Advances in Environmental Research 5 Ž2001.

175᎐196

Aquatic toxicity from pulp and paper mill effluents:

a review

Muna Ali, T.R. SreekrishnanU

Department of Biochemical Engineering and Biotechnology, Indian Institute of Technology-Delhi, Hauz Khas, New Delhi
110 016, India

Abstract

Effluents from pulp and paper mills are highly toxic and are a major source of aquatic pollution. More than 250
chemicals have been identified in effluents which are produced at different stages of papermaking. Their toxic nature
is derived from the presence of several naturally occurring and xenobiotic compounds which are formed and released
during various stages of papermaking. This article reviews the origins and effects of major pollutants present in pulp
and paper mill effluents. The progress made in their reductionrelimination via aerobic, anaerobic and abiotic routes,
as well as further scope, is also discussed. 䊚 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Pulp and paper mill effluents; Aquatic pollution; Priority pollutants; Toxicity; Aerobic and anaerobic treatment

1. Introduction approximately 40᎐45% of the original weight of the

Urban industrial activity has long been identified as
a major source of contaminants for aquatic environ-
ments, via atmospheric deposition and wastewater dis-
charge. The pulp and paper industry is the sixth largest
polluter Žafter oil, cement, leather, textile, and steel
industries. discharging a variety of gaseous, liquid, and
solid wastes into the environment. Potential pollutants
from a pulp and paper mill fall into four principal
categories ŽTable 1.. It is the pollution of water bodies,
however, which is of major concern because large
volumes of wastewater are generated for each metric
ton of paper produced, depending upon the nature of
the raw material, finished product and extent of water
reuse. Since the pulp produced corresponds to only
U and dibenzofurans Ždioxins and furans., are recalcitrant
Corresponding author. Tel.: q91-116591014; fax: q91-
116868521.
E-mail address: sree@dbeb.iitd.ernet.in ŽT.R. Sreekrishnan ..
wood, the effluents are heavily loaded with organic
matter. These effluents cause considerable damage to
the receiving waters if discharged untreated since they
have a high biochemical oxygen demand ŽBOD.,
chemical oxygen demand ŽCOD., chlorinated com-
pounds Žmeasured as adsorbable organic halides, AOX.,
suspended solids Žmainly fibers., fatty acids, tannins,
resin acids, lignin and its derivatives, sulfur and sulfur
compounds, etc. While some of these pollutants are
naturally occurring wood extractives Žtannins, resin
acids, stillbenes, lignin., others are xenobiotic com-
pounds that are formed during the process of pulping
and paper making Žchlorinated lignins, resin acids and
phenols, dioxins, furans., thereby turning pulp and pa-
per mill effluents into ‘a Pandora’s box of waste chemi-
cals’ ŽPeck and Daley, 1994.. Some of the pollutants
listed above, notably, polychlorinated dibenzodioxins
to degradation and tend to persist in nature. They are
thus known as persistent organic pollutants ŽPOPs. and

1093-0191r01r$ - see front matter 䊚 2001 Elsevier Science Ltd. All rights reserved.
PII: S 1 0 9 3 - 0 1 9 1 Ž 0 0 . 0 0 0 5 5 - 1
176 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
have been classified as ‘priority pollutants’ by the
United States Environmental Protection Agency
ŽUSEPA, 1998. and figure in the Priority Substances
List 1 ŽPSL-1. of the Canadian Environmental Protec-
tion Act ŽCEPA, 1992. as well as the ‘dirty dozen’
group of persistent organic pollutants ŽPOPs. identified
by United Nations Environment Program ŽUNEP,
1995..
It is well established that many of these contami-
nants are acute or even chronic toxins. Chlorinated
organic compounds, which include dioxins and furans,
have the ability to induce genetic changes in exposed
organisms ŽNestmann, 1985.. In particular, DNA-
damaging agents have been shown to induce inherited
genetic defects and cancer ŽLoprieno, 1982; Brusick,
1987; Easton et al., 1997., with dioxins being named as
‘known human carcinogens’ by the World Health Orga-
nization ŽWHO, 1997.. This has resulted in a growing
concern about the potential adverse effects of genotox-
icants on aquatic biota and public health through the
contamination of drinking water supplies, recreational
waters, or edible organic species ŽLoper, 1980; McGe-
orge et al., 1985.. Recognizing the potential risk early
on, WHO Ž1984., the USEPA Ž1985., and the Japan
Ministry of Health and Welfare, JIS Ž1989. initiated
control guideline levels for the principal chlorinated
organic compounds in drinking water, which have now
been adopted by most countries. It has been noticed
that the toxicity is not restricted to the aquatic ecosys-
tem alone; rather, some of the residual toxicity from
pulp and paper mill effluents also ultimately makes an
appearance in paper products such as coffee filters,
Table 1
Potential pollutants from pulp and paper mills
Type of pollutant
Gases
Effluents
Particulates
Solid wastes
paper cups and plates, facial tissues and, surprisingly,
in bread-utilizing high grade pulp too.
This paper critically reviews the current knowledge
of toxic chemicals and other objectionable components
Žpollutants. present in pulp and paper mill effluents,
compares several aerobic and anaerobic treatment
processes available for treating these effluents and
concludes with a focus on urgently required research
needs in this area.
2. Manufacture of paper
Papermaking involves five basic steps and each step
can be carried out by a variety of methods. Thus, the
final effluent is a combination of wastewaters from
each of the five different unit processes and the meth-
ods employed therein, viz.:
1. Debarking converts the plant fiber into smaller
pieces called chips and removes the bark. In this
step, the nature of the raw material used, i.e. hard
wood, softwood, agroresidues, results in the trans-
fer of tannins, resin acids, etc. present in the bark
to process waters. For instance, softwoods contain
a much higher quantity of resin acids than hard-
woods ŽLeach and Thakore, 1977., whereas
agroresidues may not contain resin acids at all.
2. Pulping turns the chips into pulp. This process
removes the majority of lignin and hemicellulose
content from the raw material, resulting in a cellu-
Typical example and source
Malodorous gases, e.g. H2 S and mercaptan
from Kraft pulping and recovery processesU
Oxides of sulfur, e.g. SO2 and SO3 from
recovery furnaces and lime kilnsU
Suspended solids including bark particles
fiber pigments, dirt from debarkingU
Dissolved colloidal organics, e.g.
hemicellulose, sugars, sizing agentsU
Chromatophores mainly lignin compoundsU
Chlorinated compounds from bleach plantU
Dissolved inorganics, e.g. NaOH, Na2 SOU4
Thermal loadsU
Fly ash from coal fired power boilersU
Char from bark burnersU
Sludges from primary and secondary treatment
and recovery sectionU
Solids such as grit, bark and other mill wastes
 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196 177

lose-rich ‘pulp’. Pulping can be carried out by sev-
eral different methods, such as mechanical, semi-
chemical, Kraft, sulfite pulping, etc., and once again
the raw material utilized decides the nature and
quantity of transfer of long chain fatty acids and
resin acids to process waters.
3. Bleaching is employed on the brown pulp obtained
after pulping in order to meet the desired color
dictated by product standards. Several bleaching
agents, including chlorine, chlorine dioxide, hydro-
gen peroxide, oxygen, ozone, etc. maybe used ei-
ther singly or in combination. It is in this step that
lignin, phenols, resin acids, etc. get chlorinated and
transformed into highly toxic xenobiotics.
4. Washing removes the bleaching agents from the
pulp. Generally an alkali Žcaustic soda. is used to
extract color and bleaching agents from the pulp
and hence this process is also known as the alkali
extraction stage ŽE1..
5. Paper and paper products are finally produced by
mixing the washed pulp with appropriate fillers
Žclay, titanium dioxide, calcium carbonate. and siz-
ing agents Žrosin, starch..
The various types of wastewaters produced from
different unit processes are summarized in Table 2.
Thus, it is apparent that no two paper mills may
discharge identical effluents since they may adopt any
combinationŽs. of the number of technologies available
in each of the unit processes involved in manufacturing
pulp and paper. As a result, no single specific tech-
nology can be applied to the treatment of effluents
from all the mills since process diversities may preclude
its acceptability. Hence, it should be borne in mind that
each pulp and paper mill is a large, complex, highly
interactive operation and that perturbations in one
area may have a greater impact than expected in an-
other area. Consequently, the treatment of wastewaters
from pulp and paper mills tends to become mill-specific
and it is for this reason that the knowledge of possible
contaminants present in the wastewater, their origins
and degree of toxicity and available treatment tech-
nologies becomes so essential.
2.1. Tannins
Tannins are, by definition, polar phenolic polymeric
compounds ranging in weight from 500 to 3000 grmol
ŽWhite, 1957. and are highly reactive with proteins
ŽHaslam, 1966; Gupta and Haslam, 1980.. Wastewater
derived from the debarking process in paper mills has
been found to contain large amounts of tannins that
contribute as much as up to 50% of the COD of these
wastewaters ŽField et al., 1988.. Moreover, since the
tannins tint these wastewaters, they tend to absorb
more light and heat and retain less oxygen than un-
processed water, thereby negatively affecting the
aquatic flora and fauna. The toxicity of tannins to
several enzymes has been well established ŽLoomis and
Battaile, 1966; Tamir and Alumot, 1969; Daiber, 1975;
Gupta and Haslam, 1980; Korczak et al., 1991; Sierra-
Alvarez et al., 1994.. They are also known to exhibit
methanogenic toxicity to an extent that depends on the
degree of polymerization ŽField et al., 1988.. The hy-
drogen-bonding reactions with proteins are postulated
to cause toxicity to bacteria, because such interactions
interfere with the functioning of enzymes ŽWhite, 1957;
Loomis and Battaile, 1966; Strumeyer and Malin, 1969;
Tamir and Alumot, 1969; Haslam, 1974; Daiber, 1975;
Ladd and Butler, 1975; Gupta and Haslam, 1980..
Tannin monomers have low methanogenic toxicity be-
cause of their limited cross-linking capacity, whereas
higher molecular weight tannin polymers and humic
acids have low toxicity because they are too big to
penetrate the bacterial proteins. The highest toxicity is
found in oligomeric tannins ŽWhite, 1957. due to their
ability to form strong hydrogen bonds with proteins
ŽField et al., 1989..
Several studies have been conducted to determine
the toxicity of tannins to microorganisms, especially to

