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Treatment of pulp and paper mill wastewater—a review D. Pokhrel, T. Viraraghavan * Department of Environmental and System Engineering, Faculty of Engineering, University of Regina, 3737 Wascana Parkway, Regina, SK, Canada S4S 0A2 Received 2 July 2003; received in revised form 29 January 2004; accepted 7 May 2004 Abstract Pulp and paper mills generate varieties of pollutants depending upon the type of the pulping process. This paper is the state of the art review of treatability of the pulp and paper mill wastewater and performance of available treatment processes. A comparison of all treatment processes is presented. Combinations of anaerobic and aerobic treatment processes are found to be efficient in the removal of soluble biodegradable organic pollutants. Color can be removed effectively by fungal treatment, coagulation, chemical oxidation, and ozonation. Chlorinated phenolic compounds and adsorable organic halides (AOX) can be efficiently reduced by adsorption, ozonation and membrane filtration techniques. D 2004 Elsevier B.V. All rights reserved. Keywords: Pulp; Pulp and paper; Wastewater; Treatment 1. Introduction The rapid increase in population and the increased demand for industrial establishments to meet human requirements have created problems such as overex- ploitation of available resources, leading to pollution of the land, air and water environments. The pulp and paper industry is one of the most important industries of the North American economy and ranks as the fifth largest in the U.S. economy (Nemerow and Dasgupta, 1991). In Canada, the pulp and paper industry accounts for a major portion of the country’s economy in terms of value of production and total wages paid (Sinclair, 1990). The wood pulping and production of the paper products generate a considerable amount of pollutants characterized by biochemical oxygen de- mand (BOD), chemical oxygen demand (COD), sus- pended solids (SS), toxicity, and color when untreated or poorly treated effluents are discharged to receiving waters. The high water usage, between 20,000 and 60,000 gallons per ton of product, (Nemerow and Dasgupta, 1991) results in large amounts of wastewater genera- tion. The pulp and paper industry is considered as the third largest polluter in the United States (US). It has been estimated that the pulp and paper industry is responsible for 50% of all wastes dumped into Cana- da’s waters (Sinclair, 1990). The effluents from the industry cause slime growth, thermal impacts, scum formation, color problems, and loss of aesthetic beauty in the environment. They also increase the amount of toxic substances in the water, causing death to the zooplankton and fish, as well as profoundly affecting the terrestrial ecosystem. 0048-9697/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.scitotenv.2004.05.017 * Corresponding author. Tel.: +1-306-5854094; fax: +1-306- 5854855. E-mail address: [email protected] (T. Viraraghavan). www.elsevier.com/locate/scitotenv Science of the Total Environment 333 (2004) 37– 58
Transcript
  • r. V

    eering

    Regin

    form

    filtration techniques.

    demand for industrial establishments to meet human or poorly treated effluents are discharged to receiving

    mentploitation 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

    The high water usage, between 20,000 and 60,000

    gallons per ton of product, (Nemerow and Dasgupta,

    1991) results in large amounts of wastewater genera-

    tion. The pulp and paper industry is considered as the

    third largest polluter in the United States (US). It has

    been estimated that the pulp and paper industry is

    responsible for 50% of all wastes dumped into Cana-requirements have created problems such as overex- waters.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

    pollutants characterized by biochemical oxygen de-

    mand (BOD), chemical oxygen demand (COD), sus-

    pended solids (SS), toxicity, and color when untreatedcoagulation, chemical oxidation, and ozonation. Chlorinated p

    efficiently reduced by adsorption, ozonation and membranePulp 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,

    henolic compounds and adsorable organic halides (AOX) can beTreatment of pulp and pape

    D. Pokhrel, T

    Department of Environmental and System Engin

    3737 Wascana Parkway,

    Received 2 July 2003; received in revised

    Abstract

    Science of the Total Environin 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

    0048-9697/$ - see front matter D 2004 Elsevier B.V. All rights reserved.

    doi:10.1016/j.scitotenv.2004.05.017

    * Corresponding author. Tel.: +1-306-5854094; fax: +1-306-

    5854855.

    E-mail address: [email protected] (T. Viraraghavan).mill wastewatera review

    iraraghavan*

    , Faculty of Engineering, University of Regina,

    a, SK, Canada S4S 0A2

    29 January 2004; accepted 7 May 2004

    www.elsevier.com/locate/scitotenv

    333 (2004) 3758das 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.

  • papermaking. High amounts of wastewater are gene-

    rated at different stages of this process.

    2.4. Thermo-mechanical pulping (TMP)

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758382.1. Mechanical pulping

    The yield of the pulp by this process is as high as

    9095% (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

    4050% 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 aThe growing public awareness of the fate of these

    pollutants and stringent regulations established by

    the various governmental authorities such as provin-

    cial and federal agencies are forcing the industry to

    treat effluents to the required compliance level before

    discharging them in to the environment. Many stud-

    ies have been conducted so far on this sector regard-

    ing the impacts as well as the control of the

    pollutants. Berube and Kahmark (2001), Kahmark

    and Unwin (1996, 1998, 1999), and Srinivasan and

    Unwin (1995) have reviewed pollution control as-

    pects of the pulp and paper industry. However, all

    these reviews have focused on the state of the art in

    integrated pollution management and lack a compara-

    tive evaluation of various treatment processes partic-

    ular to the water pollution control. This review,

    therefore, would examine the pollution control sys-

    tems and compare the performance of the effluent

    treatment measures in use.

    2. Process description

    Pulping is the initial stage of the paper making

    industry and provides the processed material. It is the

    largest source of the pollution in the whole process ofsolution of sodium hydroxide (NaOH) andThis process involves steaming the raw materials

    under pressure for a short period, prior to and during

    refining. The thermo-mechanical process is further

    modified using chemicals during the steaming stage,

    and the process is called chemi-thermomechanical

    pulping (CTMP).

    2.5. Papermaking

    The paper making operation consists of two parts;

    one is stock preparation by treating the pulp to the

    required degree of fitness and the other is paper

    making where the treated pulp is passed through

    continuous moulds/wires to form sheets.

    3. Sources of pollution

    Each pulping process utilizes large amounts of

    water, which reappear in the form of an effluent.

    The most significant sources of pollution among

    various process stages are wood preparation, pulping,

    pulp washing, screening, washing, bleaching, and

    paper machine and coating operations. Among the

    processes, pulping generates a high-strength waste-

    water especially by chemical pulping. This wastewa-

    ter contains wood debris and soluble wood materials.

