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Bioresource Technology 77 (2001) 275±286

Review paper

The treatment of pulp and paper mill e‚uent: a review


G. Thompson a, J. Swain b, M. Kay b, C.F. Forster a,*
a
School of Civil Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK
b
PIRA International, Randalls Road, Leatherhead, Surrey KT22 7RU, UK
Accepted 4 April 2000

Abstract
The manufacture of paper generates signi®cant quantities of wastewater; as high as 60 m3 /tonne of paper produced. The raw
wastewaters from paper and board mills can be potentially very polluting. Indeed, a recent survey within the UK industry has found
that their chemical oxygen demands can be as high as 11 000 mg/l. This paper reviews the processes involved in paper making and
examines the e€ects which they could have on the environment. It also evaluates the treatment processes which are used to minimise
these e€ects. In line with the majority of UK practice, it focuses mainly on aerobic biological treatment and, in particular, on the
activated sludge process. This means that there is an in-depth discussion about the problems associated with ®lamentous bacteria
and sludge ``bulking''. The paper also discusses the way in which anaerobic digestion can be applied to the treatment of liquid wastes
from the manufacture of paper. Ó 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Paper and board mills; Wastewater treatment; Activated sludge; Anaerobic digestion

1. Introduction cally so as to form a pulp. The pulp slurry is subse-


quently dried on a paper machine to produce a paper
Although the ¯attened stalks of papyrus reeds were sheet. The addition of dyes, coating materials or pre-
used by the Egyptians as a writing surface some 5500 servatives can occur at some point of the process to
years ago, paper as we know it today was developed in produce the required quality of paper or associated
China in about 105 AD. Today, in the UK, there are product. The use of wood from the UKÕs forest has
some 95 mills producing a wide range of di€erent types doubled since the 1970s from 4 million cubic metres to
of paper (Table 1). Historically, the pulp and paper in- 6.5±7.5 million cubic metres in the 1990s (Table 2). An
dustry has been considered to be a major consumer of estimated increase to 15 million cubic metres by 2020 is
natural resources (wood, water) and energy (fossil fuels, expected. Due to the shortage of wood, only a small
electricity) and a signi®cant contributor of pollutant amount of wood pulping is actually undertaken in the
discharges to the environment. Urged by environmental UK: approximately 85% of the wood required is im-
and legislative pressure, together with advancing tech- ported from overseas (Table 2). Therefore, the technol-
niques and commmitment from industry leaders, the ogies associated with the treatment of wood pulping
pulp and paper industry has reduced its environmental wastewaters will only be dealt with and only very brie¯y.
impacts to air, water and land over recent decades by The pulp and paper making industry is a very water-
80±90%. intensive industry and ranks third in the world, after the
Wood, one of the major raw materials used in the primary metals and the chemical industries, in terms of
pulp and paper industry, is composed of cellulose ®bres, freshwater withdrawal. It is believed (Kallas and Mun-
carbohydrates such as starch and sugars, as well as lig- ter, 1994) that by the year 2000, the paper industry will
nin which acts as an adhesive substance for the cellulose be the largest manufacturing user of water. The con-
®bres. The pulp and paper industry breaks down the sumption varies with the type of paper being produced
wood to separate the cellulose from the non-cellulose (Fig. 1) and can be as high as 60 m3 per tonne of paper
substances. The raw material is then dissolved chemi- produced, even with the most modern and ecient op-
erational techniques. However, the practice of recycling
*
Corresponding author. Tel.: +44-0121-414-5069; fax: +44-0121-414-
a certain degree of water is commonplace, as this re-
3675. covers some of the ®bres which have escaped in the
E-mail address: c.f.forster@bham.ac.uk (C.F. Forster). wastewater. Recycling is achieved by closing up systems,

0960-8524/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 0 - 8 5 2 4 ( 0 0 ) 0 0 0 6 0 - 2
276 G. Thompson et al. / Bioresource Technology 77 (2001) 275±286

Notation HRT Hydraulic retention time


MLSS Mixed liquor suspended solids
BOD Biochemical oxygen demand N Nitrogen
COD Chemical oxygen demand P Phosphorus
DO Dissolved oxygen SSVI Stirred sludge volume index
F/M Food to biomass ratio SVI Sludge volume index