Table 2
Types of wastewaters produced from various unit processes

Unit process Type of wastewater

Digester Leaks and spills of black liquor and gland cooling water
Pulp washing Final washrunbleached decker wash
Centricleaners Rejects containing fibres and gritrsand
Pulp bleaching Ži. Caustic extraction wastewater with high pH chlorolignin
Žii. Chlorination stage wastewater with low pH
Paper machine White water contains fibres, talc and sizing agents
Chemical recovery Spills of black liquor in the evaporators and foul
condensates
178 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
anaerobes ŽField and Lettinga, 1987; Temmink et al.,
1989; Korczak et al., 1991; Sierra-Alvarez et al., 1994..
In all of these investigations, methanogenic bacteria
were chosen as the model trophic group of anaerobic
community since they are responsible for the rate-
determining step. For example, in a study to evaluate
the effect of a tannin on the methane production from
granular sludge ŽField and Lettinga, 1987., it was con-
cluded that gallotannic acid, a hydrolysable tannin, is a
potent inhibitor of methanogenesis. It was found that
the toxicity persisted despite the rapid degradation of
gallotannic acid to volatile fatty acids and methane.
Concentrations representing 30% inhibition approxi-
mated to 700 mgrl of gallotannic acid. Toxicity, in
severe cases, resulted in a loss of activity that was
either recovered very slowly or was completely lost over
long assay periods Ž2 months. ŽField and Lettinga,
1987.. The authors hypothesized that the toxicity may
have involved the ‘tanning’ of proteins Žsuch as en-
zymes. located at accessible sites in the methanogenic
bacteria. This study thus indicated that tannins are
potent inhibitors of methanogens and that their pres-
ence should be considered while evaluating the feasibil-
ity of anaerobic waste treatment processes. ŽField and
Lettinga, 1987..
In an experiment to study the acute and sub-acute
toxicity of bark tannins in carp and the detoxifying
effect of polymerization, the bark of Norway spruce
Ž Picea abies. was added to aquaria containing carp
Ž Cyprus carpio L.. under semi-static Žsub-acute toxicity.
and flow-through Žacute toxicity. conditions ŽTemmink
et al., 1989.. It was demonstrated that condensed tan-
nins from spruce bark are toxic, not only to
methanogens at concentrations present in the paper
mill wastewaters ŽField et al., 1988., but also to aquatic
organisms, like fish ŽTemmink et al., 1989.. The oxida-
tive polymerization of bark tannins has been shown to
be an effective way of reducing their toxicity in paper
mill wastewaters since it abolishes aquatic toxicity com-
pletely ŽTemmink et al., 1989..
2.2. Resin acids
Resin acids are tricyclic diterpenes that occur natu-
rally in the resin of tree wood and bark and are
transferred to process waters during pulping opera-
tions. They are weak hydrophobic acids and are toxic to
fish at concentrations of 200᎐800 ␮grl in wood pro-
cessing wastewaters ŽMcFarlane and Clark, 1988.. Resin
acids have been measured in Chemi-Thermo Mechani-
cal Pulping ŽCTMP. wastewaters at concentrations as
high as several hundred parts per million ŽMcFarlane
and O’Kelly, 1988., even though the aqueous solubili-
ties of individual resin acids are in the range of 3᎐6
mgrl ŽNyren´ and Back, 1958.. According to Leach
and Thakore Ž1976., 60᎐90% of the toxicity in CTMP
effluents can be attributed to resin acids alone. It has
been observed that wastewater pH strongly affects the
toxicity and solubility of these acids with measured 96 h
LC 50 s for resin acids ranging from 0.4 to 1.7 mgrl for
rainbow trout ŽMcLeay, 1987.. The most commonly
monitored resin acids in aqueous pulping discharges
include abietic acid, dehydroabietic acid, neoabietic
acid, pimaric acid, isopimaric acid, sandaracopimaric
acid, levopimaric acid and palustric acid. Isopimaric
acid is considered to be the most toxic amongst all the
resin acids ŽWilson et al., 1996..
2.2.1. Anaerobic treatment of resin acids
Several workers have reported the accumulation of
resin acids in anaerobic reactors treating mechanical
pulping wastewaters ŽHo, 1988; McFarlane and Clark,
1988; Sierra-Alvarez and Lettinga, 1990; Kennedy et
al., 1992.. The toxicity of resin acids to total toxicity in
bleached CTMP ŽBCTMP. has been quantified using
the anaerobic toxicity assay ŽATA. ŽMcCarthy, et al.,
1990.. They concluded that the anaerobic toxicity in
BCTMP wastewaters was partitioned between the solu-
ble and fiber fractions and that the toxicity removed
with the fiber was methanol-soluble. Although resin
acids inhibited anaerobic activity, the toxicity of BC-
TMP wastewaters to anaerobic bacteria could only be
partially explained by the presence of resin acids. The
possibility of resin acids having synergistic effects in
conjunction with other compounds in BCTMP wastew-
ater toxicity could not be ruled out. It can be safely
concluded that the toxicity of wastewaters containing
wood resin constituents should be not be ruled out
when evaluating the feasibility of anaerobic wastewater
treatment processes ŽSierra-Alvarez and Lettinga,
1990..
2.2.2. Aerobic degradation of resin acids
Aerobic biological processes are most commonly
used for full-scale treatment of pulp and paper mill
effluents, but not specifically for resin acid degradation.
A few studies have been conducted to investigate the
feasibility of aerobic processes for degradation of resin
acids ŽHemingway and Greaves, 1973; Leach et al.,
1977; Qiu, et al., 1988; Zender et al., 1994.. In one
significant study, aerobic lagoons were employed to
treat bleached Kraft wastewaters from a pulp and
paper mill employing softwoods ŽZender et al., 1994..
The removal and biotransformation of resin acids dur-
ing secondary treatment in an aerobic lagoon was also
examined. It was observed that the total treatment
system removed 96% of the influent resin acids. The
major resin acids found to be removed were abietic
acid, dehydroabietic acid, and a variety of hydro-
genated resin acid metabolic products.
 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
2.2.3. Comparison between anaerobic and aerobic
degradation of resin acids
The literature contains several reports of anaerobic
treatment studies at laboratory ŽBissaillon et al., 1991.,
pilot and full scale ŽAndersson et al., 1987; McFarlane
and O’Kelly, 1988; Schnell et al., 1989. in which resin
acid removal was observed. However, there does not
seem to be a clear consensus on the conditions re-
quired for the efficient removal of resin acids. Also, the
reported behavior of individual resin acids under
anaerobic conditions seems to differ substantially ŽHall
and Liver, 1996a..
The fate and effect of resin acids in anaerobic and
aerobic biological treatment systems were compared
under batch reactor test conditions ŽHall and Liver,
1996a.. They concluded that a non-acclimated anaer-
obic biomass was not capable of significant degradation
of resin acids under batch anaerobic conditions, even
after exposure times of up to 24 days. Inhibition of
methanogenic activity of the anaerobic consortium was
noted at initial resin acidrbiomass ratios exceeding
0.0031 mg resin acidrmg VSS. It was observed that the
inhibited methanogenic populations were capable of
acclimation to high concentrations of resin acids after
7᎐13 days of exposure ŽHall and Liver, 1996a.. Additio-
nally, it was reported that a non-acclimated activated
sludge aerobic biomass was capable of the rapid degra-
dation of a high initial concentration of resin acids to
non-detectable levels under batch conditions in 2᎐3
days. However, the time required for removal appeared
to be independent of the batch reactor biomass con-
centration and no inhibition occurred at high concen-
trations ŽHall and Liver, 1996a..
In order to assess the contribution of partitioning on
biosolids to the overall removal of resin acids in batch
assays, solutions of five resin acids Žabietic, dehydroabi-
etic, pimaric, isopimaric and palustric acids. were con-
tacted with suspensions of non-acclimated, inactivated
anaerobic and aerobic biomass ŽHall and Liver, 1996b..
Both types of biomass exhibited resin acid partitioning
rates that were significantly greater than the rates of
removal by degradation. With non-acclimated anaer-
obic biomass, the partitioning of resin acids onto bio-
solids followed a two-phase process in which the ma-
jority of resin acids were first rapidly removed to the
biomass, followed by a slower removal phase that re-
quired from 0 to more than 5 days to reach equilib-
rium, with lower biomass concentrations requiring
longer equilibration times. The authors noted that the
partitioning of resin acids onto an anaerobic biomass
could not be described as a reversible adsorption
process. On the contrary, a constant fraction of each
resin acid studied was found to partition into the
biomass phase with the adsorbed fractions being:
pimaric acid 90%; isopimaric and abietic acids 89%;
palustric acid 86%; and dehydroabietic acid 77%. With
179
a non-acclimated aerobic biomass, equilibrium parti-
tioning also followed a two-phase process, but equilib-
rium was achieved after 12 h of contact and the parti-
tioning could be adequately described by a linear parti-
tioning model ŽHall and Liver, 1996b.. Dehydroabietic
acid was found to be the most weakly associated with
biomass in both the anaerobic and aerobic experiments
ŽHall and Liver, 1996b.. There have also been other
reports that document the degradation of resin acids
Žwith the exception of dehydroabietic acid. in an up-
flow anaerobic sludge blanket ŽUASB. reactor, al-
though anaerobes can acclimate to high levels of dehy-
droabietic acid ŽMcFarlane and Clark, 1988..
2.2.4. Microbiological degradation of resin acids
Apart from examining mixed consortia of aerobic
and anaerobic microbes for resin acid degradation,
many workers have employed pure cultures of several
bacteria and some fungi also. These include Bacillus
spp., E. coli, Fla¨ obacterium spp., Pseudomonas, Acali-
genes eutrophus, Anthrobacter, Sphinomonas, Zooglea,
Commamonas, Mortierella isabella, Chaetomium cochli-
olidae, Corticum sasaki, and Fomes annosus ŽMohn,
