AppnuoI of 1.... '0 _ 'l>< Eo....on_"w Il<M'>oo' 0( 0><1n;cabEdilOd by P. She<""". F. Kon., '" Kloin ond P!<. llo.",l<o.Cl 198~ SCOrE. I'IIbI'<h«l!>y JoI<n ",10) '" Son< Lid

3.2Sediments

1 SCHEU"ERT

GnrlJs<""""" 5,,""1«1· ""d Um~~tI"'''''~_"~mbH "'_"""'"/""''''' fi'. O'oI08U<M CIonru<1~'1ANmr ID-MJ42 .\tuM~Fninrol 1I<,...1>Ii<: 01 0<""",,)

3.2.1 l"uoducr'Qft 1373.2.2 Phj"cal Pr"l"'''~ and o...micaJ Comp<»i'ion 0( Sediments 1383.2,3 Phy,ic.1. o.emical."d Biochemical Proa:= in Sedimon" I~O

3.l,~ Labo,.,o')" To'" '0 De'.nni.. Single F..o,,,,, Affeo'i"1I ,he: h,e "fo.emi""l. in Sodimen" 148

3,2.~ Lobo""",)' Modc:l &o<)·"em. IS73,2.6 F.ield T.", IS~

3,27 Conch";o", IS<J3.2.8 Rore,ena:, 160

3.2.1 1:\'TRQDlJCTIQS

In Ihe contexl of lesling of en,ironmen,al chemicals. 'sediment' i. thecommon name gi.en 10 lhe soiVmud layer al lhe bol1om of a ",,,ter bodyresuiting from lhe sellling of suspended solid' lran_porred in Iii.. ,...1., bod)",Sedimenl compos,lion is exooodingl)' "ariable depend,ng on origin of lhe,uspended mal1er, lhe nov.' rate and ilS nuctuations .. "'en as inpn" fromhuman aeli'ilies. Benthic material is characterized in genetal by aninlerphase ,,·..er/mud layer of fine panicl~ including organic mallet in Whichlbe wale,,'oolid, ratio can be as high as 9 10 1. and a more solid sedimenl bed('an de, Harst. 1979).

The OttUrrence of chemicals of anlhropogenic origin in sediments and...>pcnded ""lids in ri,-ers, lake•. lagoons. and ,h. sea has been ,eporled innumeTOUS publica lions; 'he,efo.. , only ""me examples of references aregi'en here_ The chemicals d.,ecled includ. radionuchd... he..,)" melals.nitrogen and phosphorous compound" paraffins, polycyclic aromatich)·droca'bon•. pe<ticide_. polychlorinat.d biphenjls, p1aSliciz<:rs, and o'herman.made chemicals(e.g., DukulDI .. 1970; l.elandn,u .. 1973; Frank,1917;

138 TESTS TO PREDICT TIlE ENVIROl> \lEl>TAL 8EHAVIOI.iR OF OlE."ICALS

Mile~ 1977; Miiller~1 aI .• 1977; Miiller, 1977a--<:; Botello and MandeUi,1978; Balka. el aI .• 1978; TlJIi el aI.• 1978; Giam ef aI.• 1978; MiilIer. 1979aand b; PUCttUi and Uoni. 1980; Muller 01 "I.. 1980; Giam and Atlas. 1980;BaSliirk .. "I.. 1980; Villenem'e Of "I., 1980; SaJilloglu 01 "I .. 1980; Murray 01aI.• 1981 a and b; Amico or "I.. 1982; Pimpl and Sclliinelkopf. 1982; Geyer er,,1..1984). In order to dC"elop models and teslS to predict the bella,iour oftllese cllemicals in ""diments. pll)'Sical and cllemical processes in tile""diments. a. ".-ell as mteraction. of t!>e ""diment with water and aquaricorganisms sllould be undel'Stood, The rollo""ing sections, tllerefore. deal ";111pll~'sical properties and chemical coml"""ition of sediment' and the phy.icaland chemical proces"'" in"olved,

3.2.2 PHYSICAL PROPERTIES ANn CHE.\IlCAL CO~tPOSITlOI\ OFSEDI.\tE.''TS

The p""ido ,iu of sed,ment' resulting from the ""tiling of solids transportedin a .uspended form usually is below 0.05 mm (0.063---{1,OO2 mOl; ',ilt),""diment; 0.002 mOl; 'c1ay' sediment), 13}- COIItra't, p"rticles tran,poned atthe bottom of a n..r hy' rolling generally' haye ,i~es of 0.063-2.00 mOl('sand') or more ('gra"eJ"). Due to their relati"ely low specific surface. the""malel;al. play only a minor role in adwrption and dtgradation ofen""onmental chem,cals (Muller, 1981)

There is a continuous inlerrelationship bet"'«n the ""diments at tilebollom of a water bod~ and su,pendtd solid matter. and, as a con""quence ofchanges in particle size due to ,'ariou. ph~'sical or biological influencesincluding water mo"ement Or otller en,'ironmental factors, pa"icle, rna)' betransported bet"'cen both ph...... Therefore. ,,'hen considering the beha"iourof chemicals in sediments, " ..ter·sU>peno:k<! solid matter must be considered.

The weathering of rock produces indi"idual clay' and .ilt-sized mineralgrain. which agglomerate into coml"""ite sed,monlal) particle. duringtmn'port and deposition in lakes, ri"el'S. estuarie., and ocean',Agglomeration i. an important prerequisite for tile deposition of clay' and,ilt·.ittd mineral gmins. especially for .uspendtd maUer for "'hich senling"elocity is exceeded b\ the upward .'erl1cal.eIOClty of waters. The foll"",;ngabiotic and biological mechani.m. rna)' effect agglomeration of suspended""diments in silu

Electrochemical flocculation, a chemical pllenomenon, is theagglomeration produced ..-hen salt is added '0 a freSh_water .uspension ofcia) mineral•. F1occulation of su,pendeJ sedimen", 0CCIlf'l principally inestuane!. A second abiotic mechani'm i' coagulation or sedimentagglomeration b) di,sol.'ed molecules ..-hicll are sorbed On to immel'St:dmineral surfaces. A mechanism of biological agglomeration i. thepelietizatioo of fine'grained sedimenlS hy filter.reeding planktonic and

benrhic organisms. Finally, gro"'h of microbe' on suspended sWimenlS andrhe a...xiared Sl:crelion of slick)' mucal 'ubsrances which bind suspendedsediments rogerher. i. aDolher mechanism fDr aWorneratlon. Diaroms ha"ealso been obsl:rHd 10 agglomerate suspended Sl:dimenlS in two SoulhCarolina estuaries. Examples of the mode of grain auachmenl. anributable tofecal pellelizarion and to abiotic mechanisms of agglomeration, includinge1ectr<Xhemical nOCC\llahon. have been gIven for a bay esmary (Zabawa.1978),

The ehemkaJ eompomion of s.edimenlS "aries "idel)'. depending onge<>graphieallocation and origin, F.....il peliric Sl:dimenlS contain far Iellirhan1" of organIC m.Uer. A caleularion oflhe COmJlO'ilioD oflhe mineral fractionof pelils on a world·wide scale ga"e 5~ clay minerals. 2Mlt quanz. 8"feldspar. 1" carbon.res. 3" iron oxides. and 3" 'others' (V•• lon, 1%2)When Ihe clay miner.ls are classified according \0 Iheir layer slrucrure. illiles.re ~t .bundant On a global seale. ReC<'nt pelilic Sl:dimenlS e'hibit a higherfraction of organic matler (rangC' 1-6"; estimaled mean ,..lu" 3") thanf.....il pelitic "'diments. In " ..Ier bodies wilh a higher degree ofeutrophirnlion, Ihe organic fraction probabl)' is much higher and ofrene,,'eeds IMlt. The comJlO'ilion of the mineral fraction probably does nordiffer significantly from Ihal of f.....i1 sediments (Miiller. 1981). The miDeralfraction of suspended paniculate m.lter, in principle. has a similarcomposition; in coasral ...·.re.... quartz. feldsp.r. calcite, chlorire. kaolinile.and illire are comm"" COnSlituentS. The CQrnJlO'ition of minerals varies w'ilhdisrance offshore. mggesrrng conrrihurions from land sources and frombiogenic SOurces iD the of/shore areas (Chan and Chen, 1911).

The organic fraclions of "'diments and suspended paniculate m.ner ha"ebeeD studied and compared with rOOse of humU§ from rerrellrialenvironments. Vi""r (1982) in"estigared rhe equi"alent ...~ighto and rhenumber of e.arbox)1 and phenolic h\'drox)'l group' of moIeClllar weighlfraction, of fulvic and humic acids <ampled at ,-anou' locali"". in awarershed. He compared the result. wilh dala reponed lor humic malerialfrom orher .quaric and lerre"ri.l en"ironment<. ThIs comparison showedlhar ahhough aquatic humic compounds ha"e ""'eral propenies quire distinctfrom soil humus, in their acidic functional,roups, aqualic humic compoundsdiffer "ery hllle from humus of lerrellrial OrigiD. The 001)" dilllimilarityobsl:"ed was Ihal aquatic humic acids normall)' contain mOre COOH andfewe' phenolic OH group' lhan Iheir terreSlrial counterpa".

Since fulvic acids are defined by rheir solubllil\' behaviour in alkaline andacidic media rather than b)" chemical charaereritallOn, the 'ful,'ic acid'fractIon obtained b)' srandard fraction.rion procedure, may conrainconsiderable portions of nOn· humic mbsrances; thus. in rhe 'fulvic acid'fraolion of marine ",dimen"'. polysaccharides containing uronic acid> aredominanr componenrs (Hatcher er aI., 1980).

141) TESTS TO PREOICT THE E~VI RO~ \lE~"TAL BEllAVIOUR OF OlBllCALS

Suspended particulate maller in marine wa,er has been sho"'n to contain,after hy'drolysis. amino acids ,,'hose nitrogen content could often account for100% of 'he 'otal particulale organic ni'rogen conlenl (Sieun and Mague.1918), Chlorophyll is ano'her important organic constituen, of marinesuspended maner. and can be used to estimate the concentration of.uspended maUer in sea surface laye.. "ia the measuremen, of the spectraldis,ribu,ion of ,he sea radiance coefficient (Pelevin. 1978). Finall)'. ,heparticulate maner in continuous films on 'he sea surface coos..ts of lipidscontaining fau}' acids and other surface-ac'i"e subs,ances (Kanner andBrockmann, 1918).

3.2.3 PHYSICAL, CHE~t1CAL A."D BIOCHDtlCAL PROCESSES L"SEUlME~'TS

The 5po.li£d di.5lribu,ion of o.mhropogtnic chemical. in udimtnlJ normallydepend. on their souf'Ct's and form by' "chich they are lransported.En"ironmental chemicals in sediments originale from various sources. forexample from direct emls,ion by wa,te ""a,er, by rainfall, or by surfacerun-off of soil. TheY' may' enter the water in dis5<>I>'ed form as wen as adsorbedon particl... The tran'fer of dissolved chemicals '0 ,he sediment i, gO\'emedby adSO'l',ionjde<orp,ion processes; the 'ranspon of chemicals ad<orbed onparticles by <oil run·off is e<pecially' importan' for agTicul'ural chemicals. Theextent of pesticide run-off depends, in addition '0 the physko-ehemicalpropertie, of the chemicals, on the inteositl and duration of rainfall. soHco"er. soil lype. and slope (Weber, 1917; Johnson and Baker, 1982).Additionally. ,he spatial distribution of pesticides from run'off is affected bylimnological charac'eristics of 'he respecti"e aquatiC sy'stem.

