the brunei bay as an effluent receiving waterbody: observations...

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Pcrtanika 13(1), 123-128 (1990) The Brunei Bay as an Effluent Receiving Waterbody: Observations during the Start-up Period of a Kraft Pulp and Paper Mill MURTEDZA MOHAMED, L.L. CHIN and T.S. LIM Department of Chemistry, Faculty of Science and Natural Resources, UKM Sa bah Campus, Locked Bag No. 62, 88996 Kota Kinabalu, Sabah, Malaysia. Key words: Pulp mill effluent, receiving water, effluent disperson. ABSTRAK Kualiti air Teluk Brunei, Malaysia, selepas menerima if/uen dari satu kilang pulpa dan kertas, telah dimonitor. Beberapa parameter kualiti air yang konvensional seperti oksigen ter/arut, pepejal terampai dan permintaan oksigen biokimia, telah digunakan sebagai penunjuk untuk membandingkan kualiti air di teluk tersebut masa kini dengan kualiti garis dasarnya. Pada keseluruhannya, data yang terkumpul dalam masa 16 bulan pertama kilang tersebut beroperasi tidak menunjukkan berlakunya perubahan yang ketara pada kualiti air Teluk Brunei. Paras pepejal terampai, karbon organik total, serta sebatian l,l-diklorodimetil sulfon di dalam air teluk telah digunakan sebagai penunjuk untuk menentukan corak penyerakan if/uen di perairan pantai teluk tersebut. ABSTRACT The water quality of Brunei Bay, Malaysia, subsequent to receiving iffluentfrom a pulp and paper mill, was monitored. Conventional water quality parameters such as dissolved oxygen, suspended solids, and biochemical oxygen demand were used as indicators to compare the present status of the bay water quality with that of the baseline. Generally, data gathered during the first 16 months of the mill operation did not indicate marked changes in the bay water quality. Levels of suspended solids, total organic carbons, and 1, 1-dichlorodimethyl sulfone in the bay water were used as indicators in the determination of dispersion pattern of the effluent in the coastal areas of the bay. INTRODUCTION Wastewater from an integrated pulp and paper milling operation generally includes effluents from wood preparation, chemical recovery, bleachery, and paper making processes. Thus, two major polluting substances present in the combined effluent are dissolved organics and suspended solids. Apart from imparting biochemical oxygen demand (BOD) and colour to the receivii1g water, a number of dissolved organics occurring in the effluent is known to be toxic, mutagenic, bio- accumulating, and resistant to biodegradation (Kringstad and Lindstrom 1984; Murtedza 1987). Thus, discharge of pulp mill effluent, especially untreated effluent into receiving waters, is general- ly considered environmentally hazardous due to the potential negative impacts on aquatic lives. One of the earlier studies showed that con- centration of bleached kraft mill effluent in excess of 2-3 parts per thousand had a significantly depressive effect on metabolic activity in oysters (Galstoff et at. 1947). Experiments using untreated bleached kraft mill effluent indicated that the 96 h LC so of the effluent solution is 15-50°C for rain- bow trout (Leach and Thakore 1975). Apart from the direct toxicity problems, there are also in- direct, non-lethal effects such as avoidance reac- tions in migrating fish coming into waters con- taminated with pulp and paper mill effluent (Livingston 1975). Organoleptic (taste and odour)

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  • Pcrtanika 13(1), 123-128 (1990)

    The Brunei Bay as an Effluent Receiving Waterbody:Observations during the Start-up Period of

    a Kraft Pulp and Paper Mill

    MURTEDZA MOHAMED, L.L. CHIN and T.S. LIMDepartment of Chemistry,

    Faculty of Science and Natural Resources,UKM Sabah Campus, Locked Bag No. 62,

    88996 Kota Kinabalu, Sabah, Malaysia.

    Key words: Pulp mill effluent, receiving water, effluent disperson.