    Pulp bleaching generates most toxic substances as it

    utilizes chlorine for brightening the pulp. Pulp fibers

    can be prepared from a vast majority of plants insodium 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 8590% and the strength of the pulp is

    relatively better than the pulp from the mechanical

    pulping alone.nature such as woods, straws and grasses, bamboos,

  • or canes and reeds. Wood is the most abundant source

    of papermaking fiber. Wood consists of various com-

    pounds (lignin, carbohydrate, and extractives) which

    are hard to biodegrade, and these derivatives are

    washed away from the fibers during the washing,

    dewatering, and screening processes. Depending upon

    the type of the pulping process, various toxic chem-

    icals such as resin acids, unsaturated fatty acids,

    diterpene alcohols, juvaniones, chlorinated resin

    acids, and others are generated in the pulp and paper

    making process. The pollutants at various stages of

    the pulping and paper making process are presented in

    Fig. 1.

    It is clear that an individual pulping stage gene-

    rates different quantities, qualities and types of

    pollutants. The wastewater pollution load from indi-

    vidual pulping and papermaking process is given in

    Table 1.

    The amount of pollutants produced by an indivi-

    dual mill is an important indicator to evaluate the

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 39Fig. 1. Pollutants from various sources of pulping and papermaking (US EPA, 1995).

  • 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 1

    Typical wastewater generation and pollution load from pulp and

    paper industry (Rintala and Puhakka, 1994)

    Process Wastewater

    (m3/adt pulp

    or paper)

    SS

    (kg/adt

    pulp)

    COD

    (kg/adt

    pulp)

    Wet debarking 525 nr 520

    Groundwood pulping 1015 nr 1532

    TMP -unbleached 1030 1040 4060

    TMP-bleached 1030 1040 50120

    CTMP-unbleached 1015 2050 70120

    CTMP-bleached 1015 2050 100180

    NSSC 2080 310 30120

    Ca-sulfite (unbleached) 80100 2050 nr

    Ca-sulfite (bleached) 150180 2060 120180

    Mg-sulfite (unbleached) 4060 1040 60120

    Kraft-unbleached 4060 1020 4060

    Kraft-bleached 6090 1040 100140

    Paper making 1050 nr nr

    Agrobased small

    paper mill

    200250 50100 10001100

    nrnot reported; adtair dry ton; NSSCneutral sulfite semi-

    Table 3

    Comparison of actual emissions from pulp mills (TAPPI, 1990)

    Country Parameters

    SS

    (kg/adt)

    BOD

    (kg/adt)

    COD

    (kg/adt)

    AOX

    (kg/adt)

    N

    (kg/adt)

    P

    (kg/adt)

    Bleach kraft

    USA 5 5 2.2

    Sweden 3.8 12 68 2 0.23 0.09

    Bleached sulfite

    Sweden 6.8 17.8 145 1.8 0.3 0.10

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 375840performance of the system as well as a crosscheck

    whether the mills have followed the guidelines. Table

    2 provides performance data of selected processes and

    chemicals.mills.

    The environmental guidelines on discharge vary

    with countries. The emission data from USA and

    was three to eight times lower than it was in the softTable 2

    Typical pollution load per ton of production (kg/ton)

    Process Pollutants

    SS BOD COD Color Reference

    Deinking 11 54 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

    (Brazil)

    0.40.5 0.20.3 55.5 1920a Foelkel (1989)

    Large mill

    (India)

    31.2 13 82.4 Srivastava et al.

    (1990)

    Small mill

    (India)

    140.3 152.26 639.4 Srivastava et al.

    (1990)

    Sweden 0.7 0.2 7.6 Carlson et al.

    (2000)

    a PtCo (kg/ton).wood kraft mill. The general characteristics of the

    Table 4

    Discharge limits (monthly, semiannual, or annual verges) forTable 4.

    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 millbleached kraft pulp

    Country Parameters

    SS

    (kg/adt)

    BOD

    (kg/adt)

    COD

    (kg/adt)

    AOX

    (kg/adt)

    Reference

    Canada 9.514.5 5.530 1.41.5 TAPPI, 1990

    Finland 515 6.834 90 1.4 TAPPI, 1990

    Norway 5 90 6 TAPPI, 1990

    Sweden 0.35.8 7.517 39107 1.52 TAPPI, 1990

    Belgium 714.4 2.35.4 2263 1.5 TAPPI, 1990

    France 6.510 3.330 4895 TAPPI, 1990

    USA 3.86

    (8.47)

    2.41

    (4.52)

    Reserved 0.272

    (0.476)

    US EPA, 2000

    The U.S. EPA values are monthly average values for new bleached

    kraft mill. The values in the ( ) are daily maximum allowable.

  • The pollutants discharged from the pulp and paper

    Table 5

    Typical characteristics of wastewater (mg/l) at different processes (Bajpai, 2000)

    Process Parameters

    pH SS BOD5 COD Carbohydrate Acetic

    acid

    Methanol N P S

    TMP (1) 383 2800 7210 2700 235 25 12 2.3 72

    TMP (2) 4.2 810 2800 5600 1230

    CTMP 500 30004000 60009000 1000 1500 167

    Kraft bleaching 10.1 3774 128184 11241738 0 4076

    Kraft foul (1) 8.0 16 568 1202 421 5.9

    Kraft foul (2) 10.2 0 10,700 16,000 306 1 91

    621

    321

    61

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 41industry affect all aspects of the environment such as

    water, air and land. Makris and Banerjee (2002)wastewater produced at various process stages and

    pollution sources are given in Tables 5, 6 and 7.