Upon entf}'" into an aquatic system. pesticides attached to particulates arefractionated according to the size and densitl of the adsorbent particles; thefi""r and often less dense particles show greater mO\'emenlS. This process ofparllcle si~e segregation contributes to a posillH correlation between Ihe dllyand organic maUer contents of lake sediment and 'he dep,h of "",'eT Otdistance from shore at which the sediment is sampled. The ,imilaritl' belweenthe densities of water and organic matter and the association of organicmailer mainly with the finer mineral fraction causes the more highly' organicpartides 10 settle out in deeper wa,ers, Similarly, a vertical segregation ofpartides occurs with the coarse" partides being deposited first and the finerones lal.r, Thus Ihe finest particles 'end to constitute 'he ",'id phase a'thesediment-water interface, although this process is {)\'ershadowed ,,'here thereis substantial mixing at the interlace (Browman and Chesle... 1917). Sincesoil-sorbed pesticide. are concentrated on Ihe finer particles (e,g.. Richardsonand Epstein. 1912), this panicle siu fTactionat;on results in an une"endistribution of peSticides from soil run-off within the sediments.

'"The principle. of sorp'io~ of chemicals 10 sediment' are oomparable to

those of sorption to soil. (see Chapter 5.2). Adsorption data on sedimen.. orsuspcnokd particulate mailer hay. been $IIo--'n to fit Freundlich or Langmuirequation,; (Reimen and Krenke!. 1974; Harding and PhilUps. 1978;Karickhoff and Brown. 1978; Karidhoff rl "' .. 1979: Hiraizumi" 001.. 1979:Peck., "I" 1980; Bib<> and Miiller. 1982). As in soil,. the adsorption ofchemical> to sediments is mainly adsorption til organic maller. This applies tonon·ionic organic chemical. bul also to some metals (Leland 0' al .. 1973.Herbes. 1977; Kronmaj'cr and Streit. 1978; Karickhoff ., "I .• 1979:Kemdorlf 0' aI.• 1979; Hit.izumi.1 al.. 1979; Nriagu and Coker. 1980; Peck., ai.. 1980). A key distinction bet..-een soils and soedimcn', in !hiS CQII,ext i<particle ,ize composition, Unlike ""ii' which contain a wide range of pllrticlesizes. sediments within a gi'-en compartment may contain a ,-cry narrow rangeof partide size<. Functional dependence of ad<orption on partide 'ize could'Oar} the degree of ""rption in different ri\Or companmentS and produce anon·uniform dIStribution of sorbed pollutant wi'h,n the sediment. 'imilar tothat of pesticide, from soil run-off For given particle 'ize i",late,. the linearpartition coefficients for non.ionic organic chemical' W'ere found to bedireetly related to organic carbon content, Partition wefficien" based On theorganic carbon content of the sediment fractions (K«_values) showed abell-'haped dependence on particle size, the maximum being in the mediumOr fine silt fraction (Karickhoff., Di.• 1979). l1>e autho.. concluded Ihal.gi"en the SCt of scdimenr-independent K.,.s. the COntent of organic carbonand the masses of each size fraction. a composite adsorption COn,tan' can becomputed for any gi'-en sediment,

The K «-"alue, have been reported to be well correlated to n·octanol-waterpartition coefficient,. Octanol-w-ater partitioning prm'ide' a much benerestimator for sediment-"'arer partitioning. than doe' solubility'. because in amolecular sense, 'he partitioning of • oompound bet"-een water and eithersediment Or octanol in'-ol'-e, monomer di<tribution bet""een tWO phalts. Onthe other hand. saturated aqueous .olution. in,'o!>-e the equilibration ofprimarily di,,,,,I"ed monome", with Cl)'Slalline compound,. Ct}'stal energycontributes '0 water ""lubilitJes but docs not affenthe monomer_aSSlXiatedproperties of partition and adsorption coefficients, Since the K.,s are "'elloorrelated to octanol_water panition coefficient'. rea"""able estimation ofthe sorption beh..iour of hy-drophobic pollutants can be made from aknowledge of the particle 'ize distribUtion and a,,,,,,,,iated organic carbonrontent of the sediment and the octanol-water partition coefficients of thechemical' (Karidhoff ., at" 1979).

For tu ca,ionic pestieide paraquat ,,-hich i. sorbed mainly b)' ion exchange.sorption partition coefficients sho",ed a definite correlation "ilh the cationnchange capacity of indi,-,dual <Ize fraction' (Karickhoff and Brown. 1978).

For melals in general. hydrous oxides of manganese and iron furnish Ihe

142 TESfS TO PREOICfTHE E!'<VIRO,~\lEl'>TALBEHAVIOUR OFOIHtlCA!.S

principal control on fIXation In fresh.waler ~dlmenlS (Jenne, 1968), Someorganic chemicals are also adsorbed on Fe(lll) oxides and can bea.>pfCClpil.Oled by Fe(lIl) SlJIt! from "",er (Sridharan and Lee. 1972). Formercury (as HgO,), Ihe adSOrplion On clays. sands and specific organics wasnegalively influenced by' Ihe chloride ion concentration of Ihe water (Reime,..and Krenke!. 1974; Kerndorff., m.. 1979), The e<mlenl of Ihe radionuclideplutonium in sedimen150fthe Rhine ri"er was shown 10 be higher in sedimentfraclions ,."h I"""er panicle diameler Ihan in larger panicles (Pimpl and~hiil1elkopf. 1982).

Sediment' would be the final sink for adsorbed chemicals if exchangeceactions belween ~dimenl and waler "'ere negligible. Howe'·er. Ihi.assumplion is "ue only for sediments al "er}' deep sites of waler bodies.l"ormally. Ihere exi<l .-tmobiMatio~ prottsse> wh~h ,""suit in a conti~uou.

releas<: of chemicals into the water and.thu •• in their bioavailLbilil} and enlryinto the food chain,

One remobilization process is desorption, Adsorption/desorption equilibriamay be diSturbed by a decrease of Ihe concentration in Ihe aqueous pha~ a. a,""suit of high water flow Ules and/or of ,'oIatiliUllio~. Up,ake of theduorbcd chemicals by organisms. including planklon. in"enebrates, and fish.which. depending on Ihe properties of Ihe Chemical. may be (ollo"'ed by'metabolic reaclions re.uhing in degradation or productio~ of melabolite.with i~creased water solubihty. also conlribules to Ihe mobilization ofsediment·associaled chemicals. E""ion of sediments i. anolher importantmechanism by "hich chemicals associated 10 sediments a,e mobilized andmade available lor uplake by fish (Olsson. 1978).

In addition 10 the abo'e mohili7,alion palhw"y's. s<:diment·dwelling anddeposit-feeding animals (aqualic worms. clam,. shrimps) COfllribute 10 Ihemobili<a'ion of sedimenHlssociated chemicals by two other mechanisms. Thefirst mechanism is dir"'" uplake of lhe chemlloal from the sediment inlo Iheirbody through feeding activities Wilhoul preceding desorplion, Such uplakemay be followed by tislUe accumuiaiion and thus Ihe entry of the chemicalinto the food chain, Concentration faclors lor the uptake of some chemicaJsfrom sediment are lower than II>os.e from "'atel by ~"eral orders ofmagni,u<!e (Veda", w.. 1976; Roe;ljadi.' QI.• 1978a; F"",ler., W.. 1978;L}es. I 979); ne,erlhel~>s. s<:dimenlS mal conlribuI~ Ih~ bulk of lipophilicch~mical. to Ih~ bod} burden of worm, since ~dim~n.. r~pr~senl by far Ihelargest d~pol for these chemical. in the aquatIc system, (Fowler ~t aJ .. 1978).H"",'~'~r. th~ uplake of chemicai' by lhe IWo rOUI~S. uplake of Ih~ de50rbedsubslance in int~rstilial "'at~r and ing~stion of solid malerial wllh Iheadsorbed chemical. is nOl clearly dis"ngui.h~d in mos. of Ihe experim~n"

reporl~d (Renfro. 1973; Amiard-Triqu~t. 1974; Beasley and Fowler, 1976;Murra}' and Renfro. 1976; Courtney and Ulng\lon. 1978; Elde"" QI .. 1979;Lye•• 1979; Phelps. 1979; M<Le~se.tal .• 1980: Jennings and F"",'ler. 1980).

'"Special upl'rimtnLal ,echntqo>e$"~needed (0' the "'panuc <k'crmllUlllOll ofboth up\.lkc path",,,». In the ca.., 01 cadm,~m. 11 ha. been >hooo-n thai uptakethrough l1leestion of oedimenl i10 relau>e]) i"dfJlicn, (Luoma and Jenne.1971> aDd 1977). 'e"~k$s. ,lIis p;1th"l1\ Ina) be important for ,hemobdLtaIJOft of chemical' ..ull ..,.,. de1orplion raIn.

1M attumgb...... at pol~doIonJlal~ brphen>" '" the Pol)"Cbxlc 'M;WlIl

\UN nrnu from~~nl ..... shora 10 be directl) 'dlled 10 PCB

lXlOl:enmtioll in .edimcnt "lid '0 c'pCl&U'c time and ;m~ll "'laled to wonIII

s.tt; wmibrl). a reb...... oll<'a>lll.....1JOft 10 oedImeOI CO<lC:IOnll"llioQ and.......... oize ...,..~-ed for the lobrimp C,..",.,.."'P~ (Metee1e".J.. 1911O). 1M lliolop;aI.'-..bobdn\ of IUd in 1M oedimen..... >hown lO beIUDD&I> infJucn<:ed b) tIM: k-el ot ""adil) ulf¥tabk Il'QR (l...uoma allll Bf}lIn.19·11). 1Mrt .. ~ bmncd 'nfomuotion 0lIl correlations hc''''"ffnb;oa'-aiJabiIi.) 01 ~nl__l£d cbeRtiah and their ph)>ical Of

cbenua.l properties. The .'aibbih~ of Kdiment.oound m(Ws to thedeposn·feeding dlom. U_ IHdthOfil. ..... <kpelldeot upon theph)~mical nature of 1he meI.lJ_~mcot ilWX:iation (Luomll .ndJelllle. 19-7). -':0 ";mpk oonel",ion IIa5 bfen <:Jbs<,r.ed he,ween 1Mm.->'wbility of ""dimcnt·bound me,al. and chemical c",,,,nab,Ji'1 (Luomaand knnc. 1976: Jennings and FO""!cr, 1980), For hldrocarbon., it wasfound Ihatthe heavier molecular "ellht aromatic compounds tended to bemOre eone<:ntrated in t1j,<ue and retained for longer p"riod. of time than thehihter compounds (Roesijadi tt aI., 1978a).

The second mechanism by "hieh deposit.fude.., e'p"cially aquatic "orms,contribute to the mobihxation of adso,bed chemical. is their borrowingaeti"ity which can be "'garded 1\ 'bioloBical er"'ion', Thus, Renfro (1913)feported 3-7 times htgher losses of "'Zn when Polychaete worm, wereburtow;ng through the sediment, a. compared 10 los.." caused by .I<Wo'lynO""ing seaWateL For mercury, n is as',um«lthat tbe bentbic macrofau,,-, e.,tubifocid "'01111" could be: enurel)' ~ble for .he cl<-arance of the metalfrom tbe btd sediments of nO"'·lt1& ..."atef .)'Stem. (Bodd,ng.OfI tl aI., 1979),

Information on mig,a_ of chemical> ",'ilhin 5ediments is limIted. TIlemign.tion of "'c. in sediments _-nil and .."bout benthos M$ bttn Sludi«l(Robbins tl aI.• 1979). In sediment _"bo," benthos. 5JDlI!l bul measunblenugnlJOO of "Co ooeurred "'th an effecme moIeaaIar diJJusiou ooeffocicn, of0,02 an')f In sediment ",th tho deposol.feedmg Obgochaele TIIbt{uaJJ<ju. "'fucb feeds beloo- J an aDd ddecate< ... ....uee se<hmeol). tholabelled Iaye. "'"as huned by tho uimal. al a tale of 0.052;:; 0.00' an.day(20 "C), "'"ben labelled pa~ tntem;! tho ft«ling zone, TCs rtappum;!III .."fllCl: sedunents """aunJ a bimoc!a1 KtI'lty profile. In tirnt. tho KOn1tytended iO"'-ard a nniform dowlboot>Oll oo-er tM lIpp« 6 an, dccrc3$Ul1uponentiaJl) below this Ia,e. to ..n6tteCUbit Inds by 9 CIIl. In sediment';Ith tht deposil·fttdint Ampb,pod. Po..llp:IrN Itoyi. wbidl feeds ...