    ABSTRAKKualiti air Teluk Brunei, Malaysia, selepas menerima if/uen dari satu kilang pulpa dan kertas, telahdimonitor. Beberapa parameter kualiti air yang konvensional seperti oksigen ter/arut, pepejal terampai danpermintaan oksigen biokimia, telah digunakan sebagai penunjuk untuk membandingkan kualiti air di teluktersebut masa kini dengan kualiti garis dasarnya. Pada keseluruhannya, data yang terkumpul dalam masa16 bulan pertama kilang tersebut beroperasi tidak menunjukkan berlakunya perubahan yang ketara padakualiti air Teluk Brunei. Paras pepejal terampai, karbon organik total, serta sebatian l,l-diklorodimetilsulfon di dalam air teluk telah digunakan sebagai penunjuk untuk menentukan corak penyerakan if/uen diperairan pantai teluk tersebut.

    ABSTRACTThe water quality of Brunei Bay, Malaysia, subsequent to receiving iffluent from a pulp and paper mill,was monitored. Conventional water quality parameters such as dissolved oxygen, suspended solids, andbiochemical oxygen demand were used as indicators to compare the present status of the bay water qualitywith that of the baseline. Generally, data gathered during the first 16 months of the mill operation did notindicate marked changes in the bay water quality. Levels of suspended solids, total organic carbons, and1, 1-dichlorodimethyl sulfone in the bay water were used as indicators in the determination of dispersionpattern of the effluent in the coastal areas of the bay.

    INTRODUCTIONWastewater from an integrated pulp and papermilling operation generally includes effluents fromwood preparation, chemical recovery, bleachery,and paper making processes. Thus, two majorpolluting substances present in the combinedeffluent are dissolved organics and suspendedsolids. Apart from imparting biochemical oxygendemand (BOD) and colour to the receivii1g water,a number of dissolved organics occurring in theeffluent is known to be toxic, mutagenic, bio-accumulating, and resistant to biodegradation(Kringstad and Lindstrom 1984; Murtedza 1987).Thus, discharge of pulp mill effluent, especiallyuntreated effluent into receiving waters, is general-

    ly considered environmentally hazardous due tothe potential negative impacts on aquatic lives.

    One of the earlier studies showed that con-centration of bleached kraft mill effluent in excessof 2-3 parts per thousand had a significantlydepressive effect on metabolic activity in oysters(Galstoff et at. 1947). Experiments using untreatedbleached kraft mill effluent indicated that the 96 hLCso of the effluent solution is 15-50°C for rain-bow trout (Leach and Thakore 1975). Apart fromthe direct toxicity problems, there are also in-direct, non-lethal effects such as avoidance reac-tions in migrating fish coming into waters con-taminated with pulp and paper mill effluent(Livingston 1975). Organoleptic (taste and odour)

  • MURTEDZA MOHAMED, L.L CHIN AND T.S. LIM

    Fig. 1. Map oj the study area showing points oj sampling, 10-14.

    TABLE 1Description of the sampling site

    12

    ..·SFI PUlp &

    .j/Paper Mill

    10

    N

    t

    Distance fromeffiu'ent discharge

    point (km)

    Il.

    14.

    Depth(m)

    o I 2 kmt===:=J

    BRUNEI BAY

    115"20·13

    10 5 "2.65' 115 °30.60' 16 0

    11 5 "2.20' 115 °29.60' 20 2.7

    12 5 °3.60' 115 °31.00' 16 2.7

    14 5 °3.20' 115°30.00' 22 2.5

    S"OO·N

    Site Latitude Longitudenorth east

    ;j ~ecaUlortlJ.bu.1n Is.

    Study"e, % S'P'JIl9?~.~.~');" \ SABAHr"\~ SARAWAX. ;! BRUNEI'" I'." I)

    approximately 43 000 m3. The combined effluentis treated in a high purity oxygen activated sludgeeffluent treatment plant prior to discharge into thebay (via a telescopic diffuser pipe, 200 m inlength). The pulp bleaching at SFI utilises a (C +D). Eo.D .D. sequence, comprising pre-bleachingstages using a mixture of chlorine (C) and chlorinedioxide (D), followed by oxidative extraction (Eo),and subsequent brightening stages using chlorinedioxide.