1995; Liss et al., 1997; Morgan and Wyndham, 1997..
Many mesophilic bacteria have been isolated and char-
acterized for their ability to degrade resin acids. For
instance, Wilson et al. Ž1996. isolated two species of
Pseudomonas, IpA-1 and IpA-2, which were capable of
growing on isopimaric acid as the sole carbon source
and electron donor. These isolates were also found to
grow on pimaric acid and dehydroabietic acid. A com-
parison of their resin acid removal capacities showed
that IpA-1 and IpA-2 removed 0.56 and 0.13 ␮molrmg
protein per h. In a related study with bacteria, Morgan
and Wyndham Ž1996. grew Commamonas and Alcali-
genes in the presence of 300 mgrl resin acids. They
reported that after 8 days of incubation, these bacteria
were able to degrade six of the resin acids tested.
Genetic relatedness of these strains was also investi-
gated by using enterobacterial, repetitive intergenic
consensus sequences to amplify genomic DNA frag-
ments. A few species of fungi have also been reported
to possess resin acid degrading properties. For exam-
ple, Ophiostoma and Lecythophora spp. were grown on
lodgepole pine sapwood chips at a concentration of 50
␮g myceliumrg wood at 23⬚C ŽWang, et al., 1995. and
resin acid degradation of up to 67% was obtained.
Although several mesophilic resin acid degrading
microbes have been isolated and characterized, there
are very few reports regarding the use thermophilic
species. Recently, Mohn et al. Ž1998., obtained five
isolates, three from a thermophilic Ž55⬚C. bioreactor
and two from forestry waste compost. Of these, three
were found to use abietanes, abietic acid and dehydro-
abietic acid as the sole organic substrate, but were
unable to grow on pimeranes, pimaric acid and isopi-
180 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
maric acid. These isolates were found to grow between
pH values of 6᎐8 and temperatures of 30᎐60⬚C. The
16S ribosomal DNA of these isolates has been se-
quenced for phylogenic analysis. In an extension of the
same study, a semi-continuous enrichment method was
used to isolate two thermophilic Rubri¨ i¨ ax spp. strains,
namely DhA-73 and DhA-71. These were found to
completely degrade dehydroabietic acid ŽYu and Mohn,
1999.. The use of thermophilic bacteria is an attractive
option for the treatment of forest industry wastewaters,
since they are released at high temperatures and can
thus support the growth of thermophilic species.
2.3. Fatty acids
In addition to resin acids, unsaturated fatty acids
Ž16-C and 18-C., such as oleic acids, linoleic acid and
linolenic acid from pulp and paper mills employing
softwood are also a source of toxicity to fish, especially
salmonoids ŽLeach and Thakore, 1973; Voss and Rap-
somatiotis, 1985.. Long chain fatty acids ŽLCFA. have
been shown to inhibit methanogenic bacteria ŽHanaki,
1981; Koster and Cramer, 1987. in particular the aceto-
clastic bacteria ŽHanaki, 1981.. This makes the anaer-
obic treatment of wastewaters relatively troublesome
since methanogenic bacteria play a crucial role in
anaerobic wastewater treatment. In rumen, where
methane is produced excessively from hydrogen Žand
not from acetate . ŽHungate, 1975., LCFA were found
to be inhibitory to methane production in vivo ŽCzer-
kawski et al., 1966. and in vitro ŽDemeyer and Hen-
drickx, 1967.. Further studies on the inhibitory effect of
LCFA on the anaerobic digestion process were con-
ducted in batch experiments using synthetic substrates,
such as sodium oleate, fatty acids mixture, powdered
milk, acetate and n-butyrate ŽHanaki, 1981.. It was
found that the addition of LCFA caused the appear-
ance of a lag period in methane production from
acetate and in the degradation of LCFA and a syn-
thetic substrate, n-butyrate. Methane production from
hydrogen proceeded without a lag period although its
rate was lowered. The fermentation of glucose, how-
ever, was not inhibited ŽHanaki, 1981.. Since fatty acids
can be degraded anaerobically, it is not entirely neces-
sary to prevent them from entering the anaerobic reac-
tors, but the concentrations present in the wastewater
should be kept below the maximum allowable level so
that they do not cause significant inhibition to the
anaerobic bacteria. Another known method of check-
ing the inhibitory effect of LCFA is the addition of
calcium ions ŽCa2q . to the wastewater, because the
calcium salts of LCFA are relatively insoluble. Hanaki
Ž1981. analyzed the effect of CaCl 2 addition in cases
where the methanogenic sludge had already been ex-
posed to a fatty acids mixture. Four different exposure
periods, namely, 5 min, and 4, 8 and 24 h were selected.
The inhibitory effect was remarkably reduced when the
exposure period was 5 min. The lag period became
longer with an increasing exposure period of the sludge
to the fatty acid mixture. The addition of CaCl 2 could
not reduce the inhibitory effect of the fatty acid mix-
ture at all when the exposure period was 24 h. Another
calcium salt, calcium carbonate ŽCaCO 3 ., was tested
for its ability to reduce the inhibitory effect of LCFA.
However, being insoluble in water, CaCO 3 could hardly
reduce the inhibitory effect of the fatty acid ŽHanaki,
1981..
The fatal inhibition of methanogenesis by long chain
fatty acids ŽLCFA. can be prevented by adding Ca2q,
provided it is done so during the early stages of expo-
sure to a methanogenic population. Koster Ž1987., us-
ing lauric acid, studied the time available after the start
of exposure in which to add Ca2q. Lauric acid was
chosen as the model long chain acid because it is the
strongest potential inhibitor for methanogens among
the acids that can be present in any wastewater ŽKoster
and Cramer, 1987.. It was observed that 7.5 mM sodium
laurate caused 94% inhibition of methanogens using
acetate as the sole carbon source. At an exposure time
of zero, there was no inhibition. After 3 min of expo-
sure, 40% of the methanogenic activity was lost, while
after 20 min exposure, only 33% of the original
methanogenic activity remained. A 6-h exposure period
resulted in the retention of 4% of uninhibited activity
ŽKoster, 1987.. This was similar to the remaining activ-
ity if there was no addition of CaCl 2 ŽKoster and
Cramer, 1987.. Thus, it was concluded that after an
exposure time of 6 h, calcium addition did not produce
any immediate restoration of the methanogenic activ-
ity. The necessity of an almost immediate addition of
calcium chloride to save the methanogenic potential of
the sludge if exposed to lauric acid indicates that the
acid interacts very rapidly with the sludge. It is conjec-
tured that the rapid disappearance from solution of
lauric acid in the presence of methanogenic sludge was
caused by precipitation with calcium and other metal
ions from the cell contents. This loss of vital ions from
the cells could account for the loss of their
methanogenic activity ŽKoster, 1987..
2.4. Halogenated compounds
The pulp obtained from the pulping section is brown
in color and is bleached to increase its brightness.
Bleaching of pulp is accomplished in several stages, to
some of which chlorine is added in different forms. In
majority of the mills in the developing countries, ele-
mental chlorine is employed for bleaching, whereas it
is banned in the developed world. Instead bleaching
is accomplished by chlorine dioxide, oxygen, ozone,
hydrogen peroxide, etc. Elemental chlorine reacts with
lignin and other organic matter present in the pulp,
 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
thereby giving rise to chlorinated compounds that are
extracted with alkali ŽEklund and Josefsson, 1978..
Investigations carried out in the early eighties in the
US, Canada, Scandinavia and Japan revealed the pres-
ence of chlorinated lignosulfonic acids, chlorinated
resin acids, chlorinated phenols, and chlorinated hydro-
carbons in pulping and bleaching effluents ŽKringstad
and Lindstrom, 1984.. Dioxins and furans, two classes
of compounds that contain some of the most toxic
chemical substances ever known, have also been found
in these wastewaters. These toxic compounds are also
found to be produced when chlorine reacts with certain
substances used to control foaming Ždefoamers. when
pulp is washed between bleaching steps or when wood-
chips containing pentachlorophenol ŽPCP., a wood
preservative, are used in pulping. The majority of the
chlorolignins formed are contained in the effluent of
the first alkaline extraction stage ŽE1.. As a result, this
effluent has a strong color and organic chlorine Žas
AOX. content, as well as a high BOD and COD ŽSun
et al., 1989.. The extent to which AOX is formed
during bleaching depends to a great extent on the
amount of lignin in the pulp prior to bleaching and the
amount of chlorine applied to the pulp ŽHeimberger et
al., 1988a,b.. Thus, during the bleaching of hardwood
pulp, such as that of eucalyptus, the formation of AOX
is somewhat less than that with softwood pulp bleach-
ing ŽGregov et al., 1988.. Acute toxicity and mutagenic
activity of undiluted pulp mill effluents, especially those
from a bleach plant, were found to be toxic to aquatic
organisms ŽLeach, 1980.. They exhibited a strong muta-
genic effect that has been demonstrated by several
bioassay procedures ŽPriha and Talka, 1986., including
Ames’ tests ŽBjørseth et al., 1979.. It is well known that
chlorinated phenolics and chlorinated lignin derivatives
are among the main chemical species responsible for
the toxicity of pulp and paper mill effluents ŽWalden
and Howard, 1977, 1981.. Although chlorinated
phenolics represent less than 2% of the organically
bound chlorine in bleaching effluents, they are large
contributors to effluent toxicity ŽHeimberger et al.,
1988a. and may be mutagenic andror carcinogenic
ŽHuynh et al., 1985..
2.4.1. Degradation of organochlorides
The majority of organochlorinated compounds pre-
sent in pulp and paper mill effluents are high molecu-
lar weight chlorolignins Ž) 1000 kDa.. These com-
pounds are likely to be biologically inactive and have a
small contribution to the toxicity, mutagenicity and
BOD of pulp mill effluents. Nevertheless, they are
stable against degradation, have long half-lives
ŽSalkinoja-Salonen and Sundman, 1980; Vogel and Mc-