144 TEITS TO PREDICT THE EN\'IRO~ 'tE~TAi. 8EHAV10UR OF CIlE~lIc,o.LS

n(ar'surface sedim~nl and m<we~ through superficial sedimems in aplough-like manner. uniform acti",)' de'e1oped rapidly (-17 dII)s) dO"'T1 10 a...·ell defined deplh (l.~ cm). The mixing of sediments bl PonlOporeiJ: i.de>cribed by a simple quamila1ive model of edd) diffu.i,'e mixing of sedimemsolido. The value of th~ diffusion ooeffici~nl, 4.4 em'/yr (7 .c). was compul~dfrom a lea't ><luar~s fil of th~oreticaJ to ~"'~d profil~ broadening O"erlim~, Similarl)'. a redislribution of m~rcury in sedimenlS ....a. ob>e" ~d underIhe influence of 'ubificid wormS (Boddinglon tt ~I.. 1979),

Ch~",ical and bioch~",jcalprofesses in sedimenls are characteriZed bl' 'heaeralion profiles of lhe sediment. l>pper sediment la)ers ... bicb arecharacterized by a~robic microorgani.ms. bl' lhe occurrence of Fe-Ill-oxide.and ofl~n by higber aqua'ic plants. "al)l grea11\ in thickness. depending on lheo'\,gen suppl)" from lbe O\'~rl)'ing waler. In flo"',ng "'at~r bodies. thethickness range is belween some decimetreo 10 a few' cemimetres (Fisch~r andBaumann. 1976), On the other hand. anaerobic condition. frequently dooccur at wr)' shallow depths. Lak~ sedim~ms have the tendel\C)-' 10 becom~

C)'clicall\, anaerobic for u1end~d period., Thi' capacity is r~lated to thc size.shape, and producli'il) of the lake. Changing conditions from aerobic 10anaerobic alters significantly Ibe composilion of lhe sediment solid phase(Brow'man and o.~Sl~rs. 1977).

Wher~a, the aClivity of aerobic microorganisms is cbaracteriz~d mainl\, bI'lbe prodUClion of carbon dioxide, in anaerobic environment,; other g areformed a, metabolic end producls. These are mainly h)drogen Iphidere...lting from ,ulpbate reduction (Udluf1 and Weil. 1974; Oremland andTa)lor. 1978). methane re>ulting from bacterial decomposition of organiccompounds (Snodgrass. 1976; Oreml.nd .nd Tallor. 1978). ammonia. andfr~e niuogen resulting from deni1rification processes ....hich have been shownto in"e.... in anaerobic medium (Ande""n. 1977).

For the differemiation between aerobic and anaerobic sedim~nl zones.m~a,urememS of oxidation.redu«ion po'en'ial (Pauick. Jr.. 1966) or ofOXIgen consumptlon (Edberg and Hofst~in. 1973; Brewer n aI .• 1977) hay'ebeen r<:por<ed. Ho....e,er, it is also possible to determIne anaerobic reactionproducts bI" chemical oxidation m~lhod,. e.g, of readily oxidi~able reducedsub>lance~. Fisch~r and Baumann (1976) reponed the delerminalion of'educed subs1.nces bl rapid o'idalion wi'h a diluled poraSOlumdichromatejsulphuric acid solUlion. These '·alues. txpreSloCd a5 meq,ll 00 ml offr~h sample, sho....ed a non.li""ar. n~gat"~ correlation ....ilb redox polemia!.

The panicipalion of .n1hropogenic chem;cal, in lhe nalUral biochemicalreactions in tb~ sedimem result. in a mUltilUde of oxidalive. reduchye. orhl'drolltic metabolic conwrsion and degrada'ion produclS and 'heirconjugat.... which are not discussed here in d~tail (see Chapter -1.1: KI~in andScheunerl. 1978. Aleunder, 1981). In a~robic sediments, oxidali'emetabolic proce.... prey'aiL and carbon dioxide i. tbe final d~gradalion

'"product of en'ironmental chemical.. Enl)m~ produced b)sediment-dwelling in'-encbra'e. (Lee el aI., 1979, Gardner., al .• 1979) andhightT plants (\lOza., ai., 1974) rOOled in sediment contribute to <XmHrsionand degradation of organic xenooiOlics. Since anaerobic condi'i<mS probabl\pre'-ail in sediments, their influence on the deJ!11ldation and conv.noi"" ofen'-;'Qrlmental chemical; ",II be ,mponane The information a'ailable toda)on ,",eli con,-ersions has been obtained in experimem. nOl onl)' ","hscdimena but also "'ith other anaerobic material maintained in thelaboralOf). e.g., flooded ",il, anaerobic sewage sludge, etc.

Under anaerobic condition'. chemical••uch a. chlorinated h)drocarbons.which are normally per,iStent. rna) ha,-. shwt lile'ime' (Hill and McCan).1967). Thi' probably i. due to the fanlhatlhe fin' degradation Slep for these>ub>lance:s. reducti,-e dechlonnation. eaSIly occun in anaerobic media and isnol exclu,i'ely a biolic I'roces.>. A t)'pical u.mple IS the reduni'-edechlorina'ion of DDT to DOD In "'diments (Leland e, aI .• 1973: Miles.1977), Gla.. (1972) reponed Ihe reducti"e dechlorinalion of DDT 10 ODDby an iron redox s)'stem on ,-i"v and proposed a mechani'm for thedegradation of DDT in anaerobic soils, Electrons furnished b)' the reduce:dorgani~ substrate are transferred 10 ,he DOT molC<'ules via lhe Fe" _ions thusinitiating. free radical reaction in the absence: of o"gen_ Zoro e, aI. (I974)achie'ed onl) a very .Iow TractiQn under thrsoe conditions. They concluded'hat this reducti' e proces.s is mediated by reduce:d iron porphyrins and is !lOt aeoscntial pan of ce:1I me"boli."" This f",ding ha. con.iderable environmental.ignifkan~e since: mO>t !i'ing matenal contain' Iron porphynns bound "'ithpro'eins which. under the ,educing condi'ions in an anaerobic environ men'characteri"ic of dead and decaling malter, "'ould ~alaly", rapid con,-enionof DDT to DOD and Other produCls.

Toxaphene degradation In anoxic estuarine sed,ments IS another exampleof re<!ueti'e reactlon, in s.edimen.. (Williams and Bidleman. 1979).Re<!uctiQn occurs in "erile as "dl as non_Sterile >edim.nts and also insand-Fe"-Fe "_.y'..em, but not in a sand sy-,tem that does nOt contain theiron re<!ox comple. couple

The simulation of melabolic conversions of em'ironmenlal ~hemi~als bysimple chemicallaborato\) feaetion' i' in general problemati~ becaus.e of thestereospe<ificity of ,he enZ)meS In''ol'·ed. HO"'e'-er, since il is e,ident thatabimi. faetolS can aet upon en,-ironmenlal chemIcals In «d,men", simulatedreactions in 'he laboralO\)' rna) be u«fullO replace complicated tests, Thus,the anaerobic con'el"Sion of DDT to DOD and of DTE(1,1 ,I ,2-tetra~hloro-2,2-bis.-fp-chlorophen)llethane)to DOE (Beland e1 at..1914) can be ~rformed electroch.mi~ally (Rosenthal and Lacos'e. 1959).The complete reducti.-e de~hlorinaliOt1 of lindane in anaerobic «wage sludgeand soil. r<sulling in formation of ben2Cne. can be SImulate<! by aneleetrochemical reduction (Beland " a/ .. 1976)_ The authors reponed the

146 TESTS TO PJlEDICT THE E,I;VIR01<M.El>TAL BEHAVIOUR OF CHBliCALS

predictability of anaerobic degradation produet~ of organoha\~n

compound. in the environmenl by elec1rochemical reduclion Bas<cd on 'heirresulu. Ihey proposed lentati,'ely. that compound. wilh an E", mOre posi'ivethan - 1,521 V (versu. ",l1uraled calomel electrode) in dimeth}'I"ulphoxide"ill be anaerobicall}' degraded and compounds with an E,. more negati"ethan -1.757 V "'ill nol be anaerobically reduct'd (E,. i" Ihe interruptpotential determined by Ihe zero crossing of the Sl'cond derivalive curve;Farwell er til" 1975),

Conlrary 10 the ehmination of chlorine atomS bound 1o non-aromat;ccamon. elimination of aromatic Chlorine of Ihe herbicide diu ron Wa~ "hown 10be an exdu"i"ely biotic process and ""as performed only b)' adaptedmicroorganism. (Alla"'a)' er til ,_ 1982a and b),

Reduction reactions olher Ihan dechlonnalion arc also common Inanaerobic media, e,g, the reduction of the mtro group ofpenlachiorollllrobenzene in anaerobic soil (MuTth) and Kaufman, 1978) andof paralhion in Sl'diment" (Wahid and Sclhunalhan. 1979),

As Ihe final degradation product. carbon dioxide is formed also underanaerobic condition" When idenlical degradalion sludies of 14 em'ironmentalchemicals were carried 0\11 wilh identical soil/waler "u"pen.ions underaerobic and anaerobic condition•. Ihe amount of carbon dioxide formed fromIhe chemical under anaerobic condilions did nol greally differ from Ihatproduced under aerobIC condiuons (KoTte" dl.. 1983)

The formalion of Ihe olher degradation products li~e melhane. sulphide. orni"agen from xenobiolics has been in"estigated thus far only to a 'er)' hmitedexlent, Methodolog) ;, .. ailable 10 determine melhane as a melabolic endproduct for natural compound••uch a. acelate (Winfrey and Zei~u•. 1979),

There e,iSlS also Ihe possibilit) of SCCOfldaT) reactions of en"ironmentalchemical~wilh Ihelot n..uralend products. espceially "i'h h)'dragen sulphide,He..') mOials are immobilized as SUlphIdes, The involvemen' of h)'dragen,ulphide in Ihe dealx)'lation of aminoparathion ha' been demonstraled byWahid and Se'hunathan (1919),

Covalent binding of organic chemical•• like aniline' or phe""I•• 10 humicacid precursors and Iheir incorporation inlO humic acid macromolecules insoils. similarly could occur in Sl'din,enlS, This "'ould imply an immobilizationot 'he compound and its slow remobilization by mIcrobial degradalioo of lhehumic acids (Hsu and Banha. 1976: Klein and Scheunen. 1982),

fmeTllCt;olU be/.....n so.pt;v, '!frets dnd ch,m;cdl PFQceue. have !>cendemonstrated b)' so"eral aUlhors, Fischer and Baumann (1980) reponed apoliili"e effect 01 olidatioo on 'he sorplion of phosphate, During intensi"ereduCtion b)' sodium di,h,onlle. phosphate sorbing <i"er sedim,n.. ~ho....ed apronounced desorption of phosphate, Reoxidalion by air .auSl'd an inereaSl'in phosphate sorption up '0 fi"e tim~ the original ,'alue. Ihe le,'el of sorp,ionbeing linearly relaled '0 rhe ferric o,ide contenl of ,he samplc, A possible

SEDt~IH.TS '"uplanalion for Ihis phenomenon i. the oxidali"e pre<:ipitalion of iron(lIl)oxide. which ha"e a high surf.ce .rea and are "er)' aClive in phosphateadsorption. Fe(lll) oxides ha"e been shown 10 be .Iso important adsorbersfor hea')' metals (Jenne. I%8) and for some organic chemi<:als which art'coprecipitated from ...·.ter by Fe(lIl) lall. (Sridharan and Lee. 1972). Thus. ahigher .er.tion state of the sediment and. consequentl)'. a higher contenl ofFe(IlI) oxide' re.ull in lower bioavailabilit)· of heavy metal' todeposil·feeders (Luoma and Jenne. 1977); a similar behaviour is to beexpected for >orne organic chemicals.