    MATERIALS AND METHODSSample Source and SamplingSamplings of seawater were carried out duringSeptember 1987 - December 1988 at sites denotedby 10, 11, 12, and 14 in Fzgure 1. Description forthe sampling sites is presented in Table 1. Watertemperature, salinity, and dissolved oxygen (DO)were measured in-situ for the entire water columnat 2 m intervals, using an in-situ water quality pro-be (Hydrolab Surveyor MK 2). For the deter-mination of suspended solids (SS), BOD, and

    effects have also been reported (Gordon et al. 1980;Shumway and Chadwick 1971). Use of chlorinedioxide in the pulp bleaching process results in theformation of chlorate; chlorate in bleached pulpmill effluent has been shown to be capable of caus-ing damage to brown algae, Fucus versiculosus, evenat concentrations as low as 20 ug/L (IPK, 1985).

    There are suggestions that effects of pulp milleffluents actually observed in receiving waterswere few in number and limited to receivingwaters with poor water exchange or to areas closeto the effluent outlet. The IPK (1982) study forexample, concluded that sublethal effects of theeffluents on fish disappeared after a dilution of70-100 times. A more recent study, however, in-dicated that some mild effects were still detectableafter a 2000-time dilution (IPK, 1985). Leach etat. (1978) and Mueller et at. (1977) reported thatthe toxicity of pulp mill effluents is almost totallyremoved after a 6-day treatment in an aeratedsystem. Mills equipped with well-operated effluenttreatment facilities are claimed to dischargeeffluents which even improve the productivity ofreceiving waters (Byrd and Eysenbach 1986; Cookand Chandrasekaran 1985). It is thus apparentthat organic enrichment of receiving water withpulp mill effluent may be beneficial if toxicity isabsent and a correct level of nutrient input ismaintained. In this respect, it is therefore impor-tant that receiving water quality be regularlymonitored to determine if the prevailing conditionis favourable or otherwise.

    This report presents results of water qualitymonitoring carried out in the Brunei Bay,Malaysia. The bay has been receiving effluentfrom the Sabah Forest Industries (SFI) Pulp andPaper Mill (the only pulp mill in Malaysia) sinceApril 1987. The monitoring was performedprimarily to determine (i) possible changes in thegeneral water quality of the bay, by comparisonwith that of the baseline (Murtedza et al. 1987),and (ii) the dispersion pattern of the effluent inthe bay. For the dispersion study, a tracer intrin-sic in the effluent, viz. 1, 1-dichlorodimethylsulfone (DDS) was used.

    The SFI mill is an integrated kraft pulp andpaper mill; pulp is obtained from mixed tropicalhardwoods. The maximum annual productioncapacity of the mill is 94 000 tonnes of bleachedkraft pulp. When operating at maximum capaci-ty, the volume of effluent discharged daily is

    124 I'ERTA IKA VOL. 13 NO. I, 1990

  • THE BRUNEI BAY AS A EFFL E T RECEIVI C WATERBODY

    RESULTS AND DISCUSSION

    TABLE 2Values of selected water quality parameters for the

    study area; the baseline values versus valuesobtained during the present studyl

    n represents number of dataIYalut·s for temperature, salinity, and dissolved oxygen represent theminimum and maximum values for entire water column, lTIt'asufl'dat 2m intervals, whereas those of suspended solids and biochemicaloxygen demand represent the minimum and maximum valul's forsamples obtained at 5m depth.

    :.?PoIiUlants' level in the effiuent during the period of sampling were:sllspt·nded solids 32-197 mg/L, BOD, 23 - 85 mg/L.

    Values for five conventional water quality para-meters for samples obtained from the four sampl-ing sites are shown in Table 2. Also presented inthe same table are the baseline values, obtainedduring a three-year monitoring programme priorto the SFI Mill operation. As apparent, the twosets of values are comparable, except probably fora slight dilution effect, as reflected in the salinityreadings.