Table 1 needs to be treated to reduce any possible impacts on the


A breakdown of the paper and board industry in the UK (data from aquatic environment.
Anon., 1997)
Industry sector Number of mills in sector
Packaging board 30 1.1. The pulp and papermaking processes
Newsprint 3
Printings and writings 30
Tissue 15 1.1.1. Pulping
Other 17 North America produces more than half of the
Total 95
worldÕs pulp. Production in western Europe amounts to
20% of the worldÕs total supply, with the Nordic coun-
tries (Sweden, Norway and Finland) contributing 64%
promoting recirculation of the process waters. Thus, the of this. The other large producers of pulp in the EC
consumption of freshwater is reduced. Within the UK countries include West Germany, France, Portugal and
paper industry there is a rather uneven trend, with large Spain (European Commission, 1996) (Fig. 3).
reductions up to about 1980 (approximately 80 m3 / Woodpulp is prepared by three main processes.
tonne in the late 1960s to 60 m3 /tonne in the mid-1970s 1. Mechanical forces in the presence of water (mechan-
to 40 m3 /tonne in 1980), but a much smaller reduction ical pulping). The process involves passing a block of
since then (to about 35 m3 /tonne). An alternative ap- wood, usually debarked, through a rotating grind-
proach is to treat the wastewater to such an extent that it stone where the ®bres are stripped o€ and suspended
can be re-used within the mill. Indeed, the concept of in water.
``zero liquid e‚uent'' has been suggested for mills 2. Chemical pulping which utilises signi®cantly large
making certain grades of paper (Wiseman and Ogden, amounts of chemicals to break down the wood in
1996). The same concept would be applicable in areas the presence of heat and pressure. The spent liquor
where water sources were extremely limited (Norris, is then either recycled or disposed of by burning for
1998). However, the recovery and re-use of water can heat recovery.
increase the concentration of organic and inorganic 3. A combination of the two (chemical thermo-mechan-
species, which in turn can a€ect paper formation, in- ical pulping). The wood is ®rst partially softened by
crease bacterial loading or lead to corrosion and odours chemicals and the remainder of the pulping proceeds
(Robertson and Schwingel, 1997). with mechanical force.
The raw wastewater from paper and board mills can In the 1970s and 1980s, there was concern over the
be, potentially, very polluting (Fig. 2, Table 3). Indeed, a emissions of chlorinated organic substances, such as
recent internal survey within the industry has shown dioxins and furans, from the use of chlorine in pulp
that chemical oxygen demand (COD) values can be as bleaching. Facing market and environmental demands
high as 11,000 mg/l. Thus, wastewater from the industry for ``Elementary Chlorine Free'' (ECF) and ``Totally

Table 2
Imports/exports and consumption of wood and wood products in the UK (millions of cubic metres) (data from Forestry Commission Facts and
Figures; www.forestry.gov.ukwww.forestry.gov.uk)
Year Import Exports UK production Apparent consumption
Wood Pulp Panels Paper Total Total
1991 16.0 8.7 4.9 13.6 43.2 5.0 6.5 44.8
1992 15.6 8.7 4.9 14.3 43.5 5.1 6.6 45.0
1993 15.0 7.8 4.8 14.6 42.2 4.5 6.8 44.5
1994 17.4 8.6 5.1 16.4 47.6 5.8 7.3 49.0
1995 14.1 9.1 5.41 15.9 44.3 6.0 7.6 45.8
1996 15.0 8.2 5.4 16.6 45.1 5.4 7.1 46.7
1997 15.6 8.4 6.0 17.8 47.7 6.8 7.4 48.3
G. Thompson et al. / Bioresource Technology 77 (2001) 275±286 277

Fig. 1. Speci®c water usage (mean values) (data from Anon., 1997).
Fig. 3. Pulp production in western Europe (data taken from European
Commission, 1996).

Chlorine Free'' (TCF) bleached pulps, mills adopted


bleaching processes which use chlorine dioxide (ECF
pulp) or which use oxygen-containing compounds such
as molecular oxygen, peroxide and ozone (TCP pulp)
(L
ovblad, 1999).

