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32 ENVIRONMENT main pollutionsources for the northern of hydrocarbon fuel [Dumont,1998]. The andtransportation of intense oilextraction withpollutantsasaresulthydrocarbons (HC) can occur, ofoil as well astheentry [Efimov, 2000].Here, naturaloilseepage potential estimated at16–32billionbarrels regionsgas bearing withthehydrocarbon oil-and- CaspianSeaisoneoftherichest The bottom hydrocarbons, matter, suspendedparticulate hydrocarbons, aromatic polycyclic , marginal filters, oil, hydrocarbons, aliphatic KEY WORDS:geochemicalbarrier, ofthesea. open part filter ofthe Volga anddonotenter River the (oil andpyrogenous) donotpassthemarginal ofthesediments. type The anthropogenic HC their content isindependentofthegrain-size the region ofavalanche sedimentation,and greatest accumulationoftheHCproceeds in fresh appeared andsalinewaters. thatthe It matter, temperatures, andmixingof varying changes causedbyprecipitation ofparticulate matter andbottom sedimentsundergoes compounds, theHCcompositioninparticulate precipitation ofanthropogenic andnatural Caspian Sea.Becauseoftransformation and of the shelfofthe Volga andthenorthern River layer ofthebottom sediments and inthesurface polyaromatic) matter inthefiltered particulate composition ofhydrocarbons (aliphaticand Data are presented onthecontent and e-mail: [email protected] e-mail: P.P. Shirshov ofOceanology, Institute RussianAcademy ofSciences, Moscow, Russia Inna A.Nemirovskaya INTRODUCTION ABSTRACT SEDIMENTS OF THE VOLGA DELTA PARTICULATE MATTER AND BOTTOM DISTRIBUTION OF HYDROCARBONS IN of dissolved C supplied from theavandelta, thecontent thetransformedet al, 2003].In Volga waters by the Volga runoffalone [Shiganova River the biogenicorganic matter (OM)issupplied runoff,90% ofthetotal riverine and80%of (because oftheshallowness)receives about a littlemore than1%ofthewater ofthesea oftheCaspianSeacontaining part northern runoff [Dumont,1998; Tolosa et al, 2004]. The production, navigation, andthe Volga River oftheCaspianSeaare thecoastaloil part 0.59% C compounds andcontained from 0.031to had ratherlowconcentrations oforganic the sandybottom sediments(2003,Fig. 1) waters oftheCaspianSeashowed that inthecoastal earlier studies performed of mineralandorganic composition). The and transformation ofdissolved substances the biological zone emerges (assimilation water clearing, phytoplankton develops and compoundsand sedimentation ofvarious zone offlocculationandcoagulation).After dissolved compoundsare captured (the the physicochemical zone, colloidsand andhindered photosynthesis. turbidity In occurs;thisareafractions hashighwater water, sedimentationofsand–silty water bymarinedamming ofriverine the gravitational zone, becauseofthe physicochemical, andbiological. In gravitational,zones withspecificfunctions: [Lisitsyn, 1995])consistsofthree basic water mixing(marginaland marine filter Academician A.P. Lisitsyn,thearea ofriverine According to themodelproposed by [Agatova etal, 2005]. org andfrom 19.8to 142.1μg/gof org varies from varies 500to 667μM 60.0112:18:05 12:18:05 06.06.2011 ggi410.indd 33 i 4 1 0 . i n d d