    Baseline Present2

    (Mac'84-Jan'8 7) (Sept'87 -Aug'88)

    Depletion of oxygen in water column isnormally obvious in the case of waterbodies receiv-ing pulp and paper mill effiuent, primarily dueto the active bacterial degradation of wood fibressettled at the bottom. For the coastal areas ofBrunei Bay, however, oxygen depletion at thebottom layers was noted even during the baselinestudy period (see the representative DO profilesfor Sites 10 and 14 in Figure 2). As indicated inTable 3, this condition remained obvious duringthe present study. Nevertheless, there was noobvious evidence of further deterioration in

    Parameters

    Temperature (DC) 24.0 - 30.8 27.1 - 31.0(n = 185) n = 185)

    Salinity (103) 27.0 - 33.6 17.9 - 33.3(n=185) (n = 185)

    Suspended solids 1.6 - 41.8 1.0 - 43.4(mg/L) (n = 20) (n = 20)

    Dissolved oxygen 2.7 - 6.5 1.4 - 6.9(mg/L) (n = 185) (n = 185)

    BOD3(mg/L) 08 - 3.3 0.3 - 1.2

    (n=20) (n = 20)

    Sample Anarysis

    Suspended solids. 500 ml sample was filtered on apreweighted Whatman GFC filter paper, follow-ed by rinsing with excess distilled water to com-pletely remove solubles such as sodium chloride.The paper was reweighted after drying to aconstant weight at 105 DC and the difference inweight recorded and standardised to mg/l unit.

    BOD (30 DC). 3-Day biochemical oxygendemand diaD3) was determined by a methodsimilar to that of the Standard Method for BOD

    5determination (APHA 1981). Samples for BOD

    3determination were incubated at 30 DC over a3-day period prior to determination of finaldissolved oxygen levels by the Winkler titrationmethod.

    Total Organic Carbon (TOC) was determinedwith a TOC-TC analyser (Astro Model 1850TOC-TC Analyser).

    J,J-Dichlorodimethyl sulfone. 40 uL of a 62.8ug/mL solution of 1,6-dibromo-benzene in diethylether (internal standard) was introduced into a 500mL sample and the pH of the solution adjustedto 12. The solution was extracted with 25 mLdiethyl ether; the ether layer was then separated,dried (Na SO ), evaporated to about 1 mL and

    2 4analysed on GC. Gas chromatographic analyseswere carried out using a Hitachi Model 163 GasChromatograph with a 63 Ni electron capturedetector (ECD) and a fused silica capillary column(25 m x 0.25 mm i.d., BPI methyl silicon). Theoven and injector temperatures were maintainedat 90 DC and 300 DC, respectively. Nitrogen wasused both as the carrier gas (0.6 mUmin) and themake-up gas (30 mUmin). The injector split ratiowas 1:20. Compound identification was based onretention time comparison, and subsequent con-firmation by sample spiking/addition methodusing authentic DDS supplied by Helix Biotech,B.C., Canada. Quantification was based upon theinternal standard method.

    DDS, water samples were collected from 5 mdepth using an automatic grab sampler. Sampleswere immediately transported back to UKMSLaboratory and/or stored at 4 DC if not immediate-ly analysed. The sampling sites and methods forthe determination of in-situ parameters, SS, andBOD were identical to those of the baseline studydescribed elsewhere (Murtedza et al. 1987).

    PERTAN I KA \·OL. 13 NO. I, 1990 125

  • MURTED7.A MOHAMED, L.L. CHIN AND T.S. LIM

    oEP

    TH

    I.)

    T "

    (m)

    SITE 10

    ' ....,....\

    ,,,,•,,\\\

    / Janl.KTY ,/AuguST

    SITE H

    .,""'\,.,,\\\

    \,\..,

    Dissolvedoxygen

    profiles

    5.alini ty

    profiles

    same season (for the month ofJanuary), so as toavoid misinterpretation due to seasonal variations.

    The previous study did indicate a certaindegree of variation in the DO readings during the

    - E and S-W monsoons (Figure 2).BODpO DC), instead of BOD

    5(20 0c) was

    used in this study to assess biodegradable organicsin the receiving water. Comparative theoreticaland experimental studies for BOD/30 DC) and

    BOD5(20 DC) showed that BOD determinedunder the two different conditions were com-parable in values (Murtedza, unpublished data).As in the case of DO, analysis of the Brunei Bay

    7-

    6

    Dissolved 5_oxygen(mg/L) 4

    3-

    F(/t.]: I.nei> vj da;vlued oxygen at thefour SIte> Qj mea;ured IIlJall

    1987 (prior to pulp mill operatioll) compared to the levelsmeasured ill Jall 1988).