1.1.2. Papermaking
Western Europe plays an important role in the global
paper industry being the second largest producer and
consumer of paper, with North America being the
largest. Together they control a 60% share of the worldÕs
paper market. Western Europe produces some 80  106
tonnes of paper and board each year. This accounts for
Fig. 2. Speci®c e‚uent production (mean values) (data from Anon.,
1997).
approximately a quarter of the worldÕs total paper
production. The Nordic countries contribute about 30%
of the annual European production. Japan is the third
most important producer with 12% of total production
Table 3 (European Commission, 1996) (Fig. 4).
Untreated e‚uent loads from pulp and paper manufacture (range of
In the production of paper, pulp is diluted to at least
design values)a (data from Billings and DeHaas, 1971)
99% with water and a mineral ®ller; china clay, titanium
Paper type kg/tonne of product
dioxide or chalk; and water-soluble substances such as
Suspended solids 5-day BOD optical brighteners and polyvinyl alcohol are added
Pulps (Hentzschel et al., 1998). This is then pumped to a
Bleached groundwood 20±38 11±26 headbox and is distributed evenly along a moving wire
Textile ®ber 130±220 90±130
Straw 180±220 180±220
cloth. This even distribution is facilitated by the con-
De-inked 180±360 26±70 stant side-to-side movement and vibration a€orded by
Fine papers 22±45 7±18 the headbox. The majority of the water drains through
Book/publication papers 22±45 9±22 the wire leading to the formation of a wet paper sheet.
Tissue paper 13±45 4±13 This is then vacuum dried and pressed, to extract more
Coarse papers
Boxboard 22±30 9±18
water and form the paper sheet. Residual water is re-
Corrugating brand 22±30 11±26 moved by passing it through a series of steam-heated
Newsprint 9±26 4±9 cylinders.
Insulating board 22±45 67±110 Recycled paper is an important source of cellulose
a
Design value is dependent upon yield. ®bre for certain paper and board grades (corrugated
278 G. Thompson et al. / Bioresource Technology 77 (2001) 275±286

machine will subsequently be released in the paper ma-


chine wastewater, except where the process is operated
in a closed loop system. In contrast, chemical pulping
plants, with recovery systems in place, ®nd that most of
the organic pollutants dissolved during pulping are re-
tained in the recovered liquors which are generally in-
cinerated. The highest wastewater losses are found in
mills which operate chemi-mechanical process.
The wastewater from the papermaking and de-inking
process di€ers from the pulping process due to there
being no breakdown of raw material, other than the
rejects of cleaning and screening. The water used in this
process plays an important role in controlling the losses
of raw material from the wire. This type of wastewater
makes up the majority of the e‚uent released into UK
water sources due to the lack of pulping in this country.
The wastewater from the de-inking operation contains
ink residues which are removed from the waste paper in
the ¯otation de-inking cell and the ¯otation water clar-
i®er. The sludges do contain heavy metals: however,
these are generally no higher than the levels present in
domestic sewage. The papermaking process produces an
Fig. 4. Paper and board production in western Europe (data taken e‚uent which contains a substantial quantity of cellu-
from European Commission, 1996). lose ``®nes'' and other additives. This can be up to 50%
of the total mass. This contaminated water is frequently
referred to as ``whitewater''. Reclamation of the e‚uent
paper, newsprint). For white grades, such as newsprint,
is economically essential as the gross usage of water in
the recycled ®bre is de-inked using ¯otation, followed by
the industry is very high and the cost of e‚uent treat-
washing and screening. Soluble components such as
ment for all water assigned to drain would be too ex-
starch are removed in the wastewater.
pensive, and would also involve a loss of raw materials.
A proportion of the water is recycled to the beaters for
1.2. Pulp and papermill e‚uent use in dilution or other processes.

There is a signi®cant di€erence in the quality of the 1.3. Environmental e€ects


wastewaters from pulping and papermaking operations
(Billings and DeHaas, 1971) (Table 3). This is due to the The majority of the pulping is conducted outside the
diversity of processes and the chemicals used. The main UK and the pulp imported. Therefore, the most signif-
di€erence between the two is that pulp wastewater icant potential for environmental pollution occurs in the
contains dissolved wood derived substances which are pulping countries. In pulping countries, the e€ect of the
extracted from the wood during the pulping and e‚uent on the environment can be much greater.
bleaching processes. Another di€erence between the Studies with both bleached and unbleached Kraft pulp
pulp and paper mill e‚uents is the colour of the ®nal mill e‚uents (KME) showed evidence of impaired liver
discharge. All pulping e‚uent has some discolouration, function in ®sh exposed to these e‚uents (Oikari and
which is due to the dissolved lignin. This is more pro- Nakari, 1982) and concentrations of bleached KME of
nounced where chemical pulping methods are employed. 8±20% v/v caused mortality of striped bass prolarvae
Papermaking e‚uents may also have some discolour- after 72 h exposure (Burton et al., 1983). Studies con-
ation, especially at mills using dyes to produce coloured ducted in the US and Canada in the early 1990s dem-
paper. onstrated a variety of responses in ®sh populations
The pulping process generates a considerable amount living downstream of bleached Kraft pulp mills. These
of wastewater, approximately 200 m3 /tonne of pulp included delayed sexual maturity, smaller gonads,
produced (Cecen et al., 1992), most of which is too weak changes in ®sh reproduction and a depression in sec-
to recover, although being highly polluting. In conven- ondary sexual characteristics (Munkittrick et al., 1997).
tional mechanical pulping, the dissolved organic mate- Prior to the widespread installation of secondary ef-
rial from the wood is split between the pulp passing on ¯uent treatment plants, the main problem which oc-
to the paper machine and that going to waste. The cured in the UK was the growth of sewage fungus in
majority of the pollutants which go forward to the paper rivers receiving papermill e‚uent (Webb, 1985a,b,c,d).
G. Thompson et al. / Bioresource Technology 77 (2001) 275±286 279