correlation between the distribution ofC correlation thedistribution between 2008].Aweak statistical and Brekhovskikh, aliphatic hydrocarbons [Nemirovskaya (AHC) as 16.8–23.9%ofC channelswas,River inseveral cases, ashigh 3881μg/g). inthe The AHCfraction Volga of bothC the marginal filter) hadhighconcentrations of the Volga of (thegravitation River part sediments sampledin2004thechannels of thesecompounds. Onthecontrary, the and AHC(r=0.14)indicated different origins Delta (Fig.Delta 1). HC (PAH) andtheirtransformation inthe Volga aromatic the genesisofAHCandpolycyclic These studieswere aimedatidentificationof to channelsoftheDelta Volga) took place. the studiesof Volga (from River Konakovo and bottom sedimentswere 2009, collected. In matter continued andsamplesofparticulate shelfoftheCaspianSeawere northern 2005,2006,and2009,thestudies ofthe In Tolosa etal, 2004]. 2004; oilsupply[Nemirovskaya, a permanent higher thanthatinotheraquaticareas with 3 3 Fig. 1. The sampling scheme of the northern shelf of the Caspian Sea (2003–2009 – bottom sedi- –bottom (2003–2009 Sea Caspian the of shelf northern the of scheme 1. sampling The Fig. org (upto 8.6%)andAHC(upto org 8–22 – station nos. where the bottom sediments were sampled in2005 sampled were sediments 8–22 thebottom where –station nos. , whichwasconsiderably ments; 2006 – filtered particulate matter). particulate –filtered 2006 ments; org

concentration from water, matter, particulate and The procedure ofHCextraction layers) were byan collected grab.“Ocean“ andreduced subsurface (oxidized surface fiberglass filters GF/F. Bottom sediments Particulate matter wasconcentrated on form) [Shiganovaetal, 2003]. to bottom sediments(i.e., thetransporting OM onthepathfrom photosynthesis sources matter represents particulate atransitform of because cycle, of thebiogeochemicalcarbon part matter isanecessary aquatic particulate 2004; etal,Winkels 1998].Moreover, theHCof 2004; sediments [Nemirovskaya, Tolosa etal, matter andbottom composition inparticulate ofmoleculartracerswithintheHC comparison transformation may beidentifiedthrough Therefore, the processes ofOMtransfer and which accumulate thesecompounds. the sedimentation,fallto bottom sediments, matter and, during byparticulate easily sorbed Because oftheirhydrophobic HCare properties, METHODS 006.06.2011 12:18:05 6 . 0 6 . 2 0 1 1

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3 4 ranges: 0.18−5.77mg/lofC withinthefollowing matter varied particulate The contents oforganic compounds in . anthracene (AN), andtriphenylene (TRF) (PL),benzo(a)pyrene (BP), (CHR), perylene (PH), fluoranthene(FL),pyrene (P),chrysene identified: naphthalene(NА),phenanthrene following unsubstituted polyarenes were US Environmental Protection Agency. The polyarenes received ofthe from alaboratory using astandard ofindividual ofamixture at254nm Measurements were performed water (ina75:25volume proportion). with ofacetonitrile media wasamixture 100-5C18PAH column;theelutriation (AcoNova, Russia);Nucleosil Novosibirsk, liquid usingaMilikhrom were byhighperformance determined (PAH) concentrationsandcomposition aromaticThe polycyclic hydrocarbon squalane asastandard. GC 121-2chromatograph (France) using gas chromatography withanIntersmat composition were bycapillary determined a standard. concentrationsand The alkane 37.5, and25vol. %,respectively) wasusedas hexadecane,isooctane, andbenzene (37.5, using IRspectrophotometry. of Amixture AHC concentrationswere also determined gel usingcolumnchromatography. The wasseparated onsilicaThe HCfraction spectrometer.using aShimadzuIRAffinity-1 at2930cm-1band by IRspectrophotometry (lipids)wasdetermined fraction extractable was dissolved inCCl4, andthebulk dichloromethane after removal The extract 2004]. [Nemirovskaya, matter andbottomfrom sediments particulate added for dehydration theHCextraction during sampling. directly after Sodiumsulfate was HC werewithdichloromethane extracted standardized. and bottom sedimentswasstrictly of PAH in 2006;and0.006–0.114mg/lofC of lipids, 90−500μg/lofAHCand20–108.6ng/l highest concentrations in the coastal waters of highest concentrationsinthecoastal waters of 2006,the and 6.2–39.2μg/lofAHCin2009. In RESULTS org , 130–710 μg/l l , 130–710μg/ll org