    Legends: / Baseline values (measured in January 1987)

    / Present values (measured in January 1988)

    FIg. 2: Represelltatiu dissolved oxygen alld salillity profiles at Site10 alld 14, for the mOllths ofJalluary alld A ugust. Data wa;obtailled dun·llg the 1984-1987 samplillgs, prior to the milloperatioll.

    oxygen status in the water column following themill operation. Figure 3 presents comparison of DOreadings for the four study sites, against those ofthe baseline. Readings presented are both for the

    2- Site 10 Site II Site 12 Site 14

    TABLE 3Dissolved oxygen readings taken during five occasions

    at the four sampling sites. Values are in mg/L

    Sampling site month Sept '87 Nov '87 Jan '88 Oct '88 Dec '88

    Site 10 surface 5.77 6.26 5.93 6.59 5.40

    mid-depth 4.73 5 .. 54 3.27 5.37 5.21

    bottom 2.97 506 3.17 4.54 2.72

    Site II surface 6.00 6.62 6.84 6.82 6.60mid-depth 5.01 5.63 3.98 6.55 5.70

    bottom 2.44 4.12 3.48 4.45 4.55

    Site 12 surface 5.96 6.06 6.45 6.75 5.12

    mid-depth 4.63 5.43 3.62 4.48 3.09

    bottom 1.78 3.71 3.48 4.20 3.57

    Site 14 surface 5.98 6.40 4.00 6.91 5.68mid-depth 4.53 5.28 3.42 4.90 5.65

    bottom 1.36 3.19 3.32 3.53 5.00

    126 PER·I,\,'\IKA \·01.. J:l NO.1, 1990

  • THE BRUNEI BAY AS AN EFFLUENT RECEIVING WATERBODY

    BRUNEI BAY

    Legends:

    SS Toe DDS(mg/L) (mgll...) (ngll...)

    1I1II110 3 28

    II11I11121 8 27

    • 19 7 32~~ 19 14 33

    2km

    suspended solids (SS) were used complementaryto DDS in the effluent tracing. As reflected in thetabulated legends to Fig. 4, concentrations of thethree indicators generally indicated that the move-ment of effluent was west - southwesterly, i.e.away from the Sipitang coasts.

    CONCLUSIO

    The period during which this study was carried outmay be considered as a 'start-up' period for the SFIMill. During such a period, significant fluctua-tions in the process parameters occurred, andloading of pollutants in the effluent fluctuatedaccordingly. Nevertheless, under the conditionsprevailing during this period, it was found thatthe Brunei Bay water quality in areas within ca.10 km2 around the effiuent discharge point re-mained within the normal range expected fortropical seawater (BOD < 4 mg/L, TOC < 30mg/L, SS < 50 mg/L) (Rilev and Chester 1979;Beer 1983). Use of DDS, TOC and SS as tracersindicate that the dominant effluent movement wastowards west - southwest, away from the Sipitangcoasts.

    ACK OWLEDGEMENTFig -I. .\fap >halL"/1/g a wnplified dupcTSlon pallem oj SF! Mill

    effluent in areos near the discharge point. Abbreviations: SS

    - suspended solids; TOe -tolal organic carbon; DDS-!,!-

    dichlorodimethyl sulfone. Their average valuff (for the Jive

    samplinl!,s) are given in the legends. Level oj DDS in the

    effluent during the sampling period was 86 - 232 mg/L.

    water for BOD gave values similar to that of thebaseline. The v.iJues were within the normal rangeexpected for tropical seawater (Riley and Chester1979; Beer 1983).

    Use of DDS as a tracer for determination ofpulp mill effluent dispersion in tropical seawater

    has been suggested by Murtedza and Lindstrom(1987). This particular compound was suggestedprimarily due to its presence in a sufficiently highconcentration in the effluent to match excessivedilution of effiuent in receiving waters. Also, DDSdoes not require derivatisation prior to gaschromatographic analysis, enabling rapid samplework-up and analysis. In the present study, it wasconfirmed that DDS was absent in samplescollected from the middle of Brunei Bay. Also, toaccount for the differences in solubility and den-sity of the various effluent components, TOC and

    The authors acknowledge financial assistancerendered by niversiti Kebangsaan Malaysia.