Other problems, which may arise, occur when the that UK mills will be authorised under the EC directive
treatment processes employed to treat the pulp and on integrated pollution prevention and control (IPPC),
papermill e‚uent fail. This can result in the release of with emission data being available for public scrutiny
suspended solids, and the loss of nutrients, such as ni- via a Europe-wide Polluting Emissions Register. The use
trogen and phosphorus, which can lead to eutrophica- of primary treatment followed by secondary biological
tion in recipient bodies. treatment, which is the approach adopted by UK mills,
The Environmental Protection Act, 1990, introduced is considered to be BATNEEC for the industry.
integrated pollution control (IPC) to the UK. The aim
of IPC was to prevent pollution at source and protect
the environment overall (air, water and land) from cer- 2. The treatment of pulp and papermill e‚uent
tain prescibed processes and substances. Control of
pollution is, therefore, ``integrated'' to achieve the best The main treatment process used at pulp and paper-
environmental outcome. A number of UK mills were mills plants is primary clari®cation, and in some cases, it
authorised under IPC. As part of this authorisation is then succeeded by secondary treatment, generally of a
process, mills had to demonstrate that they were using biological nature (Fig. 5). Tertiary processes for further
best available techniques not entailing excessive cost treatment, or colour removal, are rare at present, but
(BATNEEC) to control emissions to the environment. may become more common in the future if legislation
As part of the process, data on environmental emissions becomes more stringent.
were made available by papermills to the Environment
Agency (EA) for public scrutiny via the Chemical Re- 2.1. Primary clari®cation
lease Inventory. The IPC is underpinned by a series of
guidance notes, relating to the classes of industrial Primary clari®cation may be achieved by either sed-
processes, which set out the EA view of what are con- imentation or ¯otation. Within the papermills surveyed
sidered to be BATNEEC for a particular process and in the UK, sedimentation was the preferred option.
which indicate resultant emission levels. It is also likely These units achieved a high removal of suspended solids,

Fig. 5. Generalised schematic diagram of the plant for the treatment of papermill e‚uent.
280 G. Thompson et al. / Bioresource Technology 77 (2001) 275±286

on an average >80%. However, unlike primary settle-


ment in domestic wastewater treatment plants, at pa-
permills there is little removal of organic material
(biochemical oxygen demand, BOD, and COD). A
survey of plants treating the wastewaters from paper-
mills in Finland showed that the primary clari®ers re-
moved more than 80% of the suspended solids at surface
loading rates of up to 1.4 m3 /m2 h (Saunam aki, 1997).
Dissolved air ¯otation is an accepted process for the
removal of suspended solids and has been used in many
wastewater treatment process streams, for example, to
thicken waste activated sludge (Haarho€ and Bezu-
idenhout, 1999), as a pre-treatment of dairy wastewater
prior to aerobic biological treatment (Kasapgil et al.,
1994) and in the treatment of ®sh ®lleting wastewaters
(Genovese and Gonzalez, 1994). The Shotton Paper Mill
is the largest mill in the UK, producing some 430,000
tonnes of newsprint each year and a daily wastewater
¯ow of 18,000 m3 . Thirty percent of the raw material is
recycled waste paper and the wastewater generated from Fig. 6. F/M loadings for activated sludge plants treating paper and
its processing is clari®ed by dissolved air ¯otation prior pulp mill e‚uents (* data for Finnish plants taken from Saunam aki,
to passing to secondary biological treatment (Horan and 1997).
Chen, 1998). Similarly, the use of dissolved air ¯otation
to treat the ``toxic and dicult'' streams prior to sec- (Fig. 6). The distribution of OLR values is similar to
ondary biological treatment at the Hallsta papermill in those reported by Saunamaki (1997) for papermills in
Sweden has been reported by Sanneskog and Reeves Finland. The full range of operational parameters of a
(1991). typical activated sludge plant treating e‚uent from pulp
and paper mills in the UK are highlighted in Table 4, for
2.2. Secondary treatment various types of end products. The performances
achieved by activated sludge plants being used for the
2.2.1. Aerobic treatment treatment of papermill wastewaters are given in Table 5.
Currently about 40 of the 100 or so UK mills use on These show that a very high removal eciency can be
site secondary biological treatment. There are numerous obtained both for BOD and COD removal.
biological treatment systems available, the most com- It could be argued that there are two critical opera-
mon being the activated sludge process. Activated tional aspects of an activated sludge plant; maintaining
sludge plants at UK papermills typically operate at a proper control of the dissolved oxygen (DO) con-
mean organic loading rates (OLR) ranging from 0.07 to centration in the aeration tank and maintaining a
0.21 kg BOD/kg mixed liquor suspended solids (MLSS) good settling sludge. The settlement characteristics of