Carty, 1987; Hileman, 1993. and cannot be removed by
conventional primary and secondary treatment alone.
However, long-term Žlow-rate. biodegradation of high
181
molecular weight chlorolignins may cause environmen-
tal problems. On the other hand, low-molecular weight
chlorinated neutral compounds are major contributors
to mutagenicity and bioaccumulation due to their hy-
drophobicity and ability to penetrate cell membranes
ŽCarlberg and Nashaug, 1986; Heimberger et al.,
1988a,b; Sun et al., 1989.. These compounds were found
to bioaccumulate in the aquatic food chain ŽLandner et
al., 1977; Renberg et al., 1980. especially in the body
fat of animals occupying higher trophic levels.
2.4.2. Aerobic degradation of organochlorides
Conventional aerobic degradation involves the oxi-
dation of organic chemicals, which are used as carbon
and energy sources for biological growth ŽZitomer and
Speece, 1993.. Typically, the major oxidized product is
carbon dioxide, whereas water is produced from oxygen
reduction.
To assess the ability of aerobic systems for AOX
removal, Stuthridge and McFarlane Ž1994. studied the
aerated lagoon treatment system of a New Zealand
pulp and paper mill and found that it exhibited 65%
removal of AOX. Much of this removal took place in a
short section Ž3.3-h residence time. of the system’s
main lagoon. The initial removal of AOX in the mixing
zone was observed to occur in three ways: suspended
solids present in the chlorination stage and general mill
waste-waters settled in the quiescent regions of the
mixing zone; limited alkaline dehalogenation occurred
when the acid and alkaline waste-waters mixed; and in
regions of the mixing zone where agitation of the
bottom sediments occurred, adsorption of AOX onto
resuspended solids took place. These solids then settled
onto the bottom of the mixing zone. Lime and bacterial
solids present in the treatment system were able to
adsorb AOX from the influent wastewaters. However,
only a small proportion of the organic chlorine re-
moved was found in sludges. A mass balance of aque-
ous and solid phases indicated that over 99% of the
removed AOX was mineralized. Similarly, laboratory-
scale treatability studies were undertaken to monitor
and optimize activated sludge ŽAS., facultative
stabilization basin ŽFSB. and aerated stabilization basin
ŽASB. treatment for removing AOX and chlorinated
phenolics from bleached Kraft combined mill wastewa-
ters ŽRandle, 1992.. Experiments conducted at various
operating temperatures and solids retention times
ŽSRTs. indicated that higher removal efficiencies of
total and filterable AOX were achieved in the FSB and
ASB treatment systems than in the AS system. The
FSB and ASB systems also achieved greater chlori-
nated phenolic removal efficiencies than the AS sys-
tem. Temperature was reported to have a significant
effect on chlorinated organics removal, particularly in
the FSB system. At moderate operating temperatures,
chlorinated organic removal efficiencies were not in-
182 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
fluenced by SRTs between 5 and 15 days. However,
significantly higher removal efficiencies were observed
after a two-fold increase of SRT to 30 days.
Several workers have investigated the degradation
ability of aerobic microorganisms in conventional pure
cultures ŽMilstein et al., 1988; Zhou et al., 1992; Duran
et al., 1994; Nagarathnamma et al., 1999.. These mi-
crobes are considered particularly successful degraders
of aromatic compounds because they often produce
mixed function oxidase enzymes, which initiate aro-
matic ring cleavage ŽZitomer and Speece, 1993.. In one
such study, Zhou et al. Ž1993. found that Streptomyces
chromofuscus and Streptomyces rochei, isolated from
soil, dechlorinated high molecular weight compounds
ŽHMM. from industrial bleach effluents. Compounds
of the effluents from the first chlorination ŽC q D. and
the subsequent alkaline extraction stage ŽE1. of a sul-
fite cellulose pulp mill were used as substrates for the
microbial transformations. HMM bleach effluent frac-
tions obtained by ultrafiltration were treated by free
and immobilized cells. Dechlorination was followed by
measuring the reduction in AOX as well as by estimat-
ing the release of inorganic chloride. While 38᎐45% of
the organic-bound chlorine was released from a mix-
ture of ŽC q D. and E1 stage effluents within 20 days of
incubation with S. chromofuscus, only 11᎐16% were
liberated from E1 stage HMM bleach-effluent com-
pounds by S. chromofuscus and S. rochei. In cases
where the organochlorides are extremely recalcitrant
or the dehalogenation efficiency of aerobic microbes is
not significant, simple adsorption onto microbial bio-
mass has also been employed. For instance, Ali and
Sreekrishnan Ž1999. used Saccharomyces cere¨ isiae to
remove AOX from bleach effluent of an agroresidue-
based pulp and paper mill. This helped to remove AOX
from the effluent and concentrate it in the fungal
biomass that can be then be taken up for further
treatment.
2.4.3. Anaerobic degradation of organochlorides
Conventional anaerobic biodegradation involves the
conversion of organic compounds to methane, carbon
dioxide, and other inorganic products. This process is
accomplished by a consortium of bacteria, which use
the organic compound as a source of carbon and en-
ergy. The dehalogenation of organic molecules by
anaerobic consortia has been widely studied and there
have been several reports concerning the dehalogena-
tion potentialities of fermentative, sulfidogenic,
methanogenic, and iron-reducing microbial communi-
ties ŽKuhn and Suflita, 1989; Mohn and Tiedje, 1992;
Parker et al., 1993; Fetzner and Lingens, 1994;
Hollinger and Shraa, 1994; Kazumi et al., 1995; Bradley
and Chapelle, 1996.. In fact, the literature suggests that
anaerobic bacteria may be better suited to reductively
dehalogenate highly chlorinated phenolics, while aer-
obic biological systems are suitable for less halo-
genated phenolics ŽSahm et al., 1986; Reineke and
Knackmuss, 1988; Neilson, 1990.. Pulp and paper mill
effluents have been treated successfully by employing
anaerobic means to treat the various streams. For
example, Salkinoja-Salonen et al. Ž1985. compared the
anaerobic treatment of four different pulp mill waste
streams, namely, sulfite bleaching and evaporator con-
densate wastewaters, wastewater from the displace-
ment bleaching of Kraft pulp and from thermomechan-
ical pulping. It alone removed 80᎐90% of BOD5. It was
reported that with bleaching wastewater, nearly 30% of
the COD was found to be biodegradable anaerobically
and could be removed by nearly 50% if aerobic post-
treatment was used. In a similar study, wastewaters
from a peroxide bleaching stage were treated anaerobi-
cally. Although the wastewater was found to be inhibi-
tory to methanogenic bacteria, it could still be de-
graded and removed by an acidogenic culture ŽWe-
lander and Andersson, 1985; Welander, 1988.. In a
parallel study conducted with bleach effluents from an
agro-residue-based pulp and paper mill, anaerobic
treatment was found to reduce AOX and COD by 73%
and 66%, respectively. Also, when glucose was added to
this effluent, there was generation of biogas containing
76% methane ŽAli and Sreekrishnan, 2000.. Ther-
mophilic anaerobic dehalogenation has been tested
and reported by several workers. For instance, Lepisto
and Rintala Ž1994. investigated the thermophilic Ž55⬚C.
anaerobic removal of chlorinated phenolic compounds
from softwood bleaching effluents using four different
types of anaerobic processes: an upflow anaerobic
sludge blanket ŽUASB. digester; a UASB digester en-
riched with sulfate; a UASB digester with recirculation;
and a fixed bed digester with recirculation. In all
processes, most of the chlorinated phenols, catechols,
guaiacols and hydroquinones detected in the bleached
Kraft mill effluent were either eliminated or reduced
by as much as 80᎐95%. However, 2,4-dichlorophenol,
2,-dichlorophenol, 4,5-dichloroguaiacol, 3,4,5-trichloro-
catechol and tetrachlorocatechol were accumulated or
only partially removed, except in the fixed bed digester
with recirculation where at high concentrations they
were significantly reduced. All digesters removed
30᎐70% of the COD and 25᎐67% of the AOX. A
combined approach utilizing anaerobic and aerobic
treatments for toxicity removal has also been adopted
by some workers ŽFahmy et al., 1991; Rintala and
Lepisto, 1993.. The bleaching effluent from Kraft pulp-
ing and debarking effluent and mixed effluent from
thermo-mechanical pulping were treated first in an
anaerobic fluidized bed reactor and then in an aerobic
trickling filter ŽHakulinen and Salkinoja-Salonen, 1982..
All mutagenicity, essentially all toxicity and Žfrom the
bleaching effluent. toxic chlorophenolic compounds
were removed from the effluents by the anaerobic
 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
reactor. The chlorophenolic compounds were mineral-
ized in the reactor into non-toxic end products ŽCO 2
and chloride ions.. They concluded that, in the case of
bleaching effluents, anaerobic treatment removed the
toxicity and also improved the BOD-removing capacity
of the subsequent aerobic treatment in a retention
time essentially shorter than that needed in aerated
lagooning or activated sludge plants.
There have been few reports concerning the use of
conventionally cultured anaerobic microbes for the de-
halogenation of bleach plant effluents ŽWiegel et al.,
1999.. Fulthorpe and Allen Ž1995. compared the rela-
tive organochlorine removal from bleached Kraft pulp
and paper-mill effluents ŽBKME. by Pseudomonas, An-
cylobacter and Methylobacterium strains. Ancylobacter
aquaticus A7, Pseudomonas P1 and Methylobacterium
CP13 were tested for growth on chlorinated acetic
acids and alcohols, and for AOX reduction in batch
cultures of sterile BKME from three different sources.
A7 exhibited the broadest substrate range, but could
only affect significant AOX reduction in softwood
wastewaters, while CP13 exhibited a limited substrate
range, but was capable of removing significant amounts
of AOX from both hardwood and softwood waste-
waters. P1 exhibited a limited substrate range and poor