A positive effect of adsorbing ,urface. on biodegradation has beenreported for chlorinale<! phenols (8o)'le'l Ill .. 1980; Blades·Fillmor••, al.,1982). for the herbicide 2,4.D (Watson, 1977) and for the otherorganochlorine compound, (Lee and R)'an. 1979). An indirect innuence ofsurface. on Ihe biological degradalion via effect. on microorganism growlhwas reponed for uperiments ";Ih 2.4,6-triehloropheool in waler in Ihepresence of various sediments as well as inorganic surfaces (Blades-Fillmore 11Ill.. 1982). The authors demonstrated the role of colonizable surfaces inpro'-iding optImum condition. for the biodegrad.tion of2.4.6·niehlorophenoL While the: posili'-e effect of Ihe presence of sediment.has been kn""'n for a while. often sediments wert' Ihoughtlo be sources ofspecific melaboliring bacI..ia; Ihis work ,ho"'cd tha' 2,4.6-TCP degradingb.cteria were a,'ailable in the waler. but surfaces for bacterial altachmentwere importanl in the water self.purification process,

How...·er. if degradation i. determine<! onl)' by measurement of the loss ofparent compound, adsorbing malerial containing humic substanc.. Canirre'el'S.lbl) bind and incorporate Ihe substance inlo humic acidmaeromolecule.. ,,-hich rna)' be mi.interpreted as degradation_ Thecompound 2.4,6-trichlorophenol used in the slud)' of Blades·Filimore et ai,(1982) 'hows a marke<!tendenC)'- to form such humic acid complexes in soil(Fragiadaki•• 1980). lbc: same .pplies 10 .tud,e. on Ihe blodegrad.tion of2.4.0 "ilh and wilhou, sedimenl (Watson. 1977); 2.4-D forms considerableamOunt. of bound residue. in soil (Smilh and Muir. 1980). BO)-'le ., 121. (1980).howed, using "C·labelled pentachlorophenol. that the addition of sedimenl10 the ....ater deereased the half.jife of poentachlorophenol but not the lotalamounlof "c reco'-ere<! in the .ySlem. Nevertheless, since posili,-e effe""s of.urface. on ,e.idue I""", ha,'e been ohser"ed for inorganic .urface•. and'in"" such effee\s ha"t been found in degradation studies with ''C.labelledchemical. b)' measuring "CO, (Lee and R)'an. 1979). it may be conclude<!Ihal biodegradalion occurs mOSt readil)' at the sediment/...·ater interph.se.

Oual)'tic reaction. similar to Ihose affecting the total degradation ofchemicals adsorbed on dr)' .urf.ce. (Bahadir tl.u .. 1978) do n01 occur in theaqualic environmenl; ho..-e"er. indiT«t influences ofsltJpendtd ..dim.",s onphovlysis h.,-e tlttn repone<!. If suspoende<! particles do not absorb light to a

148 TESTS TO PREDICT TIlE ENVIRO;';\IE,,'TAL BEHA VIOUll OF CHE",ICAlS

~ignifjcantexlent, then the rale~ of direct photol)~i~= be cnllanccd ill turbidwaler compared 10 dear "'at.. because of lhe increased diffusi'-eness of lighl(Miller and Zepp. 1979). If the ~u~pended panides do absorb light. lhendirect photol)'sis decreases (Oli,'er n di.. 1979); Ihis decrease. howe'-er. maybe offsel by an increne in lhe rale. of photosensilized reactions (Bedding ~I

di.• 1983).

3.U LABORATORY TESfS TO DETERMII\E SIl'iGLE FACTORSAFFECTI:\G THE FATE 0.- CHnllCALS IN SEDlME;\TS

NumerOll' laboralory lests ha'-e been reported 10 delermine single faclOrssuch as adsorplion/desorptiOn processes. remobiliUllion and accumulalion byaqualic organisms. and chemical and biochemical react,,,,... affecllng lhe faleof chem,cals in sedimenl', In laboralo') model e"""y'stems and in field lest.mosll) nalural sediment' are used, where.., in single faclor laboralOry te'l~

which ohen are used for comparative e"alualion of chemicals, Olher malerialshave been lested ,ince n",ural sediments cannot be standardized. Muller(19g I) proposed. as a standard arlificial sediment mixlure. Ihe a"erage of lhemineral composilion of sediments fTom fouT Gennan rivers (illile. 5~;kaolinite. II "'; chlorite, 5"'; quam, 19'" feldspar, 8"'; carbonate. 6"'): 8'"organ.. mailer i, added bUI lhe difficulties in'ol"ed in its standardizalionhave nOl been solved. The same problems of 'landardiUllion arise when"-ater.logged soil or nalural soii or sediment fracliom are used inslead ofinlact nalUral sedimenl samples, Therefore. symhelic malerials ha"e alsobeen used !O ,imulale lhe respecti"e component of the nalural .edimen,.which is primarily responsible for the specific fate process in,'eshga,ed. InTable 3.2.1, ..amples for laboralory lesls are listed. and Ihe malerials use<!are induded.

For ad30rplionjdnorprion of organic chemicals. an OECD lest guideline is",'ailable for soils (OECD Chemicals Testing Programme, 1991). ,,-hich may'be used also for na lmal sediments. sedi men Ipanide fraC1ion~,OT O! her ma lerials(see Chapler 5.2), AfteT equilibratiOn of the dissolved chemieal belween <oiland waler. lhe adsorplion coefficienl ;. delennined as a physieo-chemie:alsubslance propen)' characteristic of the diSlribuu"" behaviour of lhechemie:al bel""en soi~'sediment and waler. It is anticipa'ed lhat ,.-ilhin lheI;haking lime (16 hours) an equilibrium be,ween bo'h phases is ,eached andthat no significant biodegradalion occurs dunng lhis lime. FOT melal~ inprinciple the ..me melh<>d is used; lhe equilibralion time mal' be very .hon(Kemdorff e, at.. 1979: Amiard-Triquel. 1974). Since organic mailer i' themOSt importam consliluent of sediment particles for lhe adsorption ofnon·,,,,,ic organic ehemie:als. fOf lhese compounds it might be useful '0 carr),out ad<orpiion leslS only with organic adsorbent~, e.8. aulodaved yea,t cells(Herbes. 1977) Or dehldrated planklOn (Hiraizumi er al.. 1979),

rHWJ.l.! I OIJ'-.IO......--""r...........ff...... ' ... f_O(~·__..• ..__•

"d"",,110''''ftlo. I,,'n·0<l1O'"

It""""",,,., ion of .h<m icahf,om ....,,,,.,,, b~__p.

'''"' folloo<"'. "OI.o,ilu.',,",

Redu"ionlmi<!a'IO" "r>«lImen' and od""bobl<c1.ellllCali

l>ctnm,na,,,,,, of ctI<m.....,,' """,,i~ ...'e, <1""--

_...-__.... r ...OJ ...' p-'>d<,~-

""'0<10.«1 ynJl cell,

DchydfO'cd plank,,,n.qcd """,,'ed .o,oon

I'"r< m,ncul,

"1,0,

Na' "fOl ><dimcnu/><>d,"mdi,M<>nile/.i,

Ref.....".l~'

OECOQoo .. T........ "'._~__,.,l;:on<1lootf ' .• 1979K.......". ,I979H__ ,I979P«k .....,19tO__ M...... I912

l;:on,;khoff_B,_•• lmC"""""'.1Id I.......".. 1mK",nflllll"',.1Id '>'<e". "'8ll..d,.. _l't"lh",. ,mRe"......1Id K,....k... ,'J1~

Ilnbe>.I'177

H,,,I'"ml,,tN.. l9'!9

H".I""", "tN., 1mItel",." ."d Kr<"k,l, '~74

1l,!><>."dM"II.'.''Ill2

Coo, '''.~ .rld I..nl."on. 1'J18

11",11<, ."d lIa"n'.nn. I\llIO

KolJyhn,ldandl ,,'....."". l'J1S

h<1<,r ;nvali""e<t

Upl.~eof <hemical>I,om pa'l",ul",« b~

orp"i,m, vra "'aI<'

Upla~eof chem",abI,om sedi"",nl by ,lq""i'.lerd,nll inv<T,e"'''e.

1',indpk 01 ltsl

Del<Tmi • .,,,," 01..,lahlilOlion f'om"'Ole' OV<T ..,jime'"

IJctcrm,n>lion nf upla~eb'lr... alp<

ne,."",in""'n 01 uplakeby fi>h

Ani ",a" kePI in ..,jimen!>under ~'ate' in aq""ria

SCpa...le dele'Ol,nOlionof uplake of ad"",b<d0' <l<s<>rb<d ehern"al

N0' ~cr ,er<>"«!

No'"rol..,j,,,,<,,,

Nalural,.",al'­m"roparl",uta,..

N.rur.1 oed,men" orsedimen' pan"k f''''''''n,

De",,",1'"01''' add, !>enlonlt,-,prolein

NOIur.l..,jimen".a",o,ph;" "e· andMn·o,ide< ...ilh ano

set Chopl"- S,l.e.I.• ",i",iple of KllIpller" ./"I 'IlI2}

La""",,'.I,, 1979

lI"drnl, Jr" and Phillrps. Jr..

'm

Kob~lin,kiand Livinl"on. I97SCourlne~ ano lanp,on, 1930

EI<l<rtluJ.,lmRenf'O,I97)Lye>,lmPhelps, 1979M"rrayand R,-nfro, 1976M,-t......'ol" 1~Courrne,.ud La"pton, 197~

lle"lrr and Fowler. 1976Jenni'I' and !'0...1er, 19!1OAmiord.Ttiq"eI.I974Roesija<li., a1.. 19780 and bU«l. tr 01.. 1976Fowle'., a/" 1'i1~

Rrx'ij"d'" 01 , 1978. "nd h

I'help,. 19]<;1

Luuma ano Jenne. 1976 .nd 1977

Ae< u"'ul" Ion "f ,h.",kal,f,orn .<ed'n,.,,' I" foodcha''',

M,-nllon ofchemkal,in sedimen"

Conv."Io" «",10",in sed''''.""