Table 4
Activated sludge operating parameters
Mill type
Recycled ®bre, Printings/writings Printings/writings Tissue Other
Sludge age (d) 5±8 6±18 7±40 20±30
HRT (h) 8±12 5±30 11±18 50±200
Volumetric loading (kg/m3 d) 0.5±0.8 0.4±1.4 naa 1.2
Hydraulic loading (m3 /d) 28,800 0.04±1.25 naa 1220
Sludge loading/d 8.6 tonne 0.07±0.25 naa naa
DO concentration (mg/l) 0±6 0±7 0.5±9 0.1±9.9
COD (mg/l) 1500±1900 1060±2770 50±2000 0±11,000
Sulphate (mg/l) 500 140±1050 525±1750 6750
Ammoniacal-nitrogen (mg/l) 6 naa 1.90±2.70 16.5
Nitrate (mg/l) 2.50 naa 3±13.5 82.5
Phosphate (mg/l) 2.18 naa 9.9±20.3 12.3
MLSS (mg/l) 3000±7000 2300±9000 3000±6000 2200±5350
SSVI at 3.5 g/l 48±90 30±160 50±130 72±360
a
Data are unavailable.
G. Thompson et al. / Bioresource Technology 77 (2001) 275±286 281

Table 5 Although the exact mechanisms for the formation of


Plant eciencies for activated sludge plants treating papermill waste- sludge ¯ocs are unknown, it is now generally thought
water
that ®lamentous bacteria form a matrix to which the
Activated sludge Country Source ¯oc-forming bacteria will then attach. When these ®la-
eciency (%)
mentous species grow out from the ¯oc, settlement
BOD COD
problems can occur (Sezgin et al., 1978). However, it
73.5±99.2 50.0±92.2 Finland Saunamaki (1997) does seem that certain species are more likely to cause
± 90.6 Shotton Paper Horan and Chen
settlement problems than others. A survey of 80 mills in
Mill, UK (1998)
97.9±98.5 72.5±92.4 UK ± North America showed that the most prevalent species
were Haliscomenobacter hydrossis, Thiothrix I and II,
Nostocoida limicola II and Eikelboom Type 0914
(Richard, 1997). A German survey of 13 activated
sludge plants treating paper industry wastewaters iden-
ti®ed the dominant sludge species as being H. hydrossis,
Thiothrix and Beggiatoa, N. limicola and Eikelboom
Type 021N (Schmid et al., 1996) and a survey of eight
plants in the UK treating papermill wastewaters has
found that, in general, Eikelboom Type 021N, N. limi-
cola II and H. hydrossis occurred most frequently.
Much work has been published with regard to the
operational conditions associated with ®lamentous
growth of di€erent species (Jenkins et al, 1986; Wanner,
1994a,b) (Table 6). However, little is known with regard
to what causes the onset of ®lamentous dominance.
The theories for the presence and growth of ®laments
include (Dalentoft and Thulin, 1997a; Wanner, 1994a):
1. The kinetic theory which states that the ®lamentous
bacteria and the ¯oc-forming bacteria have di€erent
Fig. 7. Variation in the settlement characteristics of the activated maximum growth rates, depending on the substrate
sludge produced in the treatment of papermill wastewaters.
concentration.
2. The accumulation±regeneration theory which sug-
activated sludge, as measured by the stirred sludge vol- gests that ¯oc-formers have a greater ability for intra-
ume index (SSVI), are very variable (Fig. 7). Indeed, cellular storage of energy compounds under transient
poor settlement (bulking) has caused operational prob- (unbalanced) conditions than have ®laments. Storage
lems since the 1920s (Morgan and Beck, 1928) and ac- products are typically glycogen and poly-hydroxybu-
tivated sludge plants treating papermill wastewaters tyrate.
seem to be particularly prone to this. Indeed, the acti- 3. The starvation theory which is based on the assump-
vated sludge plant at one papermill in the UK has re- tion that organisms with a high storage response will
ported 100 incidents of bulking in the last three years. be favoured under limited-substrate conditions. The
Bulking is deemed to be occurring when the SSVI ex- storage products will then be used as energy supply,
ceeds a value of about 120 and this can result in exces- whilst the organisms with little or no storage response
sive concentrations of solids being discharged in the ®nal will be suppressed by starvation.
e‚uent when the solids handling capacity of the ®nal 4. The sludge age has a great impact on the distribution
settlement tank is exceeded. It can also create problems of individual microbial species in activated sludge
in ensuring that the correct amount of sludge is recycled and is dependent on their speci®c growth and decay
back to the aeration tank to maintain the MLSS at a rates. Thus, di€erent sludge ages can enable di€erent
sucient concentration to guarantee ecient treatment. ®lamentous bacteria to become dominant.