    REFERENCES

    APHA, American Public Health Association. 1981.Siandard Methods Jor the Examination oj Water and

    Wastewater, 15th. ed. APHA/AWWA/AWPCF,Washington, D.C.

    BEER, T. 1983. Environment Oceanography - An Introduc-tion 10 the Behaviour qf Costal Water, p. 83-93. London:Pergamon Press.

    BYRD,J.F. and E.J. EYSENBACH. 1986. The Effect ofTreated Effluent on a River and Lake Ecosystem.Tappi Uune): 94-98.

    COOK, C.R. and S. CHANDRASEKARAN. 1985. TheStan-up and Performance of an Aerated Lagoonand its Impact on Receiving Water Quality. Paperpresented at the 1985 Environment Conference, Can. Pulpand Paper Assoc. Toronto, Canada.

    GALSTOFF, P.S., W.A. CHIPMAN, J .B. ENGLE andH. N. CALDERWOOD. 1947. Ecological and Physio-logical Studies of the Effect of Sulphate Pulp MillWastes on Oysters in the York River, Virginia. Fish.Bull. Fish Wildl. Servo u.s. 51: 57-186.

    I'I·YT.\:\IK,\ \'01 .. /:: :\0. 1. 191J() 127

  • M RTEDZA MOHAMED, L.L. CHIN A D T.S. LIM

    GORDON, M.R., j.C. MUELLER and C.C. WALDE1980. Effect of Biotreatment on Fish TaintingProperties of Bleach Kraft Whole Mill Effluent.Trans. Tech. Sect. Can. Pulp and Paper Assoc. 6:

    TR2-TR8.

    IPK (Industrin Processkonsult AB). 1982. Environmen-tally Harmonised Production 0/ Bleached Pulp. IPK,Stockholm.

    IPK 1985. SSVL-85 Project 4: Production of Bleached Pulp.IPK, Stockholm.

    KRINGSTAD, K.P. and K. LINDSTROM. 1984. SpentLiquors from Pulp Bleaching. Environ. Sci. Technol.18: 236A-248A.

    LEACH, j.M., j.C. MUELLER, and C.C. WALDEN.1978. Biological Detoxification of Pulp Mill Ef-fiuents. Process Biochem. 13: 18-21.

    LEACH,j.M. and A.. THAKORE. 1975. Isolation andIdentification of Constituents Toxic to juvenileRainbow Trout (Salmo gairdneri) in Caustic Extrac-

    tion from Kraft Pulp Mill Bleach Plants. J. Fish.Res. Board Can. 32: 1249-1257.

    LiVINGSTON, R..J. 1975. Impact of Kraft Pulp Mill

    Effluents on Esturaine and Coastal Fishes inApalachee Bay, Florida, USA. Mar. BioI. 32: 19-48.

    MUELLER, j.C., j.M. LEACH, and C.C. WALDEN.1977. Detoxification of Bleached Kraft Mill Effiuents- a Management Problem. Tappi 60: 135:137.

    MURTEDZA MOHAMED. 1987. Kraft Pulp a.nd PaperMills Effluents. Sumber 3: 191-208.

    MURTEDZA MOHAMED and K. LINDSTROM. 1987.Potential Intrinsic Tracers for Determination of PulpMill Effluent Dispersion in Tropical Seawater.Pertanika 10(2): 191-196.

    MURTEDZA MOHAMED, R. STANFORTH, G. USuPandM.K. D. SINGH. 1987. Baseline Water Quality of

    Brunei Bay, Sabah. Sumber 3: 167-180.RILEY, j.P. and R. CHESTER. (1979): Introduction to

    Marine Chemistry. p. 122-149. London: AcademicPress.

    SHUMWAY, D.L. and G.G. CHADWICK. 1971.Infiuence of Kraft Mill Effluent on the Flavor ofSalmon Flesh. Water Res. 5: 997-1003.

    (Received 17 February, 1989)

    128 PERTANIKA VOL. 13 NO.1, 1990