F«<Ionl 01 fI,h withpo" kul.,c- f«<l i"l,"""".b,at",

M<a""<m<o' of radio·octi oi'y 01 ,aJ10"""h<ksa' diff.,.n' deptl" of=Ii",.n' «>Iumn'

fr.cuba'ion of ,h.",kal,wi'h =I'",.n,/.'"dl'

b".,imen" "ilh

"'10""""

S''''UlatlO'' "f .biolic,ed.... ,•• dechlo,i".. ioo

..illionl ",ganic ",,'i"l,der'''''', ,a,bona'"".akil'"

C"dks

IlIil<clay

N3Inral ;edi",.n"

Not"'al =limen"

C"ltu,. media ,,"h

"''''''''''Pol''"''

S<1lime"'-dw<lIinl w"'''',In .I/"'i,o" 'edo'.y>'.mR.due<d h.mo,i"

1;I••,,,,,,,l><mkal 'ed""tlOfl

C""""'Y'''d l.a"l',on. 19l1()..., al", seet"'" J.1.'.

Robbin",.I" ,mlloddinlton.f nl.. 1979

W.,da"dM''''''''",",19Ja"erbes, 1981Miya,,,klnal.. 1971C1a,~ and M."omo,a. 1979l'.,\>es and Sch..an. 1978110yl."IlI.. I980William' and U,dleman, 19J9Sndh.ka'·!larik and $<th,,"a'h... , 19J&>John"," ."d 1.01."" J9Jl

7'<>'0<1.1" 1914lleland "ul.. 1976"'11 and Mcea",. 1%1

l.oronal,,1974M'y kierlll.. 191S"" y of Ill.. 1'1820 or><! ItClar, and Ma"omolll. 1mZoroerlll.• 19J4

GI.... 1971Willi.mund l1i<lkman, 1978

Zoroofal.. 1974

llel.nd <I .1., T9J6

T~bl<l,l.1 /rommuroj

lkvadOlion of c~.m""l,in ..,.jim"",,

RellC"on, or ,hemlcal>wil~ la= f,om "",u'ulan><:robi< 1"0''''''''

p,inoipk or ''''

1)<I«mina"o" of dis·ai>1X"U""':< or pa«nlronlpOUOO

D<I.,mi ..."on of c~.mical·bo",.' 'CO,

IXI.,."m.,ion or ch••"ical­bo,n. "CH,

kCOClion"",hll S

Mot,,;.1 u>c<1

Na,u,al ..d,m.n"

""" robi<: >OW"lI••Iudll<

Cultu" In<dia withmk,oolpni,""

Natu,al ,«hm.n" <Iffloo<lo<1 "';1

Microorllani"'"

N.t urol >«1m="

H,S

Clalk and M."nmura, 1919ll<:>yk ... ~I.. 19lI()w.",,". 1<n1IlI,d",·hll",0/.nal.,I982Sudha'ar_lIalik and Soth'''';tha", I'f7&Wald and Ma"ulIlura, 1918

Hilla"d M,Cally. 1961

Allaway" al.• 1982> a"d bClark and Ma"umu,a. 1979

Sethunathan and Y""hid•• 1969Vockd.l981f1c,t><.and SChwan. 1978\liy.,,,ki"al,, 191~

I", ."d Kya". 1979S<thu"athan ."d MacKlIC. 19691I..be!. 1981Sodhakar-llarik a"d S<thunatha.,. 19711bJ""n",nand 1 ul,'c•• 197'GordncH' ai" 1919MacRootlal" 1967N.I",n and Z.iOu•• 1974

wrnr,<)' .nd "ci~",. 1979

W.h,d a"d S<thu" .. ha". 19J9

The dependence of adsorplion/desorplion processes on the state ofaeralion of the .edimem may Ix tested by reduction of Ihe adsorbing mixturewith sodium dilhionile and b,· reoxidation with air (Fischer and Baumann.1990).R~mobili::mion of chemical' from sediments b}' increased Msorption

following volatilization of aqueous concenlrahons. mal' be tesled by anexperimemal set·up including sediment. water. and phy'sical condilions suchas movement of "'aler or air or bolh. promoting "olalilization from theaqueous solution. Kobylinhi and Livingston (1975) reported thedisappearance of mir.. from a system induding mirex.containing sand andflowing "'aler. About 40~ of the initial mire. concentration was lost from Ihesedimem under constant flow conditions within ~ week, whereas no los,occurred in a reference slatic teS1. Volatilization of parhcle.associatedchemical, via the aqueous phase. in principle. could be determined also inapparatus for the determination of ,olalilhy Irom aqueous solutions (seeChapter 5.3), The method of Klopf/er n al. (1982). for example. could bevaried by adding paniculate mailer "ilh the adsorbed chemical to the walet;volatilization is promoted by Stirring and by drawing air o,er Ihe walersurface.

Mobilizalion of chemicals from sediments through desorplion into theaqueous phase and uplake by organism, i' delermined by adding, e.g.• algae(Harding, Jr .• and Phillips. Jr" 1978; Laube ~r al.. 1979) or fish (Counneyand Langston. 1980; Kobylinski and Livingston. 1975) to water wi'h sedimentor particulate maner comaining the Chemical If the chemical is added towaler containing both sediment and algae or bacteria. sediment andorganisms compete for Ihe adsorbable chemical. The distribution of thechemical belween water. sedimenland organi,m, can be examined by' meansof a cu"·e anal)'siS of the distribulion pallern of a Ihree compartment model(Nakamura el al .. 1977; Ramamoonhy er a/ .• 1977).

The uptake of chemical' from sedimems by deposit.feed,ng invertebrates(.quatic worms. dam,. shrimps) normally is le,ted by keeping the animals insedimenlS or other materials under water according 10 their natural Ii,ingcopdilions. The kind of adsorbing material has ap important ipfluence On theuptak~ of 'he chemicals by the an,mals, Normally. this kipd of e~periment

does not differenliat~ belween uptake 01 desorbed chemical via inte"litialwater in Ihe sediment and uplake of adsorbed chemical ,ia ingestion ofsedim~n,- However this diffeT~ntiation may be ,mportant for Ihe estimationof remobilization of chemicals with high ad;.orphon and low de'lOrptioncoefficients. Therefore, a method has be~n reported by Luoma and Jenpe(1976 apd 1977) to asse" the uptake via ingestion of sediment. This isperformed b~' comparing the amountlaken up by normal.Ii'ing animals withIhaltaken up b)' animal' living in sediment in dialysis bog"

If. in experim~nts with deposit-feeding worm,. the chemical concentrallonin Ihe sediment is monilored. the influence of the burrowing activily of wormson chemicallosse' from the sediment rna)' also be r~corded,

154 TESTS TO PREDICT THE ENVIRON"ENTAL BEllAVIOUR OF CllE\lICALS

By fccding fish wilh cocklcs contaminaled by ",dimcnHl5socialCdchemical. a crude examinale of biomagnificalion of ..c<:Jim.nl·bom. ch.micalsin aqualic food chains has Ix.n mad. (Courtn.y and Langston. 1980).Compl'l' food chain .xperim.nls. ho""...r. aro I.asibl. onl\ in laboralOl')'.COS}'sl.ms or in more complex experim.mal designs ""lh Ih. diff.r.ntlrophic I.vols k.PI ..paral, (... Soction 3,2.5 and Chapl.r 4),

For d'l.nnining lhe distribution and migration of chemicals within lhesediment. methods have been r.pon.d for radl().labelied metals by RobbInsU di. (1979) and Boddinglon u nl. (1979). In bolh ...... the migralionlhrough a ..diment column was recorded b)' radioacti"il)' mcasurem.nttechniques,

Numerous upenm.nlS ha"e Ixen carried OUI to inveSligale rom'er;s;on,e«I;o1lS in ..dimcnls. Normall\...dim.nls. ",'alcr. and lhc ch.mical inqueslion are incub'lled and Ihen lhe aqueous solulion is e,lracled andanaly..d for con".rs.ion product'. Thc ponion of uncxtraelablc rcsiducswhich are dw:eublc onl\' whcn radi().lalxlle<l ehcmicals aro u"'d. should beincludcd inlo Ihc mClabolic flaCl;"n. In comrast 10 soils. for which man)' dalaarc availablc on uncxtraetabl. residues (KICln and Schcuncrt. 1982). onl\' a"C')' limilcd number 01 publicalions ha"c dealt ""lh lhi' problcm in..dimcnts (c.g.. MIyazaki U 01 .• 1975; Hcrlxs and Schwall. 1978).

The maintenan« of aerobic Or anaerobic conditions is nol welldislinguished in SOme of Ihe con"ers.ion leSlS reponed. In general.undiSlurbed ..diment samples Oooded ""lh ..... Ier are regarded as anaerobic.and samples shaken or Slirred lhroughoullhe Incubalion period are regardedas aerobic, In order to enSure anaerobic conditions. the samples are kepiunder nitrog.n or a 95~ N/5~ CO, mixture. SimIlarly. for lesa carried outwilh culture media of microorganisms from ..dim.nts. if anacrobicconditionsar. required, culture media are redu«d wilh sodium dilhionile (2oro el di..1974) or cystein•.HO (Anawa)' e, ..I.. 1982a and b) and kepi und« nllrogen.

Abiolic reductions in ..diment rna)' Ix simulated b}' laboralOT} reactions oflhe cbemical ""ith iron redox S}'Slems (Ola... 1972; William$ and Bidleman.1978) or reduced hemalin (Zoro e, 121 .• 1974); thiS has bun achie"ed lorDDT and loxaphene rcduelions, ElectrOChemical reduotion has Ixenproposed as anolhe, melhod 10 Simulate lh. reduction of ohemicaJs. e.g,lindane. DDT, or DTE (l.l ,1.2.1'lrachlor().2 .2.bis (p-<:hlorophenll]clhane)and 10 prodiCl anaerobic degradabihl) of chemicals in ..dimenlS (Beland et

di .. 1976). Ho....e'·.r. lhe.. simulalion lests h,,'e been applied lhus far. only toa fe.... Substances and aro still far frorn being 'Uilablc a. Slandard ,eslS fororganic chemicalS in general.D~",doliofl lesU may Ix dividcd imo those determining onl\' lhe

disappearance of lhe parem compound and Ihose determinIng compleledegradalion b}' measuring ..,bon dIoxide. melhan•• or olher 101A'-molecularfragments of thc chcmical in que"ion.

SEDIMEI>"TS

If Ihe former group of te,ts is employed. caution should be used 10 a~oid

misinterpretation. due to the "oIatilized. chemica II)' altered. Or unextractableronions of the teSt substance (e,g .. Watson. 1977; Sudhabr_Barik andSethunathan. 1979a; Ward a<td Matsumura. 1978; aark and Matsumura,1979; Boyle n at.. 1980; Blade...F~lmore el ..I.. 1982). Standardized testsbased on disappearance of the parent compound. as "'ell as those based onoxygen consumption. ha"e been developed fot ",ater (see Chapter 4.2).