Table 6
Operating parameters, wastewater characteristics and predominant types of ®lamentous microorganisms
Operating conditions or wastewater characteristics Predominant types of ®lamentous microorganisms
Low dissolved oxygen concentration in activated sludge S. natans, Type 1701, Type 1863 and possibly Type 021N, Thiothrix
Low organic loading of activated sludge M. parvicella, H. hydrossis, Types 0041, 0092, 0581, 0961, 0675, 0803, 1851
N or P de®ance in wastewaters S. natans, Type 021N and possibly Thiothrix
Increased concentration of sulphide in wastewaters Thiothrix, Beggiatioa, possibly Type 021N
282 G. Thompson et al. / Bioresource Technology 77 (2001) 275±286

5. Some ®laments exhibit a preference for low concen- many countries, as can be seen from its ranking in the
trations of DO. This is especially notable at the inlet three surveys on bulking and ®lamentous bacteria
zone of aerators. (Table 7).
6. Some ®laments have a competitive edge in a low nu- N. limicola II has not been evaluated to the same
trient environment and it has been suggested that to- extent as other ®lamentous species. Indeed, there ap-
tal inorganic nitrogen should be >1 mg/l and soluble pears to be only one report of its growth characteristics
orthophosphate phosphorous >0.2 mg/l. in pure culture (Nowack and Brown, 1990). However,
7. Temperature will a€ect the growth rates of the bacte- recent work has shown that in mixed liquor, its com-
ria so that di€erent species will become dominant at petitive advantage can be controlled by increasing the F/
di€erent times of the year. M ratio (Scruggs and Randall, 1998).
8. Nutrient gradients in the aeration tank will favour Sludge bulking can also be controlled by the instal-
non-®lamentous species. Therefore, con®gurations lation of a selector or by the addition of chemicals such
which create plug-¯ow characteristics in the aeration as chlorine, ferrous salts or lime. The use of selectors is
tank are preferable. one of the most widely accepted procedures for the
A survey of nine papermills in 1994 identi®ed poor control of bulking (Forster, 1996; Dalentoft and Thulin,
oxygenation, low organic loading rates and nutrient 1997a; Marten and Daigger, 1997; Prendl and Kroiss,
de®ciencies as the main causes of bulking (Cingolani 1998; Shao and Jenkins, 1989). The selectors are placed
et al., 1994) and a study of pulp and papermill activated prior to the aeration tank and can be aerobic, anoxic or
sludge plants around the Great Lakes showed that anaerobic. The primary aim of a selector is to supress
stress, resulting from low phosphorus concentrations, the growth of ®laments in favour of ¯oc-forming bac-
produced bulking caused by N. limicola III (Richard and teria. The higher growth rate for ¯oc-formers is utilised
Cummins, 1997). under conditions with a high substrate concentration.
Type 021N is often classi®ed as a nutrient de®ciency These conditions are created by imposing a high in-
bulking ®lament. It has been found to be very common stantaneous food to mass ratio on the biomass. Marten
in conventional treatment plants (Table 7) and can and Daigger (1997) have shown that the target F/M for
usually be controlled by means of a selector (see later: an anoxic selector is 0.7±1.2 kg BOD/kg MLSS d and
Neilson et al., 1998). The reduction of sulphate by the that this, coupled with an aerobic solids retention time
sulphate-reducing bacteria is also linked to the domi- of 8±12 days, will successfully control bulking ®laments.
nant growth of 021N. Yamamoto et al. (1991, 1994, The use of chemicals, as a short-term solution to control
1996) have shown that: the e€ects of bulking, will improve settleability without
1. as sulphate reduction increased, the growth of 021N the destruction of the ®lamentous bacteria. Simpson
in activated sludge increased and the sludge settle- et al. (1991) have reported that the SVI of sludges from
ment deteriorated (1991); two trial works where bulking was occurring could be
2. sulphate reduction is the trigger for ®lamentous bul- reduced by treatment with an iron-rich mixture of metal
king by 021N (1994); salts.
3. there is a symbiotic relationship between the sul- Another option is to kill the ®lamentous bacteria
phate-reducing bacteria and the ®lamentous sulphur selectively by the addition of toxic substances such as
bacteria (1996). chlorine and hydrogen peroxide. The use of chlorine is
Types of industrial waste which promote Type 021N widely practiced, especially in the US, and can generally
bulking typically contain soluble, readily biodegradable, be dosed in the returned activated sludge stream enter-
carbonaceous substrates and a high sulphate concen- ing the aeration tank (Neethling et al., 1985; Jenkins
tration. Bulking from Type 021N often has a rapid et al., 1986). The main chemical used in the UK is so-
onset, 2±4 days, is severe, sludge volume index dium hypochlorite. The use of hydrogen peroxide is not
(SVI) > 500, and is persistent (Richard et al., 1985). as common.
H. hydrossis is related to a low food to microorgan- An alternative method is to use some form of solids±
ism ratio. It has been found to be the cause of bulking in liquid separation process other than gravity sedimenta-
tion. In recent years, research has concentrated on the
Table 7 use of ultra®ltration (Ragona and Hall, 1998). The ul-
Relative signi®cance of ®lamentous bacteria in bulking situations tra®ltration membrane acts as a barrier for microor-
Species Survey ranking ganisms: thus, any pollution in the ®nal e‚uent will be a
Germany Netherlands USA (Jenkins result of soluble components only. If this method were
(Wagner, (Eikelboom, et al., 1986) to be employed, the growth of ®lamentous bacteria
1982) 1982) would cease to be of any concern.
021N 1 6 3 Changing the operational con®guration of the acti-
H. hydrossis 6 2 9 vated sludge plant can also in¯uence the settlement
N. limicola 7 11 12
characteristics of the sludge. Sequencing batch reactors
G. Thompson et al. / Bioresource Technology 77 (2001) 275±286 283