    5. Fate and effects on the environment

    Kraft foul (3) 9.510.5 0 55008500 10,00013,000

    Sulfite

    condensate (1)

    2.5 20004000 40008000

    Sulfite

    condensate (2)

    2.85.9 37005110 980027,100

    NSSC Pulping:

    Spent liquor 253 13,300 39,800

    Chip wash 6095 12,000 20,600

    Paper mill 800 1600 5020studied the fate of the resin acid in the secondary

    treatment system. Various authors at different times

    reported the appearance of toxic effects on various fish

    species due to exposure of pulp and paper mill efflu-

    ents. Many authors reported the presence of toxic

    pollutants in fish or toxic effects on fish such as

    respiratory stress, mixed function oxygenase activity,

    toxicity and mutagenicity, liver damage, or genotoxic

    effects, and lethal effects on the fishes exposed to pulp

    Table 6

    Characteristics of wastewater (mg/l) at various pulp and paper processes

    Process Parameters

    TS SS BOD5

    Wood preparation 1160 600 250

    Drum debarking 20173171 480987

    Bleach kraft mill 34 23

    Newsprint mill 3750 250 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

    75008500 350600 0.021.55 120375

    250 800850

    8401270

    0 3200 90 55 10 868

    0 820 70 86 36 315

    0 54 9 11 0.6 97organisms 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 AOX Resin

    (Ag/l)Color

    (PtCo)

    Nemerow and

    Dasgupta (1991)

    2050 Springer (2000)

    12.5 69 Wayland et al. (1998)

    3500 16 1000 Tardif and Hall (1997)

  • BOD

    (mg/l

    98

    262

    13,08

    10

    109

    112

    36

    17

    156

    14

    1050 4870 DB Mandal and Bandana (1996)

    16 78 Vlyssides and

    56

    42

    17

    24

    wn;

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 375842or on fish attributable to the treated mill effluent.

    Table 7

    Characteristics of wastewater at various pulp and paper processes

    Process Parameters

    pH TS

    (mg/l)

    SS

    (mg/l)

    Large mills (India) 11.0 5250 1233

    Small mills (India) 12.3 15,120 4890

    Digester house 11.6 51,589 23,319

    Combined effluent 7.6 3318 2023

    TMP whitewater 4.7 91

    TMP whitewater 4.7 105

    Kraft mill 8.2 8260 3620

    Pulping 10 1810 256

    Kraft mill (unbleached) 8.2 1200 150

    Bleached pulp mill 7.5 1133

    Bleaching 2.5 2285 216

    Pulp and paper 7.8 4200 1400

    News air and land paper

    deinking

    8.3 450 400

    Paper making 7.8 1844 760

    Paper mill 8.7 2415 935

    Paper machine 4.5 503

    Paper machine 8.3 1032

    a Unit [Optical Density (O.D) at 465 nm]; DB means dark broStepanova et al. (2000) reported no clear evidence of

    mutagens in most of aquatic animals studied in Lake

    Baikal due to Baikalsk pulp and paper mill wastewater

    discharged to the lake. Wayland et al. (1998) reported

    no effect on the tree shallow, which feed on the insects

    downstream of the pulp mill.

    Howe and Michael (1998) studied the effects of the

    treated pulp mill effluent on irrigated soil in northern

    Arizona, which showed serious soil chemistry change.

    Dutta (1999) investigated the toxic effect of the paper

    mill effluent (treated) applied to a paddy field in

    Assam, India. Gupta (1997) and Singh et al. (1996)

    reported high loads of organic pollutants derived from

    the paper mill wastewater in Tamilnadu, and Punjab,

    India, respectively. Singh et al. indicated high level of

    coliform bacteria in the effluent too. However, Archi-

    bald (2000) indicated that the presence of coliform

    bacteria in the pulp and paper effluent did not neces-

    sarily mean a health hazard to the environment unless

    pathogens were observed. Skipperud et al. (1998) and

    Holmbom et al. (1994) reported the presence of various

    trace metals in the pulp and paper mill effluents at low

    levels. King et al. (1999) reported elevated levels ofMn

    accumulation in the Crayfish exposed to the paper millwastewater. Mandal and Bandana (1996) reported on

    Economides (1997)

    1 953 Black Gupta (1997)

    5 845 DB Dutta (1999)

    0 723 243 Yen et al. (1996)

    0 Dilek and Gokcay (1994)

    LY means light yellow.References

    5

    )

    COD

    (mg/l)

    Color

    (PtCo)

    3 2530 black Srivastava et al. (1990)

    8 6145 DB Srivastava et al. (1990)

    8 38,588 16.6a Singh et al. (1996)

    3 675 1.0a Singh et al. (1996)

    0 2440 Jahren et al. (1999)

    5 2475 Jahren et al. (2002)

    4112 4667.5 Rohella et al. (2001)

    0 Dilek and Gokcay (1994)

    5 250 Nemerow and Dasgupta (1991)

    6 2572 4033 Yen et al. (1996)

    0 Dilek and Gokcay (1994)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 200259 m3/ton of

    paper production (Gune, 2000). Several authors have

    suggested internal process change as a measure to

  • D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 43control pollution (Reilama and Ilomaki, 1999; Webb,

    1994; Dey et al., 1991). Raghuveer and Sastry (1990)

    reported BOD, COD, and color reduction by internal

    management measures. However, the treatment of the

    wastewater by various external processes is essential.

    Since pulp and paper industry discharges varieties of

    pollutants, the treatment methods also vary.

    6.1. Physicochemical treatment

    Physicochemical treatment processes include re-

    moval of suspended solids, colloidal particles, floating

    matters, colors, and toxic compounds by either sedi-

    mentation, flotation, screening, adsorption, coagula-

    tion, oxidation, ozonation, electrolysis, reverse osmo-

    sis, ultra-filtration, and nano-filtration technologies.

    6.1.1. Sedimentation/flotation

    Suspended matters present in the pulp and paper

    wastewater are comprised primarily of bark particles,

    fiber, fiber debris, filler and coating materials. Thomp-

    son et al. (2001) stated that sedimentation was the

    preferred option within the paper mills in the UK, and

    contributed to more than 80% removal of the sus-

    pended solids on an average. Rajvaidya and Markan-

    dey (1998) stated that the design value of the primary

    clarifier was 7080% in average. Azevedo et al.

    (1999) reported on the effect of pH on pulp settal-

    ability. Gubelt et al. (2000) reported 6595% removal

    of TSS by dissolved air flotation and it was an

    unstable unit. However, Wenta and Hartmen (2002)

    mentioned that dissolved air flotation was able to

    remove 95% of the TSS.

    6.1.2. Coagulation and precipitation

    Coagulation and flocculation is normally employed

    in the tertiary treatment in the case of pulp and paper

    mill wastewater treatment and not commonly adopted

    in the primary treatment. Tong et al. (1999) and

    Ganjidoust et al. (1997) carried out a comparative

    study of horseradish peroxide (chitosan) and other

    coagulants such as (Al2(SO4)3), hexamethylene di-

    amine epichlorohydrin polycondensate (HE), poly-

    ethyleneimine (PEI), to remove adsorbable organic

    halides (AOX), total organic carbon (TOC), and color.