Test. to determine the end products of biologicaJ degradation have beenlong utilized, for example for carbon dioxide production in soil. CarbondiOXIde is trapped by alkaline media and determined quant,tati,-ely. Blanksare run with material "'ithoutthe chemical in question. and the difference inamount 01 carbon dioxide produced by treated and untreated so~ is a meaSureof the extent of complete Oxidation of the foreign molecule (Bartha andPramer. 1%5). CO,can be determined 'Isodiroctl) in the gas leaving the 'eS'apparatu, by gas chromatography; this method is preferred ",'hen otber gase.ato to be determined simultaneousl}', S,milarl)'. in anaerobic degradationtests. the extent 01 anaerobic degradation i. estimated from the formation ofanaerobic end products of metabolism; these mal' be determined hI gaschromatograph}' (e.g.. methane; Wag""r and Briutigam. 1982) or trapped,e.g, H,S in 0.1 "cua, in 0.3 MHa (Aua",ayo, <>1 .• 1982a). Ho"'ever. sincein such experiments the origin of the gases formed is nOl kno",n. the teslS donot gi'-e accurate quan'ita,i,'e data on 'he produClion of 'he gas exclu,;"el)'from the chemical in question; furthermore. the methods are not applicable tolow chem'cal concentrations, In order to meaSure carbon dioxide or methaneoriginating exclusi,'ely from 'he foreign compound as separated from thatformed b)' degradation of normal organic nutrienu. labelling "'ith ''C isindispensable_ ''CO, ;s trapped hke unlabelled CO, and determi""dquantitath'ely by radioaetivltj' coun'ing. Ho",e"er, also in this kind of testingcaution in interpreta,ion of results is appropriate since the amount of free"CO, fon'lted docs not al"'ay. repre..nt the IOtal portion of chemicalminerali~ed as part of the "CO, formed can be roaSSimilated to naturalmostly high.molecular and unextractahle compounds. It is very difficult todistinguish these compounds from other unextractable chemical residuescontaining the foreign compound molecule or it$ con"ersion products_ Thus,''CO, e"ol"ed from" Clabelled chemicals should be 'egarded as a minimumestimate of '0,"-, degradation and as an absolute measure of total degradationonll if the poniou of unextraetable or unidentified "C is minimal.

Oosed ineubation systems have been described in ""hich the ..dioaetivecarbon dio~ide evol"ed is trapped ",ithin 'he incubation vessel by cupsOOT1U1ining. for example. oqueous alkali (Herbes and SCh....all. 1978.Sudhaka.-Barik and Scthuna'han. 1978b; Herbes, 1981). or by filter papersoaked ",-ith aqueous alkali in a centre "'ell (Lee and Ryan. 1979). Thesemethods ore suitable only fo' anaerohic degradation $tudi.. sin... $ufficient

156 TESTS TO PREDICT THE El<VIRO'-\lEVTAL BEIlAVIOliR OF CHE\lICAI.5

oxygen suppl~' cannot be guarameed fOl long period~. Futhennore. Ihele i~

the !'O"il>ility of adsorption of radiwcti"e .'olatile organic chemicals in thecarbon dioxide trapping liquids. which may be misinterpreted as radioacti~e

carbon dioxide, The use of sterilized blanks is not sufficient to eliminatepotential error.; of this ~ind since not only the unchanged parent compoundbut also ~Glatile metabolites may be absorbed in the carbon dioxide trapo.These diffiCllltie. may be o,-errome by using biometer flasks similar tG th()SCused fGr soil by Bartha alKl Promer (I%S). inserted in an aeration train.Extraction Glthe aqueGus al~ali containing '"co, by /I_hnane (MacRae.ftU.• 19b7) results in ,he removal of organic compounds carried over in theair-stream ""II' if tlte} are highly lipophilic and thu, partitioned quantitatively'Into hexane. The best method tG detennine organic ~olatile, and carbondioxide separately is ""nneeting the flas' nOt only' to separate traps for carbondioxide but also to preceding 'raps for ,'ola,ile organics. The lane' trappingcompounds can be Chromosorb W·HP ro.lted with QV·225 (JGhnson andLul'·es. 1975), loluene (M,}'aza~i er a1 .. 1975). or ethy-Iene glyrolmonomethylether (Voc~el, 1981); absorbems as use<I in soil studies may alsobe wi,able (polyurethane foam plugs. Kearney and KGn'son. 1976; Murthyand Kaufman. 1978; sulphuric acid and silica gel coaled with pol}'eth}'lene. SiiBand Eben, 1978). As ahsorbcnts for carbon dioxide. aqueous sodium orpotassium hydroxide are most rommonly' used. but Grganic bases likemGn<>ethanolamine-c,hylene glyrol (Johnson and Lulves. 1975) ormonocthanolamine-2-methoxY-'ethanol (Mi}'azaki .f ~I.. 1975) ha,-e bunreponed to be applicable ,rapp,ng solut,ons. If liquid scintillation coc'tailsare used. 'he" radioaclivit}, can be detennined directly "'thoU! takingaliquots. reluhing in much lower limits of detection (Vockel, 1981; reportedfor soils but witable also for ..,dimems; \larinucci and Bartha. 1979).

The best method to distinguish clearly between aerobic and anaerobicdegradation i. to 'eep the inCllbaling mixlmes under air/oxygen Or undernitrogen. respecti..I}. [n order to facilitate continuous ,lwking of themixtures. "apping of "olatile organics as well as carbon dioxide is nolperformed continuously but is accomplished b}" f1u,hing al appropriate time,nte"'als (Vockel. 1981).

For the determination of "C-Iabelled gaseous anaerobic degrada'ionproducts, Nelson and Zei'us (1974) have developed a method for thesimultaneous anal)-sis of "CH. and "CO,. BOlh gases as "'ell as H, wereseparated by' a gas chroma'ographic procedure on a Ca'bosie"e B column anddelected b)' thermal conductivity. Deteetor effluents were channelled into.gas proportional counter for measurement of radioactivity. Thi' me'hod wasmore rapid, sensitive. and """veniem than gas chromatography-liquidKintillation technique•.

It is surpti.ing that onJ) ~.ry limited infonnation is a~ailable on lhe testingof Tel1C'iollS of en.itr}""'.nt~i c,,"mic"', with h}'drogcn ,ulphide wh,ch is

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158 TESTS TO PREDICT THE ENV1RO"ME,-TAL BEHAVIOUR OF Olf..'\ICALS

th~ mass balana:$ of critical system-Incl \'ariablcs. thuS indicating miCl1X:llSmr~'pon", to introduced ch~micals, Gas dlnami"" w~r~ .hown 10 ~ mOSI"'nsitiv~ to Slr~" in this aquatic mod<I cooslsl~m,

M,~~d l~rr~strial-aqualic mod<I ~ooolot~m. ha'e been de"gned 10 a....,,,m,,,,emenl. aCCUmulalion and d~gradalion. mainl}' of chemical. applied 10crop> (Melcalf., ~I,. 1971~ Melcalf, 1974: Lichlen"e,n., aI., 1978; Liangand LichtenSlein. 1980, Vinanen ., al.. 1980), The mod<l. include alerrestrial componenl v.hich i' fall...... or OO'o'e,..,d wilh crop plan,•. alerreslrial-aqualic interface. and an aqualic portion including "'aler ....diment. aqualic plan", and animals of various Imphic levels, Simulated .. indeliv'ered <><:caoionall} to the lerr~,trial parr rt'sul" in soil run·off which i.channelled inlo lh~ aquahc companm~n, wilh its laler of lake bonom mudand i" animal and planl inhabitants (Licht~n\l~in c' al.. 1978; Liang andLich'en"ein. 1980). Be.ide. this Transporr of chemical from lhe lerre'trial 10'he aqualic part of the 'l'stem. lhe lran<pOrt via food chain inleraction.(for e~ample, crop planl - in",et larvae algae - "'ail I dialOm. ­plankton - mosquilo larvae - fi.h) has also been Sludicd (Metcalf c, aI.,1971, Melealf, 1974), In addition 10 providing a wealth of information on lheindiv'idual chemical. Sludied. material Nlana:. oblained wilh the'" model.,..,veallhal soil and ",dimen" may be the main conlributors 10 regulaling thefale of lhe chem;cal in Ihe model. a fact tha' mal be e~trapolaled to Ihe realenvironmenl (Virtanen c, al., 1980).

3.2.6 FIELD TESTS

Onll a limit~d number of field le.l, for in,'eSligating the lale of chemical' in...diment. have been reported. Since lhe... are complex and e~pen.iv'e. lhelcannot be r«:ommended a••,an(iord ..:reening procedures for a large numberof chemical', but Ihe} are indispensable in e"alualing Ihe e~1rapolation oflaboralory leSI data 10 predicl en..ronmenllll behaviour. MOSI informal;on isa"aUable on applicalion of chemicals 10 small ponds. Submerged chambersand enclosures haye also been used.

In pond tc,I•• ,h~ chem,cal under in"esHgalion" applied to the waler. Theconcentralion in sediments i. monitor~d a. well as 'hal in water. during acenain lime period: bioaccumulalion (iola is included in lhe anall'.is. Whereasexp<:riments wilh unlabelled chemicals (Ria: r, al.. 1974 ~ Mauck e' al.. 1976~Gasilh and Perry. 1980) g;"e informal;on onl}· On lhe .ccumulalion andpersi.tence of the parem compound and well_known. easily delectablemetaboliles. experimems with radiolracer chemicals (Salon~n andVaajakorpi. 1974: Krieger. 1981: Schauene r, al .. 1982a) can pro"ide (iolawhich will include all con"ersion products containing Ihe I.belled carbon, Insuch e~periments. ;t was found lhat radioacti,·c residues, derived from .hechemical appli~d, p<:rsiSl for long lime p<:riods in sediments. ev'en ,,'hen

'59

rc~idu(s in Wa'Cr are no long<'T delectable. From 'hi' residual source.chemical' arc ,..,distributed into organi,ms ,,-here their aCC\lmuTation ,11.0,","1 aIlme-courst cu"',, .imilar 10 a dampW oscillation (Krieger. 1981; Schauenecr a1" 1982.). Thi. i. true n01 onl' for persi'lenllipophilic chemical. but e,"cnfor the h)drophilic biodegradable delergen! n-<lodeC)lbcnzene ,ulph",,",e(Krieger. 1981). This fae1 confirm' the eminem imporlance of ..dimcn!' as adepot and source for redistribution of chemical. in the en,-ironment. and 1hu•.the importance of developmen! of all kinds of ..dimeo! lOS's. Instead oftreating ... hole pond ....ilh lhe chemical, PVC<ompanmem. embe<lded intothe pond sedimen, rna)" be ".oted with lh. chemical (Schauen. tI al .• 1982b).Although such compartments ha'. been u<e<l primaril) to .Iudy effens ofohomical, On Ihe aqualio biOI •. ,hey m.y be used 10 "ud)" physioal. ohemioal.nd bioohemical re.c.ion. in ,"diment. as well. In s,udie, on 'he fa,e ofohemicals ,n sediment•• it should be considered 'ha' persis,ence in suohenclosure is enhanoed due 10 decreased "ola'iliza'ion as a consequence ofd=ased "'1I'OT lurbulence.

Since 'he phy.ioo-ehemical as well as ecologic.1 s.itUalion in small ponds i.quite differenl from 'hal in larger wa,er bodies. Ihe rcoulls ob'ained in .mallpond tes,s can no, be extrapolaled to lake, Or to marine systems. For the'""'1Iler bodies. enclosures h",'e 10 be used. Son.ogni el aI. (1977) u",dlarge submerged chambers 10 measure ;11 ";IU ",d,m.nl_",..ter interanions.The C)lindrical chamber, ",aled alone end. is ron"lUeted of opaque PVCm"erial and i. embedded in the lake b<>uom. en,rapp,ng aboul 1.2 m' of",..t.r above I m' of sedimenl. The chambers were designed to Study sedimentphosphorous release and would be suilable also to 'tudy ,he behaviour oforganic chemical> in >edimcnlS.