to negligible reductions in AOX levels from both
wastewater types. Mixed inocula of all three species
combined and an inocula of sludge from mill treatment
systems removed as much AOX from softwood wastew-
aters as did pure populations of CP13. An extended
study along the same lines was conducted by Prasad
and Joyce Ž1993., who explored the efficiency of a
mixed aerobic᎐anaerobic treatment method for AOX
removal. E1 stage effluent from a softwood Kraft mill
bleach plant, containing 190 mgrl of AOX was sub-
jected to treatment with Phanerochaete chrysosporium
Burds. ŽBKM 1776. in a rotating biological contactor
for a 2-day detention period. An approximately 65%
color reduction, 42% AOX reduction, 45% total COD
reduction and 55% total BOD reduction was observed.
This efficiency was constant for approximately 20 days,
when treated effluent was replaced with fresh effluent
every 2 days. The fungus degraded both high and low
molecular weight chlorolignins without preference. Se-
quential biological treatment using the fungus followed
by an anaerobic treatment was attempted. This anaer-
obic stage removed an additional 40% AOX, 45%
soluble COD and 65% total BOD at a loading of 0.16
kg CODr m3 day, corresponding to a 20-day hydraulic
retention time. Overall, AOX reduction was 65%. Ex-
pectedly, the anaerobic digestion did not affect color.
In a second system, the effluent was treated in an
aerated lagoon and then in an anaerobic digester,
which resulted in an AOX reduction of 49%. Thus,
treatment was more effective in the fungal-anaerobic
digester system. The degradation of 2,4,6-trichlorophe-
183
nol, 2,4-dichlorophenol, and 4-chlorophenol, contained
in industrial pulp bleaching wastewaters ŽBWW., was
studied under aerobic andror anaerobic conditions,
using an adapted biofilm in fluidized sand bed fermen-
tors ŽFahmy et al., 1991.. In one configuration, BWW
was treated anaerobically, and then aerobically, in a
single pass, whereas in a second configuration, BWW
was treated anaerobically, and after that, aerobically,
and then the wastewaters of the aerobic fermentor
were partly recirculated to the anaerobic fermentor.
With a retention time of at least 11 h, the fractional
removals were constant in all three fermentor systems
Žincluding a single stage aerobic digester.: COD,
19᎐30%; total organic carbon, 15᎐25%; and AOX,
16᎐27%. The three chlorophenols were almost com-
pletely removed. All removal rates were almost always
proportional to the loading rate. At a lower residence
time of 7 h, with three undiluted wastewaters as feed,
the removal activity decreased. Only the second fer-
mentor configuration still had a quantitative removal of
85᎐90% for the three compounds, with residual con-
centrations below 70 nM. Similarly, in a study by Rin-
tala and Lepisto Ž1993., the Kraft mill chlorination
stage ŽKC. and alkaline extraction stage ŽKE. effluents
from softwood pulping were mixed Ž20% KC, 30% KE,
50% tap water. and fed to anaerobi᎐aerobic and aer-
obic reactors Žeach 250 ml. operated at 55⬚C and
partially packed Ž25᎐40%. with polyurethane. Heated
air was supplied to the aerobic reactors, and all or part
of the effluent from the anaerobic reactors was pumped
into an aerobic post-treatment unit. The feed COD was
1000᎐1100 mgrl. The average COD removal was
39.7᎐44.9% in the anaerobic process, and 37.9᎐43.8%
in the aerobic treatment. During days 20᎐65, the COD
removal averaged 43.6% in the aerobic process and
40.5% in the anaerobic process. Lower AOX values
were achieved in the anaerobic treatment than in the
aerobic treatment. The aerobic post-treatment re-
moved less than 10% of the COD and AOX present in
the anaerobically-treated effluent. Thermophilic anaer-
obic and aerobic treatments both provided 36᎐56%
AOX removal at loading rates of 1.3᎐2.5 kg CODm3
day, corresponding to hydraulic retention times of
17.6᎐30 h. COD and AOX removals were found to be
comparable to those obtained using mesophilic sys-
tems.
2.4.4. Abiotic degradation of organochlorides
Since organochlorides are inhibitory to both aerobic
and anaerobic microbes, an acclimation period is,
therefore, essential before these microbes can success-
fully achieve dechlorination. Acclimation may vary from
several days to months and is thus a time-consuming
and enlongated procedure. Moreover, there are com-
plexities associated with microbial contamination, the
requirements of co-metabolism and mycelial clogging
184 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
of bioreactors. It has, therefore, been realized that
abiotic methods, either alone or following a biological
treatment, produce much cleaner effluents ŽChen and
Horan, 1998.. To overcome this time lag, several abi-
otic methods have been employed and also were found
to be successful in AOX removal ŽVuoriranta and
Remo, 1994; Zhang and Chang, 1999.. The removal of
AOX and COD from bleached Kraft mill effluent was
investigated in laboratory- and pilot-scale aerobic sus-
pended carrier ŽSC. reactors and abiotic thermo-al-
kaline reactors ŽStrehler and Welander, 1994.. Labora-
tory treatment focused on the determination of the
loading capacity of the SC process and operation of the
process at elevated temperature and pH to combine
abiotic thermo-alkaline dechlorination and biological
treatment in a single reactor. At pH 7, 37⬚C and
hydraulic retention times ŽHRTs. longer than 3.5 h, a
maximum COD removal of 55% was achieved in the
SC process. The COD conversion rate at the minimum
HRT was 2.6 kg CODrm3 day. The SC treatment was
operated successfully at pH 9.0 and 45⬚C and at pH 7.0
and 50⬚C with over 50% COD removal with a HRT of
4 h. AOX removal at pH 9 and 45⬚C Ž50%. was higher
than at pH 7 and 37⬚C Ž39%.. Sequential thermo-al-
kaline and biological treatments were studied on a pilot
scale. Thermo-alkaline treatment at pH 10, 54⬚C and a
HRT of 2 h, followed by biological treatment at pH 8,
35⬚C and a HRT of 4 h, removed almost 80% of AOX
and 50% of COD from the Kraft mill effluent.
To optimize the reduction of AOX, chlorate and
high molecular weight chromophores and toxicity while
maintaining high COD and BOD removals, Boyden et
al. Ž1994. examined the biological treatment and post-
ozonation of mature eucalyptus Kraft mill bleachery
effluents. Biological treatment was adequately modeled
with Monod kinetics, using biodegradable COD
ŽbCOD.. Sludge yields were of the order of 0.76 g
biomassrg bCOD. Treatment was most effective Ž70%
total COD reduction, 95% BOD5 reduction. with sludge
ages of over 20 days and FrM ratios of 0.2᎐0.3
BOD5rkg day. The use of intermittent decanted aer-
ated reactors proved effective for removal of 70% of
the total COD Ž90% of bCOD. and 95% of the BOD,
with a hydraulic retention time of 8 days. Biological
treatment did not reduce total AOX or color, but
reduced chlorate by 63% in preliminary trials. As-
pergillus sp. p2 reduced color by 54% when supple-
mented with 1% Žwt.rvol.. glucose. Ozonation as a
tertiary treatment reduced AOX by 60% and the color
decrease followed first-order kinetics with respect to
ozone consumption.
In a parallel study, radiochemical and biochemical
oxidations were employed for the degradation of recal-
citrant chlorinated organics ŽBerge et al., 1994.. A
high-energy electron beam ŽEB. treatment of Kraft
mill bleach effluent removed approximately 40% and
70% AOX at dosages of 10 and 50 kGy, respectively.
Higher removals were expected at higher EB dosages.
These removals represented the elimination of AOX
through dechlorination, rather than transferring to an-
other form of waste. Chemical pre-treatment with acid,
base, oxygen or nitrogen bubbling and hydrogen perox-
ide addition was ineffective at high EB dosages. How-
ever, neutral environments resulted in slightly higher
AOX removals. Biological post-treatment removed up
to 28% of remaining AOX after various treatments,
but no significant enhancement of biodegradation of
EB-treated effluent was observed. The use of specific
microorganisms acclimatized to effluent quality may
have resulted in higher AOX removals according to the
literature, indicating the possibility of higher removals
of AOX from effluent when combined with EB treat-
ment.
2.5. Color
Color in pulp and paper mills is largely due to lignin
and lignin derivatives and polymerized tannins ŽGoring,
1971; Sankaran and Vand Lundwig, 1971; Sundman et
al., 1981; Crooks and Sikes, 1990; Reeve, 1991., which
are mostly discharged from the pulping, bleaching and
recovery sections. It has been demonstrated that lignin
is converted to thio- and alkali-lignin in the Kraft
process and to lignosulfates in the sulfite process. The
major by-product in the bleaching of wood pulp with
chlorine is chloroligin, of which large quantities Ž1᎐4
kg organically bound chlorine per ton of pulp pro-
duced. are released to the receiving waters ŽKukkonen,
1992.. Thus, effluents from the E1 stage are highly
colored and contribute 80% of color, 30% of BOD and
60% of COD to the mill’s total pollution load, although
its volume is very low ŽMehna et al., 1995.. Lignin and
its derivatives have been found to offer resistance to
degradation due to the presence of carbon-to-carbon
biphenyl linkages. The double bonds conjugated with
an aromatic ring, quinone methides and quinone groups
are responsible for the color of its solution ŽSankaran
and Vand Lundwig, 1971.. Goring Ž1971. reported that
lignin molecules have a tendency to undergo self-con-
densation, particularly in acid media, explaining its
resistance to degradation to simple molecular species.
Until recently, color was not considered to be a major
problem, being classified as a non-conventional pollu-
tant. However, it has now been realized that the dis-
charge of colored effluent from pulp and paper mills is
not only a serious aesthetic problem, but also has other
ramifications since there is a marked change in the
algal and aquatic plant productivity caused by the re-
duced penetration of solar radiation.
Numerous attempts have been made to remove color
using physical, chemical and biological means. Studies
have proved that lignin and its derivatives are quite
 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196 185