    The authors indicated that modified chitosan was far

    more effective in removing these pollutants than othercoagulants. Wagner and Nicell (2001) investigated thetreatment of foul condensate, defined by phenolic

    compounds, and toxicity using microtox assay from

    kraft pulping by horseradish peroxide and H2O2 and

    found a total phenol reduction below 1 mg/l and

    toxicity (microtox assay) reduction by 46%. Dilek

    and Gokcay (1994) reported 96% removal of COD

    from the paper machine, 50% from the pulping, and

    20% for bleaching effluents by using alum as a

    coagulant. Rohella et al. (2001) stated polyelectrolytes

    were better than the conventional coagulant alum to

    remove turbidity, COD, and color. Sheela and Distidar

    (1989) reported on black liquor treatment by precipi-

    tation with CaSO42H2O in the presence of CO2. Theremoval of dissolved solids was reported to be 63%.

    However, Wang and Pan (1999) reported that the use

    of coagulants such as polyethylene oxide (PEO),

    worsened the settlability and increased COD levels,

    turbidity, and suspended solids of the treated effluent

    when the dose was between 25 and 250 ppm. Cher-

    noberezhskii et al. (1994) reported that coagulation

    with aluminum sulfate or modified adsorbents was the

    best option for color removal from the sulfate and

    sulfite wood pulp and paper industry.

    6.1.3. Adsorption

    Murthy et al. (1991) reported a high removal of

    color by activated charcoal, 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 waste-

    water produced by the Union Camp Facility at Frank-

    lin, VA, can be treated by activated carbon and ion

    exchange to reduce color and chloride to levels ac-

    ceptable for reuse. Das and Patnaik (2000) investigated

    the lignin removal efficiency of the blast furnace dust

    (BFD) and slag by the adsorption mechanism. Their

    study showed 80.4% and 61% removal of lignin by

    BFD and slag, respectively. Narbaitz et al. (1997)

    reported that PACTk process was an effective processto 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 photo-

    catalytic oxidation of kraft pulp bleaching wastewatershowing that the removal largely depended on the

  • D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 375844concentration of COD and chloride below a certain

    level. Zamora et al. (1998) reported on the use of

    horseradish peroxide to decolorize kraft effluent by

    50% within three hours of reaction time. The degra-

    dation of phenolic and polyphenolic compounds pres-

    ent in the bleaching effluent was studied using

    advanced oxidation systems such as photocatalysis

    with O2/ZnO/UV, O2/TiO2/UV, O3 and O3/UV. The

    authors concluded that O2/ZnO/UV and O2/TiO2/UV

    were the best systems to oxidize the effluent in a short

    period of time. Perez et al. (2002c) reported that the

    combination of Fenton and photo-fenton reactions

    proved to be highly effective for the treatment of

    bleaching kraft mill effluent. Verenich et al. (2000)

    reported on the improvement in biodegradability of an

    effluent from 30% to 70% by wet oxidation method.

    Hassan and Hawkyard (2002) studied the removal of

    color by combined oxidation with ozone and Fentons

    reagent and stated that 100% color removal was

    achieved at a pH of 45 in the case of ferral (derived

    from natural clay sources, which contains 2% ferric

    sulfate and 6% aluminum sulfate) and ferric sulfate.

    Dufresne et al. (2000) reported on the oxidation of

    total reduced sulfur (TRS) giving odor free products

    by catalytically enhanced oxidation.

    6.1.5. Membrane filtration

    Jonsson et al. (1996) reported on the treatment of

    paper coating color effluent treatment by membrane

    filtration suggesting that the composition of the color

    had a significant influence on the performance. Mem-

    brane separation techniques were reported to be

    suitable for removing AOX, COD, and color from

    pulp and paper mills (Zaidi et al., 1992; Afonso and

    Pinho, 1991, Falth, 2000). De Pinho et al. (2000)

    compared the efficiency of (1) ultrafiltration and (2)

    ultrafiltration plus dissolved air flotation. The results

    showed 54%, 88%, 100% removal of TOC, color,

    and SS, respectively by ultrafiltration alone. Ultrafil-

    tration plus dissolved air flotation resulted in 65%,

    90% and 100% removal of TOC, color, and SS,

    respectively. Dube et al. (2000) reported that 88%

    and 89% removal of BOD, and COD, respectively

    was achieved by reverse osmosis (RO). Merrill et al.

    (2001) stated that membrane filtration (MF), and

    granular membrane filtration (GMF) were suitable

    for removing heavy metals from the pulp and papermill wastewaters.6.1.6. Ozonation

    Yeber et al. (1999) reported that a substantial

    removal of COD, TOC, and toxicity from pulp mill

    effluent and increased biodegradability of the effluent

    were achieved after treatment with ozone. Korhonen

    et al. (2000) reported a 90% removal of ethylenedia-

    minetetraacetic acid (EDTA) and a 65% removal of

    COD by ozone treatment of the pulp mill effluent.

    Hinck et al. (1997) reported that neither EDTA nor

    diethylene triamine pentaacetic acid (DTPA) are bio-

    degraded in aerobic conditions. Oeller et al. (1997)

    reported high removal of COD and DOC from the

    pulp effluent by ozone treatment. Freire et al. (2000)

    reported a 12% reduction of total organic carbon, total

    phenols reduced to 70%, and effluent colors to 35% of

    bleached pulp mill effluent after 60 min of ozonation.

    Several authors reported on toxic compounds, COD,

    and color removal by ozone treatment (Hostachy et

    al., 1997; Zhou and Smith, 1997; Yamamoto, 2001).

    Roy-Arcand and Archibald (1996) reported that bio-

    treated kraft effluents yielded a substantial decrease in

    the biologically recalcitrant residual adsorbable or-

    ganic halogens (AOX), converted COD to BOD and

    yielded large decrease in color. Laari et al. (2000)

    investigated the removal of lipophilic wood extrac-

    tives from TMP wastewater by ozonation. The authors

    indicated that a high dosage of ozone (100300 mg/

    dm3) was required to remove 50% of lippphilic wood

    extractives. Korhonen and Tuhkanen (2000) reported

    that ozone doses of 0.2 mgO3/initial mgCOD elimi-

    nated over 90% resin acid. Torrades et al. (2001)

    reported high removals of TOC, COD, AOX, and

    color from bleached kraft mill effluent (BKME1)

    using heterogeneous photocatalysis and ozone treat-

    ment. Sevimli and Sarikaya (2002) reported a 95

    97% color removal for high doses of ozone in 15 min

    of ozonation. Kallas and Munter (1994) suggested

    post treatment of bleached mill effluent by ozonation

    and adsorption.