Polyelhj'lene enclosures were suspended in Saanich Inle'. Omada (Lee.,aI., 1979). Polycyclic aromaHe hj'drocarbons d"",I"ed in crude oil ""ereadded to the ....",.r. Radioaeti," labell.d benzo (a)-p)'rene "'."s al'" applied,Concen.rations 01 aromalics ""ere d.t.rmin.d in wa'.r, zooplank,on, O)'''.rs•• nd bottom ..,dimenlS. II was .ho....n Ihal loCdimenlation and photoohemicaloxida'ion were primarilj responsible for ,he deer.a.., in concentration. of ,h.higher weighl aroma'ies. Similarlj', fibregla" box", di"ided ,ntO three equalcomparlmenlS, each ....i'h bollOffi' offibreglass scrccns, were in"'rled into 'he..,diment in Ihe in'.nidal ZOne of Sequim Ba)' (Rocsijadi 01 oJ .• 197Ila),

3.2.7 CONCLUS10;>;S

The r.sull. of labor4tol)' le.t. reponed Ihus far on adsorption/desorp,ion,remobilization and bioaccumulalion of eh.mical. in ..,dimenl' reveal 'lialscdimenlS pia)' a key' role in Ihe dimibution of eh.mical. in Ihe aquaticen,·i,onm.n,. This key posi,ion i' confirmed b}' laboralo')' model eoos)'''emdala a......n a. by field lesl data reported, In view of ,hi. importance, Ihe 1e,·.1

160 rrsn TO PRI;OICT TUE Et-VIRO"~lE"TAl BEHAVIOUR OF OlE~"CALS

of lesl lechnolog} and data interpretalion i. not appropriate. There exi.l no'tandardized and internationally recognized tesl procedures for anI ph}'s,calor chemical pro:ess relaled 10 sediment>. An OECD adsorptioll/desorptionle,1 designed for soil and OECD biodegradalion lesls designed fOl "'aler can,..ith cellain varialioflS, be applied to sediments. The same consideralionsappl}' 10 Ihe lesling of ,olatihl\' of chemicals flom sedimenlS "ia Ihe aqueousphase. Apart from Ihe problem of ~landar<JiUtion of te~1 malerial. whichexim also for soils. Ihc lesl methods fOl adsorplion/desorvtion andlemobilization!blooccumulat,on line been bener elaboraled lhu. far lhanlhose for Olhe, par.metclS. The OECD leSl fOl .dsorvlion/desorvlion and.,'ail.ble tests fo' "olalilily should be .dapled to sediments and thens.and.rdiled. Sim,larl~'. for Ihe accumulahon and ,emobiliUl;on of chemicalsfrom sedimen" due 10 Ihe act,,'i.\ of olgani~m~weh a~ WOlm>, Slandald teSlSshould be de,eloped.

Fo' some of the chemical and biochemical p'ocesse~ and inleractions insedimenls. as discussed in Section. 3,2.3 and 3,2.4, ,,'hi<h ha"e eT>OlmOuSimponance in de.ermining lhe final global fate of chemicals.•hele exi~1 onlyspoladi< expelimemal d.la for indi"idual chemical~. whi<h has not beenextended 10 OIhe' chemical groups 10 form geneT.lly applicable leSlmClhodologies, The role'·.nce of Icponed Ie" da.. 10 prediCt .heen"ironmemal beha,ioul ofchemical~in nalulal sedimenl~ ha~ been examinedonl\' in a few case, b\ means of field sludies. Therefore. laboralory test< as..ell .. field studies should be impro'ed a. a furthe' 'lep to..'ar<J, theunderslanding of the role of sediments in tbe en,'ironmemal beh.,·iour ofchemicals.

3.2.8 RHERESCESAI..aPdet. \1. (1981) BlOd<gladat;on 0( chcmiall. 0( en,ironmental ~,n.

Sc"'''''''. 111. 132_138,Amblosi. D., lseosee, A. R., ond M.""hi., J, A (1978), Oi,t,ibution of o,ad'"",n and

J>houIone in an aqll3tic «<"l"em, J, "8"'-' f<><>d Chtm.. :16. 50-53Amiard.Triquet, C, (t974), eontominatioo b~ ""Iinm_1 H and "",,_59 of 0 Kdimc:nl

"'ith Meni""la manna. Cuh. Bioi. Ma, .. I~. 4~l-\9-4 (in Flench)Am,,,,,. V .• OIillemi. R., lmpelhzzc:ri, G., Oriente, G" Pi.t1elli, M., SCiu'o, $.. and

Trinpli, C. (1982), L<:,·el. of chlorinated h~'<!ro<a'bons in ",diments from 'he""ntraJ MC<!iterra....n. Sci- roo>! En,·''''''.,::-.I. 9t_99

Af>(\<rsen, J. M. (1971). Importa""" of lhe denitrification pro<e.. fo, ,he rat< ofdegradation of oll"",e ma"el;n lah sedimen". In I",,,oc,,on' M""<t" StdirMmsand Fmh 11'0"". Ploc. In'. Sjmp., 357_362. Am"erd.m, !'<th<r1and.

Alt...·aj·. H H.. Campel .... D.. ond PaJntel, \1 J B. (1982a), Anaerobi< microbialdcgnldat;oo of d,ulon b~ po>r<I sediment. P""i< Bi«lr<m, Ph.,·siol .. 17. %--- WI.

AltO"")' H. H., Pa)O«I, \1 J, 8., ond Campe"" D, (1982b), DeVlldation of",I««d pheojlnl,," hc'b'eld<, bj .n•• .-ooic pond >ed'menl.J. E".'-",,,. Sci- lI.oilh.Pari B, P",u:, food Conlam. Ag"•. 11'...,.., 17. 683~699

Baha<!;,. \1, Gab. $.. SChm'l!cr, J.. and Kort•. F. (1978). Degr.dat;oo "f ca,F,;form.tion of CO, upon :ro.orption on ~ka:o sand Ch<mo'pM", 7. 9~ 1_94:

SEDIMENTS '"Balka•. T. I., Salihoglu, I" T"oeel. G .. Tugrul, S. and Ram.Io,,·. G. (1978), Trace

m.....I' .nd ",gan<:><hl"'In' ""du. oon'.n' of M"lIidae f,mily fishe' and ",dimen"In ,he 'ian"y of ErdemJi (1<>:1). Tur~.y·, /Vft Jou",". Elud. Poilul/O"" An/aI.'a,CI,E.S. If" n9-16J,

Banha. R.••nd P"mer, 0, (19M). f ••lure.of. n••k and metbod f'" m.a'"'1Og theper>i<teno< and biological .ffect. of pe.1idde In ..,d. Sod Se,,, 100.68-70,

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M,)ozokl. $.. S,kk•. H. c.,.nd L)neh. R. S. (197S). \'e ...poi,,,,, of di"hlobtn'l b)microorgani"", in ,h. aqnati" .n, """men'- J. Agrk. FOO<1 CMm., 23. 365_]68.

\lou. P.• W.i'ierbotr. l., Kltln, W.. and Kort•. F. (1974). MttabDIi'm 012.2' -<lithl<>robiphc:n)·I.I'(; in ''''''' p1an,~"..ter.."'i1 'l'I"m', Bull t·n"inm. Con'o'"Toxicol.. lZ.5al-5a6

MuJlc:r. G. (1977.). In" ..."pl>"" "" drilli"g cor.. of iediment> of !.-al. C""stan<t. 1Profil... of , ... poI)'-'}'di' ."""atit h)dmc:art>on,. Z. .\o""p""h.. 3lt. 703-711 (i"Germ,n),

Mull... G, (l977b). Pollution rt>t,r<h on dolt<! stdim.nt cor.. from Lak. Con".n<tll, Hi>'orical e,,)Iu""" 01 h...·) m..ol.-t'tlo'ionship '0 ,he e"oln'iorJ 01 poI)'<)'cll""""""'" h)'droearbons. Z. \o"'.!<>""h" 3lt. 913-919 (in Germ.n),

Muller. G. (1977c) Pollu'""n ....arch On dalt<! ..dimen, core,lrom Lt.e C""",n<tllT, Historical .voln'i"" of N· .nd P--e<>mpounds_rtlotlonship 10 the <I<".lopmtn'of he:o') mela" and poI)<)dl" aroma"" h)drocor\>on•. Z \olu,p""h .. 32<.920-925 (in G.rman).

Mul~r. G. (1979.). He4''l ""'410 in ,he: ..dim.nt of Rhin. ri"er-<:h,ngts sin".1971 UlOUl:hou, 79, 778~78J (in Germ,n),

Mullc:r. G. (19791». C>dmium in m\Od----<>ld Ond """" probl"m., ,\.,""''''.. 66.JS9--3W (i" German).

Muller. G. (1981). llle "'e",i' comJlO'iu"" of peliti" ",d,m.n" ('muds') wi'h "gard'0 the ....bli,hm."' of '","dord ..diments·, Un""bh...." (in G.rman)

Muller. G .• Grimmer, G ...nd BOhn.e, H. (1977). sedim"n'.,,!, rtmrd of h...), m.talsond poIlcl<lic arom..'" h)droeart>on' in Ltke eon"ancc \.'u",'i<1<n>th. 6-1.421-431

\lulltr.G.. Dominik. L R.uthe" R., Mol>"'h. R .• sehul .., E.. Acker, L ••nd lnon. G

166 TE:;-n; TO PREDICT THE f1;VIRO:;\lE:o<TAL UEHAVIOUR OF CHEMICALS

(198Q). Se,hm~n~~ r~d of .n"iroom.nlal poIlulioo in 1!lc Western Baltic Sea.,\'0"''''';.13."",6.,67,595--600.

Murr.)·, C. 1\...nd R.nfro. W. (1976). up..... of plu,onium from "'.",,'.r and",dim.nt b)' a m.ri"" poI)·dI.. 'e ""ITO. ,,'ipl">" Koi}'O Gokui-Sioi. n. 2~9_2S2,

Mu''>)', H. E.• Ra), L. E.• and Oia",. C. S. (198h). Anal)'''' of marin. ",dimen'.",.'er .nd b."a for ",1«1e<! oriOnic pollu,an'.. ar.:"""p~rt, 10. 1327_13J.l.

Mum). H. E., RA). L. E...nd Oia",. C, S. (l9fllb), Ph,b.b.:acid ..to". 'otal DDT••and pol)l:hlorina'ed bipben) I. in m.ri.....mpl.. from Oal,'."on Ih), T.""•. Bull,E:m';ro~. CO~lam. Tox;ro<" 26.769_774

Munh). N. B. K.• and Kaufman. D. D. (l918). o.voda'>on of pontxhloroni'r<>­b<nnn< (PCNB) in ana.rol>i< ..,iI-<. J, Atrlr. FocJ 0,,,,., 26. 115 I_II 56.

Nohmu,>, R.• Su'u,i, Y" and Ued.t. T, (l977). Di<trib.ti<ln of ..di<lnudkle••mongg...n .Ig.., marin< ..dim.nt>.nd ... ""t~r, J, Rod"". R.... 18. J22_JJO

,\;.Ison, D. R.. and Zeiku.. J. G. (1974), Rapid m~,_ f<>r ,be rodioi:lOlO!»C .""1)";.of Pse<>IU .nd products of aN~rol>i< m~..boIi.m. Appl, !olj,robioi" 28. 258-261.

NriaC•. J, 0" and Coker, R. 0, (1980), Tr""" .....,.J, in humic and luluc .cids fromLa•• Ontario se<!i!O¢n ... Eo,'i..",. sa, r"'h-wl.. I~. 4~3-446.