Table 3 considered to be commercially viable ŽPrasad and Joyce,

Cultures used for decolorization of pulp and paper mill 1993.. Moreover, the problem remains unsolved, since
effluents Žmodified from Hakulinen, 1988. lignin undergoes a spatial rather than chemical change
and thus persists albeit in a different form.
Culture Reference

Bacteria
Pseudomonas o¨ alis
Pseudomonas aeruginosa
Bacillus cereus
Algae
Microcystis sp.
Chlorella, Chlamydomonas
Fungi
Trametes ¨ ersicolor
Phaenerochaete chrysosporium
Tinctoporia borbonica
Schizophyllum commune
Aspergillus niger
Gloephyllum trabeum
Trichoderma sp.
Paecilomyces ¨ ariotti
Phlebia radiata
Bjerkandera sp.
Kawakami, 1975 2.5.2. Bacterial cultures
Blair and Davis, 1980 Several species of bacteria have been evaluated for
Bourbonnais and Paice, 1987 their decolorization abilities and a few of them have
Bourbonnais and Paice, 1987 also been used commercially. For instance, Pseudomo-
nas aeruginosa is capable of reducing Kraft mill effluent
color by 26᎐54% or more under aerobic conditions
Lee et al., 1978 ŽBlair and Davis, 1980.. Bourbannais and Paice Ž1987.
Dilek et al., 1999 tested Bacillus cereus and two strains of Pseudomonas
aeruginosa for the decolorization of bleach Kraft ef-
fluent. However, it was found that color was primarily
Kirk et al., 1976 removed by adsorption with little depolymerization of
Eaton et al., 1980 lignin derivatives. Kawakami Ž1975. found that Pseudo-
Fukuzumi, 1980
monas o¨ alis degraded alkali lignin more readily than
Belsare and Prasad, 1988
Kannan, 1990
Kraft lignin sulfonate. It has been observed that al-
Galeno and Agosin, 1990 though numerous bacteria can decompose monomeric
Prasad and Joyce, 1991 lignin substructure models, only a few strains are able
Calvo et al., 1991 to attack lignin derivatives obtained from different
Moreira et al., 1999 pulping processes ŽBajpai and Bajpai, 1994..
Palma et al., 2000