    6.2. Biological treatment

    6.2.1. Aerobic treatment

    6.2.1.1. Activated sludge process. The performance

    variation of the activated sludge due to the changes in

    pH, temperature, and H2O2 and DTPA was reported

    by Ginkel et al. (1999), Norris et al. (2000), and

  • D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 45Larisch and Duff (1997, 2000), respectively. Knudsen

    et al. (1994) reported a high reduction of BOD and

    soluble COD by a two-stage activated sludge process.

    Shere and Daly (1982) claimed that TMP wastewater

    was readily degradable by the activated sludge pro-

    cess. Hansen et al. (1999) suggested upgrading the

    activated sludge plant by the addition of Floobeds

    (floating biological bed) in series that increased COD

    and BOD removal from 51% to 90% and 70% to

    93%, respectively. Chandra (2001) reported efficient

    removal of color, BOD, COD, phenolics, and sulfide

    by microorganisms such as Pseudomonas putida,

    Citrobacter sp., and Enterobacter sp. in the activated

    sludge process. Mohamed et al. (1989) reported

    removal of chlorinated phenols, 1,1-dichlorodimethyl

    sulfone (DDS), and chlorinated acetic acids in an

    oxygen activated sludge effluent treatment plant.

    Demirbas et al. (1999) reported AOX removal by

    the activated sludge process. Junna and Ruonala

    (1991) reported 90% BOD7, 70% COD, 4060%

    AOX, and 6095% 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 20002500 mg/l and

    an aeration time of 68 h were required to remove

    8388% of BOD. High removals of BOD, COD,

    AOX, and chlorinated phenolics have been achieved

    in the activated sludge process (Saunamaki, 1997;

    Schnell et al., 2000a). Kennedy et al. (2000) reported

    that the activated sludge was successful in removing

    nearly all detectable Microtoxk toxicity frombleached kraft pulp mills at low level whereas the

    PACTk was slightly better in removing highly toxicconcentrated 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 1546% 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. Chernyshet 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 3040% in a full-

    scale lagoon and 6070% in a pilot-scale plant.

    Stuthridge et al. (1991) reported 65% removal of

    AOX from bleached kraft pulp and paper mill

    effluent. Junna and Ruonala (1991) reported removal

    of BOD7 ranging between 50% and 75% and chlo-

    rinated phenolics 1050% by an aerated lagoon.

    Achoka (2002) reported that an oxidation pond

    removed chemical compounds greater than 50%.

    Schnell et al. (2000a) reported removals of BOD,

    AOX, chlorinated phenolics, and polychlorinated

    phenolics respectively from an aerated lagoon.

    6.2.1.3. Aerobic biological reactors. Many authors

    have reported high removals of organic pollutants of

    kraft mill wastewater by sequencing batch reactor

    (SBR) treatment (Franta et al., 1994; Franta and

    Wilderer, 1997; Milet and Duff, 1998). Reid and

    Simon (2000) reported 100% removal of methanol

    and 90% removal of CODsol by SBR. Substantial

    removal of COD, TOC, BOD (Magnus et al.,

    2000a), lignin and resin acids (Magnus et al.,

    2000b) of TMP wastewater using high rate compact

    reactors (HCRs) at a retention time of 1.5 h had

    been reported. Removal of COD by a moving bed

    bifilm reactor (MBBR) had been demonstrated (Jah-

    ren et al., 2002; Borch-Due et al., 1997). Magnus et

    al. (2000c) reported 93% and 65% removal of BOD

    and COD, respectively by a biological compact

    reactor. Berube and Hall (2000) showed that approx-

    imately 93% removal of TOC could be achieved by

    a membrane bioreactor. Asselin et al. (2000) con-

    cluded that suspended carrier biofilm reactor (SCBR)

    was highly efficient in removing chronic toxicity

    from the effluent. Rovel et al. (1994) achieved

    76%, 62%, 81%, and 48% removal of BOD,

    COD, SS, and AOX, respectively, using a biofilter.

    Rudolfs and Amberg (1953) demonstrated that aer-

    obic treatment of whitewater (high strength) was

    able to achieve 7080% removal of BOD. Typical

    efficiencies of aerobic systems are presented inTable 8.

  • D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758466.2.2. 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 (3002000 mg/

    l BOD) (Bajpai, 2000) and were not suitable for

    anaerobic treatment. Anaerobic filter, upflow sludge

    blanket (UASB), fluidized bed, anaerobic lagoon, and

    anaerobic contact reactors are anaerobic processes,

    that are commonly used to treat pulp and paper mill

    effluents. Pretreatment of the kraft mill black liquor

    was investigated by Poggi-Varaldo et al. (1996) and

    they reported that continuous anaerobic treatment of

    wastewater contaminated with black liquor was fea-

    sible at low to medium loading rates, with a total COD

    removal of 4880% and biodegradable COD reduc-

    tion of 8796%. 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

    Table 8

    Typical efficiencies of aerobic systems (Springer, 2000; *Kantar-

    djieff and Jones, 1997)

    System Aeration

    time (day)

    Organic loading

    (lb BOD/1000 ft3)

    Efficiency

    (%)

    Aerobic biofilters

    (sulfite mill)*

    3.4 kg/m3/day 7492

    Aerobic biofilters

    (TMP)*

    7490

    Aerobic stabiliztion

    basin

    510 50 8090

    Activated sludge 38 h 50 8085and presence of toxic substances that affects metha-

    nogens. Sandquist and Sandstrom (2000) developed a

    new treatment technology [the process consists of

    three steps: (1) stripping of sulfides and other volatile

    components from condensate; (2) regenerative ther-

    mal oxidation of stripper off gases; (3) adsorption of

    sulfur oxide] to treat foul condensate (sulfide) from

    the black liquor. Removal efficiency for foul conden-

    sate was reported to be more than 99% at a pH of 4

    and removal of methanol was 90% at a low liquid/gas

    ratio. Jackson-Moss et al. (1992) found 50% removal

    of COD and color by anaerobic biological granularactivated 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 Univer-

    sity of Roorkee, India. The author concluded that

    anaerobic biological treatment of black liquor was

    not feasible, as the pollutants were not readily de-

    gradable. Perez et al. (1998) evaluated two anaerobic

    systems (anaerobic filters and fluidized bed) in labo-

    ratory-scale reactors and reported that 81.5% organic

    removal efficiency was obtained in the case of fluid-

    ized bed with porous packing and 50% removal was

    obtained in the case of anaerobic filters on corrugated

    plastic tubes. Rajeswori et al. (2000) reported a 50%

    reduction of BOD of debarking wastewater by a

    fluidized bed reactor. Thompson et al. (2001) reported

    that COD removal efficiency of 80% was constantly

    achievable but the residual COD was around 800 mg/

    l meaning that additional treatment was essential.