OECD O><mi..l. T."ing Programme (l981). OECD GuUftli... pr Te.o,;"8 ofC~mit:ab. 100: A4wrplJtm'd<>orplion. Um..'elll;>uO<le..m, &<1in: 23 POKes

Oli,·~'. B. Go> Coop-o"., E. G.. and Ca,.)·, J. H. (1979). Ellec' of "'''P''nded..dLm~n" on ,h~ p,,"'oI)~i. of organics in ,",'''." E:m';ro~. 5<;, T«hrwl" lJ.I07S_I077

01,""". M. (1978). Seasonal ,..ri..ioo of PCB l..~J.,n n.h_an importanl f.",or >np1.nni"i .qua'ic moni'orinl: program>. Ambio, 7.66-69

o..mland. R. S.• and T.)·lo1". B. F. (1978). Sulfa" ,~d....,ioo.nd"""hallOFnesi. inmorin~ sedi"","". Gtochim. C"'mo<hiln. A,,.,, ~l. 209-21~

P..rick. Jr" W H, (1966). Appu..... for oontroliin~ ,h. o,Kla'ion·rcducrion pot.n"alof ,"".t.rlou:ed ..,ils, Saturt, 212, 1278_1179

Peck. D, E" c..:.r..in. D L.. and Farmer. W J, (1980). AdooI;>t~iooofdiuron by frc.~ ....",r sedim."".J, CO";'M. Q""I.. ,. 101-106,

Pol..·,". V. N. (1978). E..1....'i"" of .".ponded mal .., .nd chlorophyll ~ntr."oo,in 'h< "a f,om tb. up"'-.lli"l1 radiation >p«1rum ........."'d lrom a bel""",,<'­Ok,4-w10giY4. 18. 428-43~

Phelps, H. L (1979). Cadmi"m sorp'ion in ."....nn< mud.'ypo sed,,,,,,n' and 'ho."""mula,ion of cadmium in 'ho 001,·"'<11 d.m, .If}" """...ria. Ui""rln. 2.40-\.

Pimp!, M" .nd SC~""e1k"l'f, H (1982), Co"tamina,ion of Rhine m'or "'ithp1u'onium-p1.lOni"m =n,.. ,ioo ao • f""",;on of p.onicl. di.meter of..dim~"l" KFK R'P'On 3074. K"nforschun,.,~n'rum Karl""h~. Federal R.pubh.of Gennan)·. 27 poge. (In G~rman)

POIUUa. 0, B" Ad.m.. v, D" Me<!in~. A J" and Co..-"". P. A. (1982). U.iolll~=-pbo" .qua'ic mi<rocosm. 10 ...... I..~••nd im""",. of clIemical. ,n mictllbiolcomm.n;"~•. "'alt. Ru.. 16, ~89-4%

Puca:tti. 0 ...nd ~i. V. (1980), PCB.nd HCB in tho >«1im~ntsand ""t."of thoTib<r "'001)', .lfo' Poil",- Boll.. II. 22_25.

Rom.rooonlly. S" Springthorpe, S.. and Kushn.r. D, J,. (1977), Competi'ion lorm~rcury bet""'.n m'er ..dlm~", and bact<na. Bull. En"lron. COnl4m. Toxicoi .• 17.~Q5-5\1.

R.imen. R. S.• and ;;,.n~e1. P. A (197~). Kinetics of ""''''''ry od..,rptioo .ndde>nrption in se<!,,,,,,0l. J. W"It, Poilul. C",,'ro! F'd., 46. 3~2-3S6.

Ronlro, W. C. (1973). Transfer of "'Zn lrom sediments b)' marin< poIych.e'. """"'•.If",. Bioi., 21. 30S_316.

Rke. C. P.. SiHha. H. C. and Lynch. R. S, (1974), P....." .... of d>chlobe"il in • f.""IX'nd. J, Arne. FocJ Ch'm .. 21, 333_534

'"RichHd<an, E, M" and £\,,1.''', E. (1972), Retention of 'hru in>C¢licides 0<1 d,ff.ren,

.0:< ooiJ particles ..spond<d in "',,'e. S<>d Sci. 50<. A"""" Prrx.• JS, 884-887,Robbin>.). A.. McCall. r. L. Fishtr, J. 6., 00<1 "'0""";. J. R. (1979). Effect of

de?,,";' feede" "'" mi;rotion of '''Cs in lake ..diment>. u.nh Pla",', Sci. Ull.. 4l.217-287,

Roe.,).di. G .• And<rwn.). w.o.nd Blll)l<><:l.). W, (19780), Uptake of hyd.ooarbo",from m.n"" oedi"","" contaminated "ilh Prud""" B.~ crude ",10 innu<occ off«<iina lH>¢ of ,eo, spec;e, and ....i1.\lHny of poI)qclic >"',,na,i< hl'dr<><arl>ons, J.FISh. R... 800rd CO"" J!. 608-614.

R"'''Jadi. G .. W<><>druff. D. L. and And""",n, J. W (1978b), Bioa".ilabilil} 01naph,....I.n•• from m.nl\¢ ",dIme,," ."iHri,lI) contami".,w ..ith Prudhoe 8.)<rude: oil, fA,-iron. PoOuJ., IS. 223-229.

R_n,h.l. 1.. and l..a<o<'o, R J. (l9S9). A 'j'ot.ma,;" poIar<>p;tphic "00) of lh.OfQm>tic <hl.".<><th."••. 1. Am. Chm.. So<., 81. 3268_3270.

5.aliliosJu. I" F.goodi. J., .00 Slim. J. (1980). Chlorina'ed h)<!ro<arboo' (poo,"";de,and PCB.) in 5<lm< mari". <>rganil'" and ..di....nl> in an ."pc:rim<ntally pnlJu'.d.""')'tem in ,he l0i""" <>I S'runjan (North Adri.tie) and its "",,,,,,,nding. R,,',1M. Od~""gr. .'>ltd" $8, 3_9

Salon,n, l .. and Vaajo'orpi, H A (1914). Bioa=mul.,;"n 01 ''CDDT in ••m.npond In MEA (Ed.) Co",p.r~'i•• &l«Ii.. of Food ond En"iro"",,"'olCon,."",,,,,i<>ll. Int.,n.l;"n.1 A,om", Ene'iY Agene; ST~Il'UBI348: 201_211,Vienna

5<""u."....... Lay, J, P.• KI.in, W., .nd K""., F. (1982a). Lo<Ia-1erm f... <>I0'P.-.oe!lJorine ,en<>l»o,ies;n .quati......~>tem•. D;"ri""1Oon. ",,;.;lu.l be""";oo"and met.bolism of ~."c~lorobenl''''', pc:ntachloronltrobenu".. and 4-<hloro-­aoili". io .moll e>pe,im.n"l por>d" Eccwx. En.'i'<>II. 54ftr,., •. 560_569

5ebau."e, W" La), J, P., Kl.in, W" and Ko"., F, (1982b), In~llell« <>I~.4.6-triehlomphenol and pen,acMorop/lenoi On the bi<I,o of &<1"""••~>"m..CMmospMr<. II. 71_79

Selhun.o,h.n. N., .nd M.cR." L C. (1%9). P,,,,,,,,,,,,, and b;odegrodat;on ofdiuinon in ""bme'll.d .oih I. Agric. FlHHi Ch,,,,.. 11,221_225

SethuWlthilJl, N., IlJId Yos.hid., T, (1%9), Fale <>I diarinon in SUbmerged soil,Ac:umul.,,,,,, <>I hyd'oI;>i. prod"", J, Agfi<', food Ch,,,,., 17, 1192-1195.

S....n. R. J., and M.alle, T. H. (1978). Amino otid> in ....pended p""ieul". ma"etfrom """.nK: .nd COIIst.l ....te" of the Pacifl< . .\fa'. CM"'" •. 21 S_23I.

Smi'h. A. E...nd MUir, D. C. G. (1980). Det.""io.,;o" of """,obl. ondnon-.:."aet.bIe rodioacti,i'; f,om p,.,ri. >Oili ,,,,.,,d .. i,h ..rbox~·I••ndrilll-I.belled ''C -2,40. Wud Rtf.. le, 123_129.

S00<I8'.... W. J. (1976). P",.mial .If... of m<,h.a.... o.;cu,i"" an<!nltrif"""i",,-d,ni,rif""'lIon On ll>e '''lgeo budget of Hamilton Harbo,. Walt. Poil""Re>. C.n" II, 101_107,

Sonzogni. W C.. La""o. D. P.• Malueg, K. W., and S<h~ldt. M. D. (1977). 1,,'.. 01I..., ...brnerled chambers to ....."'....dime'''·....'er in,."""i"",. W."" Rts" II,461-164

Sridharon, N" and lu, G. F. (1972). Cop'e<:ip't.hon of o,••ni< eompoul>ds f,om 1.1.water by iton ..1". En.i"'n, S<-i. Tn:hnoI., 6. 1031-1033

Sudhah,·B.nl••nd Se'hun.'han, N, (19780). Biological hj'd'ol~'sis 01 parath'"" innotunll «01~·"em•. J. E,n·i"",. QIUli.. 7, 346-:<41

Sl>dhal<ar·Barik, and Se,h~n.than.N. (l978b) Me..boIi<m of .utropbcnoh in flooded",,10.1. En'·;ron. Q-..I., 7, 349_3S2.

SuD, A, and Eben, C. (197Dj, Dcgra\lauon of monolinu'on in ~jffen:"1 ""l~. lo"",aIfor PI.nt N"!n'tion IlItd S<Jii S<-ienc•. \41,217_229 (in Germ.n),

Titu., J. A.. Pa""",. J. E.••nd Pfi"er. R. M. (1980). Tra""ocalion of m.n:ury and

168 TESTSTO PREDICT TIlE E1<VIROK'IENTAL BEHAVIOUR OFOIEMICALS

microbial odapta'Km io a m<i<l<1 aq....'ic ')"<"'. Buil, En,·i,.".. e"",,,,.,. Toxieol.,15, ~S6-l64

T..i. F.·C., Bochan.n. Jr.. E. B., .rKI Drok<. L. (1978).~ .....Il ... of sedi",c""from ,I>< Iowa ri'<r. Sd. To'ul Environ.. ,. 277_28S,

Udluf', P.. orKI Wcil. L. (l97~), Condi,io", lOT ,be: biog<nic form.,ion of bydr~n.ulphl<le in .. 'ural w"c,.. W.uu'· an4 Ab .........T·Fo>Khans, 7. 10-13 (inGe'",oo)

Ueda. T. ~.ka",oro. R...rKI Suzuki. Y. (1976). Compo"son 01 ca<!",ium-ll~ '".ccu",ul.,ion in sedlOl<n" .nd ... wa'<r 1»' poIyc,,"e" worm,. Boll. Jup.:5o<. xi.riJh., 42, 299_306,

ViTlc""u'"", J. P.. Eklc'. O. 1...rKI fUk.i, R. (1980), Oistnbu,ion of poI)'ctllorinaINbiphenyl, in ......"" .nd ..dl",<n" I""" 'h< op<n M<di'<rra"".n .... y..JO'S",~UEns<! PoIiwk»u. Cqli.';, CI.E.SM.• 251-156

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V;"'r, S. A. (1982). Acid luoc,i"".l groop con'en' of .qa.tic hamic "",n<r: its<kp<n<knce 01"'" oriJin, mol«\lllor .'ei&h' and deir« of bomif...,ion of ,be:m.,c'''I. J. E,m"",. xi. H't:ldo. A 17, 767_788.

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Ward. C. T" and M."umu,", F. (1978), file 0I2,3,7,8.t<,,,,chl<Jrodibenz"1'-dio.in(TeDD) in • model oqa"'ic <nvironmen'. A"'h. En'·;"'n. Con<am. TMicoJ" 7.349-357,

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Wilh.m,. R. R".nd Bidl.m.n, T. F. (1978). To,"pllcne dcgrad.,ioo in "'aarlnc..dimen" J. ASri<-. Food Ch,,,,,, 16, 28Q-282,

Winfrey, M R" and zeitu,- J G. (1979). A""crobic met.boh,m ol,,,,mccli.,,me,ha"" p,ecu""," In Latc Mer><lota. App/. En\'",,,,,. I/ioo/};o/" 37, 244-253

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