2.5.3. Algal cultures

toxic. For instance, a study by Roald Ž1977. showed
that the growth rate of young rainbow trout exposed to
a concentration of ) 160 mgrl of lignosulfonate was
lower than that of control fish. Nazar and Rapson
Ž1980. in an assay of the mutagenicity of Kraft pulp
bleaching plants found that the component of pulp
mainly responsible for the mutagenicity produced by
chlorination was lignin. Physical and chemical processes
are quite expensive and remove high molecular weight
chlorinated lignins, color, toxicity, suspended solids and
COD, but BOD and lower molecular weight com-
pounds are not removed efficiently. Biological methods,
on the other hand, use several different classes of
microbes to degrade the polymeric lignin-derived chro-
mophoric material ŽTable 3..
2.5.1. Physical and chemical methods
Several physical and chemical processes for color
removal have been extensively studied ŽProuty, 1990.,
including rapid filtration through soil, ultrafiltration,
ion-exchange chromatography, lime precipitation and
modified bleaching sequences, such as peroxide addi-
tion during extraction, the replacement of chlorine by
hypochlorite, sorption on hypo- and alum-sludge, acti-
vated carbon and on allophanic compounds ŽClark et
al., 1994; Frostell et al., 1994; Streat et al., 1995;
Bhattacharya and Sarma, 1997; Diez et al., 1999., etc.
However, these processes are expensive and none are
Some algae, such as Microcystis sp., have been re-
ported to decolorize diluted bleach Kraft mill effluents
ŽLee et al., 1978.. Both pure and mixed algal cultures
were found to be capable of removing up to 70% of the
color within 2 months of incubation. All cultures exhib-
ited a similar reduction pattern, in which color removal
was demonstrated to be most effective during the first
15᎐20 days of incubation after which it declined. Com-
plete color removal, however, did not occur. It has
been shown that color removal by algae is caused by
the metabolic transformation of colored molecules with
limited assimilationrdegradation of molecular entities.
Adsorption was not amongst the major color removal
mechanisms ŽLee et al., 1978.. Recently, Dilek et al.
Ž1999. used a mixed algal culture including Chlorella,
Chlamydomonas, Microcystis, etc. for AOX and color
removal. They reported that there was nearly a 70%
AOX reduction, while color was reduced by 80% in 30
days under continuous lighting conditions. Analysis of
alkaline extraction of algal biomass and material
balance findings indicated that the main color removal
mechanism was metabolism rather than adsorption.
2.5.4. Fungi
Amongst the microbes, fungi, especially the white
rots, have been shown to be the most efficient de-
graders of lignin. Several species of white rot fungi
have been tested for their lignolytic capability including
Schizophyllum commune ŽBelsare and Prasad, 1988.,
186 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
Tinctoporia borbonica ŽFukuzumi, 1980., Phaene-
rochaete chrysosporium ŽEaton et al., 1980. and Trametes
¨ ersicolor ŽKirk et al., 1976; Pallerla and Chambers,
1997., Aspergillus niger and Trichoderma sp. ŽKannan,
1990; Prasad and Joyce, 1991.. One of the most effi-
cient lignin degrading and, hence, decolorizing white
rot fungus discovered so far is P. chrysosporium, which
has, therefore, been studied in much detail ŽKirk et al.,
1976; Keyser et al., 1978; Eaton et al., 1980, 1982;
Jeffries et al., 1981; Sundman et al., 1981; Campbell et
al., 1982; Kirk and Shimada, 1985; Bergbauer and Eg-
gert, 1992; Moreira et al., 1998.. Lignin metabolism in
P. chrysosporium is a secondary metabolic event and is
triggered by carbon᎐sulfur or nitrogen limitation, even
in the absence of lignin ŽKirk et al., 1976; Eaton et al.,
1980; Kirk and Shamada, 1985.. Based on the success
of earlier workers, a mycelial color removal ŽMyCoR.
process has been patented ŽCampbell et al., 1982..
Bench scale studies using the MyCoR process have
shown that decolorization is first order below 10 000
units per liter of effluent and zero order above that
concentration, and that the decolorization rate exceeds
65 000 color units per day per square meter of mycelium
surface. Because E1 effluents usually contain less than
10 000 color units per liter, concentrating the effluents
prior to decolorization can be considered. The MyCoR
process has also been successfully attempted by Huynh
et al. Ž1985. for the treatment of the chlorinated low
molecular weight phenols of the E1 effluent. In an-
other study, continuous bio-bleaching of anaerobically
digested black liquor using jute immobilized P. chrysos-
porium cells was successfully carried out for 21 days
ŽMarwaha et al., 1998..
Coriolus ¨ ersicolor is another white rot fungus that is
a proven efficient lignin degrader ŽEaton et al., 1980;
Livernoche et al., 1983; Royer et al., 1983, 1985.. The
culture conditions favoring lignin degradation are simi-
lar to those favoring decolorization. Livernoche et al.
Ž1983. showed that C. ¨ ersicolor in liquid culture re-
moved over 60% of the color of combined bleach Kraft
effluent within 6 days in the presence of sucrose. Bel-
sare and Prasad Ž1988. reported the decolorization of
bagasse-based pulp and paper mill effluents by Schizo-
phyllum commune. However, this fungus could not de-
grade lignin unless a more metabolizable carbon source
was made available simultaneously. Under optimum
conditions, S. commune removed the color of the
effluents by 90% and also reduced BOD and COD by
70% and 72%, respectively, during 2 days of incuba-
tion. There are also reports of significant decoloriza-
tion with other, less studied species. Kraft waste liquor
was reported to be decolorized to a light yellow color
by Tinctoporia borbonica ŽFukuzumi, 1980.. Approxi-
mately a 99% color reduction was achieved after 4 days
of cultivation. The addition of a carbon and nitrogen
source was found to improve the decolorization of pulp
and paper mill wastewater by the fungus Aspergillus
niger, leaving 19% of the original color and removing
approximately 43% BOD and 41% COD after 2 days of
incubation ŽKannan, 1990..
Prasad and Joyce Ž1991. used Trichoderma sp., one
of the fungi imperfectii, to decolorize the hardwood E1
stage effluent. Under optimal conditions, total color
and COD decreased by almost 85 and 25%, respec-
tively, after cultivation for 3 days.
Other ligninolytic fungi evaluated for their decol-
orization abilities include Poria placenta, Gloeophyllum
trabeum ŽGaleno and Agosin, 1990., Paecilomyces ¨ ari-
otii ŽCalvo et al., 1991., Merulius tremellosus ŽLankinen
et al., 1991., Bjerkandera sp. ŽMoreira et al., 1999;
Palma et al., 2000. Phanerochaete sordida, Phlebia radi-
ata, Stereum hirsutum ŽMoreira et al., 1999..
Although several white rot fungi have been shown to
be efficient lignin degraders, especially P. chrysos-
porium and T. ¨ ersicolor, the requirements for high
oxygen tension and a growth substrate constraint pre-
clude their wide scale implementation for fungal decol-
orization. Moreover, lignin peroxidase production from
P. chrysosporium is hampered by several factors, such
as the expression of these enzymes under nutrient
limitation and unbalanced media, sensitivity of the
fungus to high shear forces in the fermentor ŽKirk et
al., 1978., and rapid inactivation of these enzymes even
in the absence of mycelia. To overcome these bottle-
necks, genetically engineered microorganisms ŽGEM.
have been developed. Thus, the optimization of het-
erologous expression has been explored in various hosts.
For instance, the heterologous expression of a lignin
peroxidase and manganese peroxidase of P. chrysos-
porium has been successfully obtained in baculovirus
ŽJohnson and Li, 1991. and Aspergillus oryzae ŽStewart
et al., 1996.. In E.coli, LiP H8 Žthe major lignin peroxi-
dase of P. chrysosporium. was expressed as inactive
inclusion bodies and the activation was obtained in
vitro ŽDoyle and Smith, 1996.. More recently, the het-
erologous expression of P. chrysosporium lignin peroxi-
dase was reported in A. niger ŽAifa et al., 1999..
The environmental friendliness of biopulping and
biobleaching notwithstanding, the costs involved are
prohibitive, which is one of the primary reasons why
microbes have yet to establish a firm foothold in the
paper manufacturing process. The feasibility of employ-
ing GEM for wastewater treatment has not gone un-
questioned, and it is now generally accepted that the
genetic, as well as the ecological, stability of GEMs
needs to be confirmed before they can be used in
actual field conditions ŽFujita et al., 1991.. A more
economically viable option would be the development
of hardy, ligninolytic strains that can grow in non-sterile
conditions by utilizing other wastes as their substrates.
 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
3. Treatment of pulp and paper mill effluents
With stricter environmental protection regulations
being formulated and enforced, coupled with higher
public awareness, the possibilities for the discharge of
untreated industrial wastewaters have become severely
limited. As a result, the treatment of effluents from
pulp and paper mills has become an essential prerequi-
site prior to their discharge to receiving water bodies.
In general, remedial action taken to reduce the pollu-
tion load from pulp and paper industries is of two main
types:
䢇 treatment at source Žprocess internal measures.,
wherein ‘cleaner’ technologies are adopted to re-
duce the toxicity at each stage of papermaking; and
䢇 end-of-pipe ŽEOP. treatment, which deals with the
effluents discharged.
3.1. Inno¨ ations in the pulping stage
The pulping process plays a central role in the
pollution load and the composition of wastewaters pro-
duced at pulp mills. Mechanical and thermochemical
pulping give high yields and, consequently, low pollu-
tion loads. Semi-chemical and chemi-thermomechani-
cal pulping wastewaters are of intermediate strength
and contain higher amounts of lignin ŽWelander and
Andersson, 1985.. In chemical pulping, a high-strength
effluent is produced containing the highest amount of
residual lignin. Removal of even an incremental amount
of this residual lignin can significantly reduce the
volume of bleaching chemicals needed to achieve tar-
get brightness, thus lowering the bleaching chemical
costs and reducing the amount of chemicals formed in
the bleach plant effluent that must be treated and
discharged. Thus, different processes have been devel-
oped for extended delignification to remove as much
residual lignin as practicable without sacrificing pulp
yield. These are outlined as follows.
3.1.1. Modification of cooking time or temperature
In this process, either the cooking time or the pulp-
ing temperature is increased to provide extended delig-
nification. However, extended cooking generally leads
to the loss of pulp yield above 95% lignin removal and
may result in the loss of pulp strength.
3.1.2. Extended cooking
The pulping process is extended by adding cooking
liquor to the pulp in stages rather than as a single
‘dose’. Lignin removal is as high as 97% and the
volume of bleaching chemicals is reduced by up to
35%. However, extended cooking also increases the
187
solids content of the black liquor, making additional
demands on recovery furnace capacity, necessitating
the installation of a larger furnace.
3.1.3. Oxygen delignification
In this process, a mixture of elemental oxygen ŽO 2 .,
sodium hydroxide ŽNaOH. and magnesium hydroxide
ŽMgOH. is mixed with the pulp following pulping and
pumped into a pressurized reactor to provide up to a
50% reduction in residual lignin. However, capital costs
involved must be taken into account since this is an
expensive method of delignification.
3.1.4. Ozone delignification
Similar to oxygen delignification, this process em-
ploys ozone ŽO 3 . and sulfuric acid ŽH 2 SO4 . with the
pulp in a pressurized reactor prior to pulp washing,
resulting in up to 50% reduction in residual lignin.
Since ozone is less selective in the solubilization of
lignin than oxygen or Kraft pulping chemicals, there is,
thus, a loss of pulp yield and strength.
3.1.5. Biopulping
Recently, there has been a growing interest in the
use of various microorganisms, particularly lignin-de-
grading fungi Že.g. white-rot fungi. and enzymes
Žligninases and xylanases . for the treatment of wood
chips prior to pulping. Ligninases attack lignin and
degrade it, while xylanases degrade hemicelluloses and
make the pulp more permeable for the removal of
residual lignin. Termed ‘biopulping’, this process re-
moves not only lignin but also some of the wood
extractives, thus reducing the pitch content and ef-
fluent toxicity. When biopulping is followed by mechan-
ical pulping, there is as much as a 30% energy saving,
whereas when it is followed by sulfite pulping, the
cooking time is dramatically reduced. The paper
strength properties have also been found to improve
after biopulping. However, this process is still in its
infancy and no full-scale biopulping plants are in oper-
ation at the moment.
Apart from these processes, several other alternative
pulping methods are being developed, such as acetic
acid and organosolvent pulping. The primary aim in
their development is to reduce the use of sulfur com-
pounds in pulping, thereby reducingreliminating air
emissions and nuisance odors caused by the presence
of sulfur.
3.2. Inno¨ ations in the bleaching stage
Residual lignin in pulps imparts a dark color to them
that is removed by multistage bleaching. Conventio-
nally, this has been achieved by the use of chlorine,
which has resulted in the generation of AOX. This in
188 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
turn results in the discharge of effluents that have high
toxicity and low biodegradability and pose a serious
challenge for biological treatment of these wastewaters.
Thus, several new, cleaner bleaching technologies have