    Schnell et al. (1992) concluded that anaerobic treat-

    ment systems were less suitable for treatment of

    sulfite-spent liquor compared to an aerobic system.

    The anaerobic treatability of different processes are

    given in Table 9.

    6.3. Fungal treatment

    Taseli and Gokcay (1999) isolated fungal specie

    (Pencillium sp.) which was able to remove 50% of the

    AOX, and color from the soft-wood bleachery efflu-

    ents in a contact time of 2 days. Several authors

    reported on the capacity of different fungal species

    to remove color from kraft mill effluent (Gokcay and

    Dilek, 1994; Duran et al., 1994; Sakurai et al., 2001).

    Prasad and Gupta (1997) reported on a substantial

    reduction of color and COD by the use of white rot

    fungi T. versicolor and P. chrysosporium. Saxena and

    Gupta (1998) showed that white-rot fungi P. chrys-

    osporium in combination with other white-rot fungi

    (P. sanguineus, P. ostreatus and H. annosum) and with

    the use of the surfactants were able to remove color,

    COD, and lignin content. Choudhury et al. (1998)

    found that lignin, BOD, COD and color removal wereachieved to the extent of 77%, 76.8%, 60%, and 80%,

  • Table 9

    Anaerobic degradability of pulp and paper mill effluent (Rintala and Puhakka, 1994)

    Wastewater from COD (mg/l) Anaerobic

    degrad. (%)

    Inhibitors

    Wet debarking 13004100 4478 Resin acids

    Thermomechanical

    pulping

    10005600 6087 Resin acids

    Chemothermomechanical

    pulping

    250013,000 4060 Resin acids,

    fatty acids, sulfur, DTPA

    NSSC-spent liquor 40,000 nr Tannins

    NSSC-condensate 7000 nr Sulfur, ammonia

    Kraft condensate 100033,600 8392 Sulfur, resin acids,

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 47respectively, by the fungal specie Pleurotus ostreatus.

    Zhang et al. (2000a) examined the removal of most of

    the detrimental organics from whitewater by com-

    bined enzyme and fungal treatment. The removal of

    lignin was >90% whereas resin and fatty acids were

    reduced by 20%. Zhang et al. (2000b) showed that

    fungus such as T. versicolor and fungal culture filtrate

    (FCF) obtained from these organisms were able to

    efficiently degrade the dissolved and colloidal sub-

    stances. Mendonca et al. (2002) suggested fungal

    pretreatment of P. taeda wood chips by C. subvermis-

    pora. The performance of fungal treatment is summa-

    rized in Table 10.

    Spent condensate 750050,000

    Chlorine bleaching 9002000

    Sulfite spent liquor 120,000220,0006.4. Integrated treatment processes

    An integrated or hybrid system is designed to take

    advantage of unique features of two or more process-

    es. A combination of coagulation and wet oxidation

    removed 51% of COD (Verenich et al., 2001); and

    Table 10

    Performance of fungal treatment

    Treatment process Parameters

    COD Lignin

    Influent

    (mg/l)

    %

    Removal

    Influent

    (mg/l)

    White rot fungi 39,012 40.74 2870

    White rot + surfactants 39,012 75.35 2870

    White rot (T. versicolor) 77.7

    White rot (P. chrysosporium) 79.4 83% of color and 75% of lignin (Verenich and Kallas,

    2001). A combination of ozone and biofilm reactor

    removed 80% COD (Helble et al., 1999). A combi-

    nation of chemical oxidation with ozone removed

    90% of wood extractives and 50% of the COD from

    TMP wastewater at 150 jC (Laari et al., 1999).Athanasopoulos (2001) suggested post treatment

    methods such as electrolysis or ozonation to reduce

    COD, and NH4+N concentration to the permitted

    level. Nakamura et al. (1997) reported on efficient

    degradation of lignin using a combined treatment of

    ozone and activated sludge process. Jokela and Keski-

    talo (1999) reported that a combination of dissolved

    air flotation and chemical precipitation removed 93%

    fatty acids, terpenes

    5090 Sulfur, organic sulfur

    3050 Chlorinated phenols,

    resin acids

    nr nrSS, 50% BOD7, 57% COD, 92% phosphorus, and

    52% nitrogen.

    A combination of activated sludge and with

    ozonation (as tertiary treatment) removed 8797%

    COD, and 97% BOD (Schmidt and Lange, 2000).

    Kabdash et al. (1996) showed that a combination of

    Reference

    Color

    %

    Removal

    Influent

    (mg/l)

    %

    Removal

    16.38 34,940 34.49 Saxena and Gupta (1998)

    65.84 34,940 81.29 Saxena and Gupta (1998)

    1875 93.8 Prasad and Gupta (1997)

    1875 83.5 Prasad and Gupta (1997)

  • Table 11

    Performance of physicochemical treatment processes

    Treatment process Parameters Reference

    TSS COD TOC AOX Color Lignin/Resin*

    or Fatty# acid

    Influent

    (mg/l)

    %

    Removal

    Influent

    (mg/l)

    %

    Removal

    Influent

    (mg/l)

    %

    Removal

    Influent

    (mg/l)

    %

    Removal

    Influent

    (PtCo)

    %

    Removal

    Influent

    (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:

    (Wet oxidation)

    10,000~19,000 80 3500~4100 80 Verenich et al. (2000)

    (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 8590 8591 9398 Zaidi et al. (1992)

    Nanofiltration 9396 99.299.9 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.Vira

    raghavan/Scien

    ceoftheTotalEnviro

    nment333(2004)3758

    48

  • Table 12

    Performance of aerobic biological treatment processes

    Treatment process Parameters Reference

    TSS BOD COD AOX Chlorinated phenolics

    Influent

    (mg/l)

    %

    Removal

    Influent

    (mg/l)

    %

    Removal

    Influent

    (mg/l)

    %

    Removal

    Influent

    (mg/l)

    %

    Removal

    Influent

    (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

    (period 1)

    270 >95* 660 (F) 60 22.5 36 0.255 74 Schnell et al.

    (2000a)

    (period 2) 270 >98 660 (F) 70 22.5 40 0.255 83 Schnell et al.