are a time-orientated rather than a space-orientated followed by a conventional activated sludge system. The
version of the activated sludge process (Dennis and Ir- load applied to the Kaldnes-tank was 10±15 kg COD/m3
vine, 1979) and in laboratory studies, they have been d and that to the activated sludge system was 0.1±0.4 kg
shown to be more resilient to shock loads of KME than COD/m3 d (Dalentoft and Thulin, 1997b). The use of
aerated lagoons (Weeks and Oleszkiewicz, 1993). Ar- the Kaldnes process as a pre-treatment can also a€ect
guably, the ®ll mode is the most important phase of the the characteristics of the subsequent activated sludge.
process. It can be done with no aeration, with partial Dalentoft and Thulin (1997b) have shown that, in such a
aeration or with full aeration. Of these, the unaerated ®ll process stream, when the Kaldnes stage was out of op-
mode has been shown to prevent ®lamentous bulking eration, the SVI of the sludge in the activated sludge
(Norcross, 1992, Yu and Gu, 1996). This technology aeration tank was >300. When both the processes were
does not appear to be used by the UK paper industry, in operation, the SVI was around 120.
but it is a process which is used in Canada (Cocci et al., Other types of bio®lm process have also been used in
1998) and it has been reported that its use has reduced the treatment of papermill wastewaters. For example,
capital costs by about 30%, compared to conventional high-performance trickling ®lters using plastic media
secondary treatment systems (Villeneuve and Tremblay, have been used successfully as a pre-treatment stage
1995). The best sludge settlement properties and highest prior to an activated sludge plant (Moebius et al., 1990).
COD removal were found to occur with a sludge age of Biological aerated ®lters (BAF) have also been used to
20 days, a ®ll-phase of 30 min and a react-phase of 12 h treat wastewaters from papermills. As is shown in Fig. 8,
(Franta and Wilderer, 1997). mean removal eciencies of >80% for both COD and
The Kaldnes process can be thought of as another BOD could be achieved with hydraulic retention times
activated sludge variant and is one which has success- (HRT) of about 0.75 h. (Kantardjie€ and Jones, 1997).
fully been applied to the treatment of papermill wastes
(Dalentoft and Thulin, 1997b). In e€ect, the process is 2.2.2. Anaerobic treatment
converted from one which is ¯oc-based to one based on Anaerobic digestion is a process frequently employed
attached bio®lms. This is done by introducing a plastic for the secondary treatment of industrial wastewaters
support medium (approximately 10 mm diam:  7 mm), but, whilst investment in this technology is increasing
either into the aeration tank itself or into a separate tank (Pearson, 1990), it is not used as widely as the activated
which preceeds the main aeration tank. Typically, the sludge process by the pulp and paper industry. It has
media occupies 67% of the tank volume and will provide many potential advantages in comparison to aerobic
a speci®c surface area of about 500 m2 /m3 . The e€ect of treatment, such as lower sludge production, lower
doing this is to increase the mass of biological solids chemical consumption, smaller land requirements due to
available for degrading the pollutants in the wastewater. smaller reactors and energy production in the form of
This, therefore, means that higher loads can be applied. methane. Typical COD removal data for the treatment
The results from one full-scale plant at a mill producing of papermill wastewaters shows that a relatively con-
customised ®ne paper show a COD removal eciency of stant removal eciency of about 80% can be achieved
85±95%. The plant was con®gured as a Kaldnes-tank and that the treated e‚uent has a COD concentration of

