal, fullers earth, and coal ash showed better results for color removal. Activated coke alone was able to remove 90% of the COD, AOX, DOC, and color. Chemical oxidants such as ozone + photocatalysis, and ozone + UV are reported to be efficient in removing COD and TOC and color. However, the efficiency largely depends upon the concentration of the COD. Ozone alone is able to remove 90% of EDTA and AOX, and over 80% of COD. However, it is rather expensive (Perez et al., 2002b). Ozonation

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is not commonly adopted in most countries, not even in Europe but it is emerging in North America. Membrane processes are efficient in reducing over 90% of color, TSS, and AOX in most of the cases. Fouling of membranes is a problem in the case of soft wood effluent treated by membrane filtration. In secondary treatment processes, activated sludge is the most commonly used. UASB and fluidized beds are also gaining in use recently. The problem with activated sludge is sludge bulking. Reported results have shown that activated sludge can remove all types of the pollutants pertaining to the pulp and paper industry. However, the removal of AOX is below 50%, BOD around 95% in most of the mills, and COD removal averages around 70%. This system is also efficient in removing chlorinated phenolic compounds (over 75%) most of the time. Dalentoft and Thulin (1997) reported that Kaldnes (anaerobic + aerobic) process in series with an activated sludge, could be an efficient, stable, and a competitive combination process, considering both investment and operating costs. Aerated lagoons are efficient in removing BOD over 95% in most of the reported results. COD removals are moderate between 60% and 70%, AOX around 50%, and a high removal (85%) for chlorinated phenolics. Anaerobic contact reactors are efficient in removing biodegradable organic compounds such as BOD, and COD. The performance data from various mills showed that anaerobic contact reactors were able to remove over 90% of BOD and 65% of COD in most of the cases. Anaerobic filters and fluidized bed reactors are suitable in reducing organic pollutants only. Both the reactors achieve almost same efficiency in terms of BOD (>80%), and COD (>70%) removal (refer to Table 14 for details). UASBs are able to remove over 80% of BOD and 50 80% of COD in most of the mills (refer to Table 14 for details). Fungi are efficient in removing especially color and COD from the pulp mill wastewater. Removal of color using white rot fungi was above 80% in most of the reported cases and COD removal was above 75%. White rot fungi particularly P. chrysosporium and C. versicolor are suitable for efficient degradation of the refractory material (Bajpai and Bajpai, 1994). The reported results have shown that high removals are achieved in the case of the combination of two or more physicochemical

processes or combination of physicochemical and biological processes. The confirmation of the reported results, their applicability in the real field, and economic evaluations are very important in adopting the process. For example, the anaerobic treatment process for pulp and paper mill effluents is still in an initial application phase. However, comprehensive evaluations made by various authors lead to a better understanding of the various treatment processes and their adaptability. For example, Jemaa et al. (2000) stated that chemical precipitation, evaporation, membrane technology, and ion exchange were the established options for the removal of colloids and metal ions. Perez et al. (2002a) conducted an economic evaluation of various advanced oxidation processes to remove organic contaminants. Ozonation was stated to be effective but rather an expensive process. Rintala and Puhakka (1994) stated that operation costs of the activated sludge was about three times greater than that of anaerobic systems. Bajpai (2000) presented comparative costs of the anaerobic and activated sludge treatment, which showed that activated sludge was almost twice as expensive as anaerobic reactors. The recent paper by Perez et al. (2002b) reported a high efficiency of COD and TOC removal when iron ion was used with ozone/UV treatment system. The authors showed that the presence of iron ion in the ozone/UV treatment brought a complete removal of COD in 90 min while TOC removal was higher than 90%. The report stated that the overall cost was reduced by 50%, which is encouraging news for the industry. Mobius and Cordes-Tolle (1994) suggested that sand filters, biofilters, low capacity trickling filters, flocculation and precipitation with inorganic salts in combination with filtration or flotation are the emerging systems for adoption by pulp and paper mills.

8. Conclusions Based on the above literature review, the following conclusions are drawn: (i) Both aerobic and anaerobic treatment systems are feasible to treat wastewater from all types of pulp and paper mills except that bleaching kraft effluents are less suitable for treatment by

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53

(ii)

(iii)

(iv)

(v)

(vi)

(vii)

(viii)

anaerobic means, as they are more toxic to anaerobic bacteria. The anaerobic treatment of high strength wastewater requires further treatment as it contains high residual COD. A combination using an anaerobic process followed by an aerobic treatment system is a better option, as it can make use of the advantages of both the treatment processes. Color is removed efficiently by fungal treatment, coagulation, chemical oxidation, and ozonation. Chlorinated phenolic compounds and AOX can be removed by adsorption, ozonation and membrane filtration. Combinations of two or more physicochemical processes produce a high removal of toxic pollutants. Combinations of physicochemical and biological treatment processes with optimization of the process provide a long-term solution for pulp and paper mill effluent treatment. More studies are needed on the removal of AOX and chlorinated phenolic compounds.

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