    (2000a)

    Pulp and

    paper mill

    96.63 96.8 96.92 Chandra (2001)

    Paper mill 1000 99 1533a 85 Knudsen et al.

    (1994)

    62

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 49Aerobic stabilization basin

    Kraft mill

    (period 1)

    270 >95 660 (F)chemical and biological methods (bioferic) resulted

    in 4050% additional removal of COD compared to

    the activated sludge system. Jahren and Oedegaard

    (period 2) 270 >98 660 (F) 73

    Kraft mill 206

    (1) F means fraction of COD or soluble COD.

    (2) Period 1: operating conditions for activated sludge-HRT 2 days, SRT

    (3) Period 1: operating conditions for aerated stabilization basin-HRT 15

    (4) Period 2: operating conditions for activated sludge-HRT 1 day, SRT 2

    (5) Period 2: operating conditions for aerated stabilization basin-HRT 15a Means soluble COD and * means BOD7.

    Table 13

    Performance of biological treatment processes

    Treatment process Parameters

    BOD COD Metha

    Influent

    (mg/l)

    %

    Removal

    Influent

    (mg/l)

    %

    Removal

    Influe

    (mg/l)

    Biological reactors

    HRC (TMP Mill) 1150 98 3340 79

    Total plant

    efficiency

    1490 99 5000 86

    MBBR

    (HRT 4.5 hrs)

    6575 8595

    SBR 98 8593

    Anaerobic (GAC) 1400 50

    Kraft mill Windsor 1429a 69 2036a 59 1095a

    a Unit in g/d.22.5 53 0.255 85 Schnell et al.

    (2000a)(1999) found that Kaldnes (anaerobic followed by

    aerobic) moving bed biofilm reactor at 55 jC re-moved about 60% of soluble COD from TMP

    22.5 55 0.255 86 Schnell et al.

    (2000a)

    5 1770 Chernysh et al.

    (1992)

    25 days, Temp. 30 jC, VSS 1800 mg/l.days, SRT 15 days, Temp. 30 jC, VSS 60 mg/l.5 days, Temp. 30 jC, VSS 2800 mg/l.days, SRT 15 days, Temp. 20 jC, VSS 70 mg/l.

    Reference

    nol Color

    nt %

    Removal

    Influent

    (mg/l)

    %

    Removal

    Magnus et al. (2000a)

    Magnus et al. (2000a)

    Borch-Due et al. (1997)

    Franta and Wilderer (1997)

    1300 50 Jackson-Moss et al. (1992)

    84 Dufresne et al. (2001)

  • whitewater. A combined anaerobicaerobic treat-

    ment system was suggested to treat bleached kraft

    pulp and paper mill effluents (Duncan and Thia,

    1992; Wang et al., 1997). Lescot and Jappinen

    (1994) showed that a combination of an aerated

    lagoon and a secondary clarifier was able to treat

    bleached kraft mill effluent in Finland resulting in

    87%, 96%, 65%, 53%, and 22% removal of SS,

    BOD7, COD, AOX, and color, respectively. Carlson

    et al. (2000) reported that 77%, 9899%, 72%, and

    81% removal of COD, BOD, TN, and TP, respec-

    tively, was achieved after upgrading the aerated

    basin at Monsteras mill. The system comprised of

    an anoxic selector, an aerated basin, and a secondary

    clarifier in series. The removals of extractives, resin

    and fatty acids were 96% and 98%, respectively,

    whereas the system reduced Microtoxk by 99%.Welander et al. (2000) reported on the performance

    of an aerobic biological process called LSP (low

    sludge production) to lower the biological sludge by

    8090%. The system configuration was primary

    clarifier, aeration basin, and secondary clarifier. A

    combination of physicochemical, biological, and ef-

    fluent polishing in the aerated lagoon removed 98

    Table 14

    Selected anaerobic process performance (Bajpai, 2000)

    Mill location Wastewater source Loading rate

    (kg COD/m3/d)

    BOD5(mg/l)

    COD

    (mg/l)

    TSS

    (mg/l)

    BOD5Removal%

    COD

    Removal%

    Anaerobic contact reactor

    Hylte Bruk

    AB, Sweden

    TMP,

    groundwood, deink

    2.5 1300 3500 520 71 67

    SAICA,

    Zaragoza, Spain

    Waste paper alkaline

    cooked straw

    4.8 10,000 30,000 94 66

    Hannover paper,

    Alfred, Germany

    Sulfite effluent

    condensate

    4.2 3000 6000 97 85

    Niagara of Wisconsin

    of USA

    CTMP 2.7 2500 4800 3300 96 77

    SCA Ostrand,

    Ostrand, Sweden

    CTMP 6 3700 7900 50 40

    Alaska Pulp

    Corporation, Sitka

    Sulfite condensate,

    bleach caustic and

    pulp whitewater

    3 3500 10,000 85 49

    Upflow anaerobic sludge blanket

    Celtona, Holland Tissue 3 600 1200 75 60

    Southern paper

    converter, Australia

    Wastepaper 10 10,000 > 80 > 80

    9

    12.

    18

    20

    13.

    15

    12.

    35

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 375850Davidson,

    United Kingdom

    Linerboard

    Chimicadel,

    Friulli, Italy

    Sulfite

    condensate

    Quesnel River

    Pulp, Canada

    TMP/CTMP

    Lake Utopia

    Paper, Canada

    NSSC

    EnsoGutzeit, Finland Bleached

    TMP/CTMP

    McMillan Bloedel,

    Canada

    NSSC/CTMP

    Anaerobic filter:

    Lanaken, Belgium

    CTMP

    Anaerobic fluidized Paperboardbed: D Aubigne, France1440 2880 90 75

    5 12,000 15,600 90 80

    3000 7800 60 50

    6000 16,000 80 55

    5 1800 4000 75 60

    7000 17,500 80 55

    7 4000 7900 85 70

    1500 3000 83.3 72.2

  • 7077%, and 8094% removal of BOD, COD, and

    resin and fatty acids was provided by biological

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 51treatment. Tardif and Hall (1997) reported 100%,

    96%, 76%, and 34% removal of resin acid (RA),

    fatty acid (FA), dissolved chemical oxygen demand

    (DCOD), and total dissolved solids (TDS), respec-

    tively at temperatures 2040 jC by an SBR. AnMBR removed 100% RA and FA, 84% DCOD, and

    37% TDS at 4050 jC. Malmquist et al. (1999)reported a COD removal of 7090% 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 1065% 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 1114.