Fig. 8. The relationship between removal eciency and hydraulic re-


tention time for a BAF system treating wastewater from a ®ne pa- Fig. 9. Performance of a full-scale anaerobic digester treating paper-
permill (Kantardjie€ and Jones, 1997). d, COD; m, BOD. mill wastewater. d, E‚uent COD; m, Removal eciency (%).
284 G. Thompson et al. / Bioresource Technology 77 (2001) 275±286

about 800 mg/l (Fig. 9). This COD concentration means Treatment Directive for COD are applied. Even after
that some form of additional treatment is required. In full biological treatment, the e‚uent from a papermill
Netherlands, Industriewater Eerbeeck operate an an- can contain appreciable concentrations of COD. For
aerobic up¯ow sludge blanket reactor as a pre-treatment example, a study by Oeller et al. (1997) has reported
for the e‚uents from three papermills before the ®nal data from six papermills showing COD:BOD ratios
treatment in a ®ne bubble di€used air activated sludge ranging from 67:1 to 14.5:1. Treated papermill e‚uents
plant (Paasschens et al., 1991). can contain colour. This may come from the production
The high sulphur content of pulp and paper mill ef- of coloured toilet tissue or from lignin (Franta et al.,
¯uent might seem to suggest that anaerobic treatment 1994). In the UK, regulatory bodies are moving towards
would not be an appropriate treatment option because stringent colour standards based on River Quality Ob-
of the potential for hydrogen sulphide production jectives. These are based on speci®ed absorbances at a
(Lettinga et al., 1991). However, the work reported by range of wavelengths (Churchley, 1994). In the future,
Hamm et al. (1991) suggested that H2 S toxicity was less toxicity-based consents may also be imposed (Wharfe
important than the e€ect of high concentrations of Ca‡‡ and Tinsley, 1995).
and SOÿÿ 4 . Sulphide removal has also been achieved in The main tertiary treatments which have been em-
reactors based on the colourless sulphur bacteria which ployed to date at a few sites in the industry are mem-
convert the sulphide ions to elemental sulphur (Buisman brane processes, especially ultra®ltration. This process is
et al., 1991). Using bio®lm reactors, removal eciencies a pressure driven separation, based on the selective
of up to 90% were obtained with hydraulic retention permeability of a membrane, which can serve as a sec-
times as low as 19 min. Chen and Horan (1998a) have ondary clari®er as the ®nal liquid±solids separation step.
reported the use of a two-stage anaerobic±aerobic ap- Numerous physico-chemical processes have also been
proach to remove COD and sulphate from the waste- developed to remove a variety of toxic materials from
waters generated at an integrated newsprint mill. COD pulp e‚uents and to reduce parameters such as colour
and sulphur removals were 66% and 73%, respectively. and COD. They include ozonation and adsorption, of-
In general, anaerobic digestion is carried out at meso- ten in combination with coagulation, which is used as a
philic temperatures, 35±37°C. However, the use of the pre-treatment stage. A study by Chen and Horan
thermophilic temperature range is worth considering (1998b) compared the use of ozone and coagulation and
(Rintala et al., 1991) as it will give faster reaction rates demonstrated that chemical coagulation followed by
and a higher gas production rate. dissolved air ¯otation and multimedia ®ltration would
be the most suitable tertiary treatment option. Dissolved
2.2.3. Alternative processes air ¯otation, coupled with coagulation with alum and an
Although activated sludge plants have been the most organic polymer, were also selected as the tertiary
common wastewater treatment process, there are several treatment option for the Braviken papermill in Sweden
problems with the process. It produces sludges with very and gave ®nal COD concentrations of <100 mg/l
variable settlement properties, it is sensitive to shock (Thoren et al., 1997). Research by Hostachy et al. (1997)
loading and toxicity, and its capacity to remove poorly has shown that ozonation is particularly e€ective
biodegradable toxic substances is limited. Studies were whereas Oeller et al. (1997) showed that COD removal
conducted in Finland on the use of pre-ozonation to eciencies achieved by ozone were variable.
prevent process failure, to improve the puri®cation ef-
®ciency and to reduce pollution to receiving water-
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