been developed to replace chlorine.
3.2.1. Elemental chlorine free bleaching
Elemental chlorine free ŽECF. bleaching involves
the replacement of chlorine with chlorine dioxide, re-
sulting in a high-brightness pulp with acceptable
properties and wastewater with lower AOX concentra-
tions. The AOX loads are reduced, ranging from 0.7 to
0.9 kg ty1 air-dried pulp ŽADP. for mature eucalyptus
and from 0.4 to 1.0 kg ty1 ADP for plantation Žyoung.
eucalyptus ŽNelson et al., 1993..
3.2.2. Totally chlorine-free bleaching
Since 1990, totally chlorine-free bleaching ŽTCF. has
been used, largely in response to market demands for
non-chlorine bleached pulp. TCF bleaching has been
made possible after the action of a pre-delignification
step with pressurized oxygen, which leads to a pulp
with a considerably lower kappa number. This can be
followed by bleaching with oxygen, ozone, hydrogen
peroxide or even enzymes, thus eliminating chlorine
and chlorine dioxide completely ŽByrd et al., 1992;
Lapierre et al., 1995..
In a recent study, Vidal et al. Ž1997. analyzed the
methanogenic toxicity and anaerobic biodegradability
of ECF and TCF effluents from oxygen-delignified eu-
calyptus Kraft pulp. The effluents from chlorine and
ECF bleaching sequences had similar methanogenic
toxicities, with 50% inhibiting concentrations Ž50% IC.
of 0.65᎐1.48 g of COD per liter. Only the TCF bleach-
ing effluent was distinctly less toxic, with a 50% IC of
2.3 g CODrl. The fact that the ECF effluent was no
less toxic than that of chlorine bleaching, combined
with the residual toxicity of TCF, indicates that there
are other substances apart from the organohalogens
that contribute to the high methanogenic toxicity in
bleaching effluents ŽStauber et al., 1996..
3.2.3. Enzymatic bleaching
Two enzymes, namely, xylanases and ligninases, have
been predominantly employed in the bleaching of pulp.
These commercially available enzymes reduce the need
for bleach chemicals required to produce high-bright-
ness pulps.
3.2.3.1. Xylanases. As mentioned earlier, xylanases
improve delignification by the degradation of hemicel-
luloses. Thus, they are being employed as enzymatic
pre-treatments in Kraft pulp bleaching processes at
mill scale. Although there are different hypotheses to
explain the exact mechanism on the fiber-bound subs-
trate, it can be concluded that two types of phenomena
are involved ŽViikari et al., 1994.:
1. hydrolysis of the re-precipitated xylan, formed dur-
ing delignification, renders the pulp more perme-
able, thus facilitating the removal of residual lignin;
and
2. partial hydrolysis of xylan, located in the inner
layers and possibly linked to lignin, is likely to
facilitate further bleaching.
Thus, a pre-treatment step with xylanase increases
brightness of the pulp and decreases the use of bleach-
ing chemicals. Other positive features are the low cost
of the enzyme and the low investment costs if the
enzymatic stage is performed in the brownstock storage
tower. However, the use of xylanases will always re-
quire some further chemical delignification for com-
plete pulp bleaching and, consequently, will not permit
large chemical savings even when the process operates
at higher enzyme dosages ŽGarg et al., 1996..
3.2.3.2. Ligninases. White-rot fungi are well known
for their outstanding ability to depolymerize and min-
eralize lignin. Lignin biodegradation is initiated by sev-
eral extracellular oxidative enzymes excreted by white-
rot fungi, including lignin peroxidase ŽLIP. ŽTien and
Kirk, 1984., manganese-dependent peroxidase ŽMnP.
ŽGlenn and Gold, 1985., manganese-independent per-
oxidase ŽMIP. ŽDe Jong et al., 1994., laccase ŽEggert et
al., 1996. and hydrogen peroxide generating oxidases
ŽKersten and Kirk, 1987.. Purified ligninolytic enzymes
have been shown to cause limited delignification and
bleaching of unbleached Kraft pulps, provided that the
hydrogen peroxide is carefully dosed and the enzymes
are co-incubated with low molecular weight cofactors:
veratryl alcohol for LIP ŽArbeloa et al., 1992., man-
ganese, organic acids and surfactants for MnP ŽPaice et
al., 1993. and n-substituted aromatic compounds for
laccase ŽBourbonnais and Paice, 1992.. The role of LIP
in pulp bio-bleaching by whole cultures is not clear
because this enzyme has generally not been detected
during fungal biobleaching in many of the good bio-
bleaching strains ŽMoreira et al., 1997a.. Laccase and
MnP, on the other hand, are excreted at varying levels
by different white-rot fungal cultures when bio-bleach-
ing occurs ŽMoreira et al., 1997a..
Thus, it is apparent that the application of enzymatic
bleaching to the pulp and paper industry is still to be
developed. The main drawback of the hemicellulose-
aided bleaching is that it is an indirect method, not
directly delignifying pulp. On the other hand, both
laccase and MnP can achieve a more substantial delig-
nification than xylanase, but there are obstacles to be
overcome before either enzyme can be used in a cost-
effective manner ŽLema et al., 2000..
 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
3.2.4. Totally effluent-free processes
Recent research work has established that even with
reduced AOX discharges, mill effluents can exert sig-
nificant impacts upon the receiving environment. For
instance, effluent from a mill using 70% chlorine diox-
ide substitution caused the induction of liver mixed
function oxidase enzymes, an index of pollution stress,
in a largemouth bass. Even after oxygen delignification
and full substitution of the chlorine by chlorine diox-
ide, enzyme induction resulted in fish being exposed to
4% and 12% effluent in artificial streams ŽBankey et
al., 1995.. Similar findings were made for trout exposed
to effluent from a mill employing increased chlorine
dioxide substitution ŽHaley et al., 1995. and a positive
dose᎐response relationship was observed. In addition,
other studies ŽBarker et al., 1994. have documented a
variety of lesions in fish sampled adjacent to a mill
using sodium hydrosulfite as a bleaching agent, with no
chlorine chemicals in use. Overall, such studies demon-
strate that while environmental improvements can be
achieved by process changes and that the elimination
of chlorine based chemicals is a key factor in such
improvements, effluents from all processes are toxic to
some degree. Indeed, these and similar findings led to
increasing suspicions that chemicals other than the
AOX components present in pulp and paper effluents
Že.g. fatty acids, resins. were at least partially responsi-
ble for observed changes in fish populations. As a
result, there are two distinct elements to the debate
about environmental protection from pulp and paper
operations. While Malinen et al. Ž1994. proposed the
development of treatment plants to address the resid-
ual problems, Myreen Ž1994. considered that total ef-
fluent-free ŽTEF. production is now accepted by the
industry as the decisive step towards environmentally-
friendly pulp and paper production. In light of research
findings and the realization that all pulp mills can emit
endocrine disruptive chemicals on a large scale, the
closure of the mill circuits may be seen as an environ-
mental imperative for the industry. In most geographi-
cal areas there appear to be clear present and likely
future environmental, market and fiscal incentives to
move towards TEF production.
Currently, zero effluent operation appears to be
restricted to plants producing bleached chemical ther-
mal mechanical pulp and non-chlorine bleaching agents
ŽEdde, 1994.. A key impediment to fully closing mill
circuits is the difficulty of closure of the bleach lines.
Although problems exist with closing both ECF and
TCF lines, those involved in closing ECF lines appear
to be the most difficult and costly to resolve. The
presence of high levels of chlorides in an acid bleach
medium has been associated with severe corrosion
problems, and hence, the possibility of an explosion in
recovery boiler systems. Moreover, the presence of
189
organochlorines in both the filtrates of ECF bleach
liquors and in sludges from treatment plants means
that they cannot be incinerated without the emission of
products of incomplete combustion, including dioxins
and furans.
4. Summary and conclusions
The high polluting potential of pulp and paper in-
dustry wastewaters can no longer be ignored. However,
the major concern lies in the fact that even after more
than 30 years of consistent efforts, a satisfactory treat-
ment of these effluents still remains elusive. This is
primarily due to two reasons:
1. the processes employed in pulping as well as pulp
processing Žincluding pulp bleaching. are so diverse
that the composition of the resulting wastewaters
Žin terms of critical components. are very different
and no single process or combination of processes
can apply to all; and
2. the wastewaters invariably contain considerable
quantities of materials that are toxic either to the
wastewater treating organisms or to the aquatic
species present in the recipient waters or both.
A more distressing fact is the complete contrast
between the practices adopted by pulp and paper mills
in the developing countries and those encountered in
the developed world, particularly USA, Europe and
Canada. The mills in the developing world employ
elemental chlorine for bleaching, release large volumes
of wastewater and practice little or no effluent treat-
ment; on the other hand mills in the developed world
have moved on to ECF and TCF processes and closed
loop systems. Even where effluents are discharged,
their volumes are considerably reduced and secondary
aerobic biological treatments are employed.
Interestingly, in spite of such stringent regulations
being observed by mills in the countries mentioned
above, the ultimate eco-friendliness of their effluents
remains debatable. The problem is compounded by the
fact that, so far, few concrete, realistic resolutions
regarding discharge regulations have been adopted.
For instance, the Canadian Environmental Protection
Act ŽCEPA. in 1991 regulated the discharge of BOD,
suspended solids, acute toxicity and dioxins but none
on the discharge of AOX ŽSprague, 1990.. Similarly,
the USEPA Žthrough its final cluster rule in 1998.
discontinued the use of elemental chlorine, but gave
the nod to ECF processes. In the early 1990s, it was
believed that the substitution of elemental chlorine
with chlorine dioxide would eliminate the formation of
190 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
furans and dioxins and reduce AOX levels by almost
90%. However, it has been realized lately that, in spite
of the use of ECF processes, organochlorines have not
been eliminated from discharges, merely reduced. In
fact, Swedish research has shown detectable levels of
toxicologically chlorinated dioxins and dibenzofurans in
the effluents from mills that use ECF technology. This
stems from the fact that ECF processes are not free of
elemental chlorine. Commercial chlorine dioxide gen-
erators in many cases co-generate molecular chlorine.
Moreover, chemical reactions and pH-dependent
chemical equilibria in pulp bleaching reactions involv-
ing chlorine dioxide liberate molecular chlorine. This
molecular chlorine then reacts with chemicals released
from the wood, resulting in the formation of
organohalogens. The debate between ECF and TCF
may not be resolved soon, but the fact remains that
TCF technology has many advantages over ECF and is
more eco-friendly in the long run.
Apart from organohalogens, aquatic toxicity due to
wood extractives like phytosterols, stillbenes and
retenes is also of major concern. These compounds
cause chronic effects and long-term bioassays need to
be conducted to study them.
Thus, aquatic toxicity due to pulp and paper mill
effluents is an acute problem that needs to be ad-
dressed urgently on a worldwide scale.
For any reasonable measure of success in treating
pulp and paper mill effluents, future abatement pro-
grams should include a two-pronged strategy for the
use of alternate, cleaner technologies Že.g. the replace-
ment of chlorine for bleaching, oxygen delignification
and prolonged cooking. on one hand, and the develop-
ment of economically viable and efficient technologies
to treat these effluents on the other. Particular empha-
sis should be laid upon the dechlorination of phenolic
and aliphatic compounds and improved delignification
using hardy microbial strains.
Perhaps more than anything else, regulatory and
research agencies need to work in conjunction, not only
to have more realistic regulations, but also to hasten
the search for a technologically and economically vi-
able solution. Pollution from pulp and paper mill ef-
fluents is a complex environmental problem; its perma-
nent solution will require comprehensive system con-
siderations as well as multidisciplinary and holistic ap-
proaches.
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196 M. Ali, T.R. Sreekrishnan r Ad¨ ances in En¨ ironmental Research 5 (2001) 175᎐196
Muna Ali is a fourth year doctoral candidate at the Depart-
ment of Biochemical Engineering and Biotechnology, In-
dian Institute of Technology, New Delhi. Her dissertation,
under the supervision of Dr Sreekrishnan, is on the treat-
ment of pulp and paper mill effluents via biotechnological
means. She holds a Masters degree in Biotechnology and a
Bachelors degree in Zoology.
T.R. Sreekrishnan is an Associate Professor at the Depart-
ment of Biochemical Engineering and Biotechnology, In-
dian Institute of Technology, Delhi, New Delhi. He holds a
Bachelors degree in Chemical Engineering and Masters
and Doctoral degrees in Biochemical Engineering. His
research interests are in the area of environmental biotech-
nology, novel bioreactor development for treatment of in-
dustrial effluents and biological treatment of toxic solid and
liquid wastes.