    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%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, 8090%

    BOD7, 50% AOX, 90% ClO3. Shaw et al. (2002)

    showed that a combination of aerobic reactor fol-

    lowed by anaerobic reactor removed 94% color, and

    66% TOC. Schnell et al. (1997) found that 8795%,and 75%, respectively (Das and Jain, 2001) evenwhen the production has been increased. Trotter

    (1990a,b) evaluated biotechnological applications

    such as genetic modification of plant, biopulping,

    and biobleaching to reduce chlorinated organic com-

    pounds as an emerging technology for internal pollu-

    tion control. Enzyme treatment for pulp dissolving,

    improving tensile properties by treating mechanical

    pulp with white rot organisms and enzymatic beating

    of chemical pulps, hemicellulose, and decolorization

    by white rot fungi were given as possible biotechno-

    logical options.

    Among the various treatment processes currently

    used for pulp and paper effluent treatment, only a few

    are commonly adopted by pulp and paper industry

    especially for tertiary treatment. Some of the treatment

    processes such as ozonation, fentons reagent, adsorp-

    tion, and membrane technology are efficient but are

    more expensive. Sedimentation is the most commonly

    adopted process by the pulp and paper industry to

    remove suspended solids. The performance data given

    by Springer (2000) showed 8090% removal of

    initial suspended solids from most of the mills except

    a deinking mill. Flotation is also commonly used in

    the pulp and paper industry but most of the time as a

    tertiary treatment. Coagulants are a preferred option

    for removing turbidity and color from the wastewater.

    Reported results have shown that they are also capable

    in reducing COD, TOC, and AOX to some extent.

    Among the coagulants, modified chitosan showed the

    highest performance for color and TOC removal.

    Polyelectrolytes are better than alum and they produce

    less sludge and pose less problems with sludge

    dewaterability than alum. Adsorption processes are

    useful to remove color, COD, and AOX. They are

    rather expensive and it is not known whether the pulp

    and paper industry are employing them widely. How-

    ever, laboratory-scale experiments are usually

    reported. Activated charcoal, 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

  • ious authors lead to a better understanding of the

    various treatment processes and their adaptability.

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 375852is not commonly adopted in most countries, not even

    in Europe but it is emerging in North America.

    Membrane processes are efficient in reducing over

    90% of color, TSS, and AOX in most of the cases.

    Fouling of membranes is a problem in the case of

    soft wood effluent treated by membrane filtration. In

    secondary treatment processes, activated sludge is

    the most commonly used. UASB and fluidized beds

    are also gaining in use recently. The problem with

    activated sludge is sludge bulking. Reported results

    have shown that activated sludge can remove all

    types of the pollutants pertaining to the pulp and

    paper industry. However, the removal of AOX is

    below 50%, BOD around 95% in most of the mills,

    and COD removal averages around 70%. This sys-

    tem is also efficient in removing chlorinated phenolic

    compounds (over 75%) most of the time. Dalentoft

    and Thulin (1997) reported that Kaldnes (anaero-

    bic + aerobic) process in series with an activated

    sludge, could be an efficient, stable, and a compet-

    itive combination process, considering both invest-

    ment and operating costs. Aerated lagoons are

    efficient in removing BOD over 95% in most of

    the reported results. COD removals are moderate

    between 60% and 70%, AOX around 50%, and a

    high removal (85%) for chlorinated phenolics. An-

    aerobic contact reactors are efficient in removing

    biodegradable organic compounds such as BOD,

    and COD. The performance data from various mills

    showed that anaerobic contact reactors were able to

    remove over 90% of BOD and 65% of COD in most

    of the cases. Anaerobic filters and fluidized bed

    reactors are suitable in reducing organic pollutants

    only. Both the reactors achieve almost same efficien-

    cy in terms of BOD (>80%), and COD (>70%)

    removal (refer to Table 14 for details). UASBs are

    able to remove over 80% of BOD and 5080% of

    COD in most of the mills (refer to Table 14 for

    details). Fungi are efficient in removing especially

    color and COD from the pulp mill wastewater.

    Removal of color using white rot fungi was above

    80% in most of the reported cases and COD removal

    was above 75%. White rot fungi particularly P.

    chrysosporium and C. versicolor are suitable for

    efficient degradation of the refractory material (Baj-

    pai and Bajpai, 1994). The reported results have

    shown that high removals are achieved in the caseof the combination of two or more physicochemicalFor example, Jemaa et al. (2000) stated that chemical

    precipitation, evaporation, membrane technology, and

    ion exchange were the established options for the

    removal of colloids and metal ions. Perez et al.

    (2002a) conducted an economic evaluation of various

    advanced oxidation processes to remove organic con-

    taminants. Ozonation was stated to be effective but

    rather an expensive process. Rintala and Puhakka

    (1994) stated that operation costs of the activated

    sludge was about three times greater than that of

    anaerobic systems. Bajpai (2000) presented compara-

    tive costs of the anaerobic and activated sludge treat-

    ment, which showed that activated sludge was almost

    twice as expensive as anaerobic reactors. The recent

    paper by Perez et al. (2002b) reported a high efficiency

    of COD and TOC removal when iron ion was used

    with ozone/UV treatment system. The authors showed

    that the presence of iron ion in the ozone/UV treatment

    brought a complete removal of COD in 90 min while

    TOC removal was higher than 90%. The report stated

    that the overall cost was reduced by 50%, which is

    encouraging news for the industry. Mobius and

    Cordes-Tolle (1994) suggested that sand filters, bio-

    filters, low capacity trickling filters, flocculation and

    precipitation with inorganic salts in combination with

    filtration or flotation are the emerging systems for

    adoption by pulp and paper mills.

    8. Conclusions

    Based on the above literature review, the following

    conclusions are drawn:

    (i) Both aerobic and anaerobic treatment systems

    are feasible to treat wastewater from all types

    of pulp and paper mills except that bleachingprocesses or combination of physicochemical and

    biological processes. The confirmation of the reported

    results, their applicability in the real field, and eco-

    nomic evaluations are very important in adopting the

    process. For example, the anaerobic treatment process

    for pulp and paper mill effluents is still in an initial

    application phase.

    However, comprehensive evaluations made by var-kraft effluents are less suitable for treatment by

  • pulp and paper mill effluent treatment.

    D. Pokhrel, T. Viraraghavan / Science of the Total Environment 333 (2004) 3758 53(viii) More studies are needed on the removal of

    AOX and chlorinated phenolic compounds.

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