lipid compositionwas74.7% onaverage = 0.93. r(lipids–AHC) withinthe Their fraction contents ofthesecompoundswasobserved: correlation the between AHC andastrict matter consistmainlyof of particulate coastal waters oftheCaspianSea,lipids the 2009; Lisitsyn,1995].In [Kravchishina, formationduring of thenepheloidlayer by thesupplyfrom thebottom sediments may becausedbythesmalldepthsand insignificantly,concentrations varied which ofthe mainwaterthe direction flow, their zones ofincreased AHCconcentrationsin increase again. With thedistancefrom the the “ooze plug,” theAHCconcentrations concentrations. Later, atS=4.6–5.4‰in precipitates causingadecrease intheAHC matter particulate oftheparticles, stability S >0.2‰,dueto thelossofaggregative of themarginal filter [Lisitsyn,1995].At inthefreshwater iron, andbacteria part matter,of particulate humicandfulvicacids, promoted bythepresence oflarge amounts 2004]. (1–10 μm)[Nemirovskaya, This is mattercomponents, onfineparticulate ofemulsified,sorption mainlyanthropogenic concentrations grow, whichiscausedby (S)[Lisitsyn,1995].AtS=0.2‰,their salinity forms compoundsiscontrolled ofvarious by the content ofdissolved andparticulate waterarea mixing, andmarine ofriverine standard the deviation(σ)of20μg/l. In AHC was140μg/lonaverage withthe channel: and atastationintheBakhtemir near theexitfrom thenavigable canal matter were alsoregistered atastation AHCconcentrationsinparticulate Increased parts ofC parts AHC content isonlytenths oreven hundredth bottom sediments from unpolluted areas, the areas. themostrecent samples ofmarine In innear-harboraquatic which isusuallyobserved the OMcompositionwasashigh39.4%, was aslow55.5μg/g, within theirfraction the AHCcontent inthebottom sediments 2008], area andBrekhovskikh, [Nemirovskaya canal dredging. 2003,atastation inthesame In placebecauseofthenavigable dumping takes with themaximumatastationwhere ground the CaspianSeawere found near Tyulenii Island org [Nemirovskaya, 2004]. 2004]. [Nemirovskaya, 006.06.2011 12:18:06 6 . 0 6 . 2 0 1 1

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On thecontrary, inthecompositionofC is usuallyincreased 2004]). [Nemirovskaya, (in oil-polluted areas, ofAHC thefraction = 1.2). H the n-С25–С27oddhomologues(CPI= molecular rangethemaximumisconfinedto ofphytoplankton), while in thehigh- (autochthonous associated withn-C17–C18 the low-molecularrange, themaximumis ofthehomologues(Fig.distribution 2).In biogenic substanceandshowsabimodal istheclosestto thatofthe the alkanes near Tyulenii Island, thecompositionof andJeffrey,[Kennicutt 1988].Atthestations ofHCoilandphytoplanktoncharacteristic within1.0–1.3,whichis of thesamplesvaried index inthehigh-molecularrange)most preferencehomologues (CPI,orthecarbon becausetheratioofoddto even of alkanes, were byauniform characterized distribution matter presence ofoilHC.AHCparticulate respectively, whichmay indirectlypointto the lipids andAHCincreased to 65.3and48.3%, channel, whereof Bakhtemir thefractions The exceptions were found atstationsinthe AHC was23.4%orbelow(16.5%onaverage). or below(21.4%onaverage); of thefraction most ofthesamples,was25% theirfraction lipids were nottheprevailing In fraction. 3 5 Fig. 2. Chromatogram of the alkanes in an integrated sample of particulate matter igh-molecular alk from the aquatic area near Tyulenii Island Tyulenii near area aquatic the from anes prevail: org , of transformation ofdifferent HCclasses. sources oftheirformation orto ahighdegree AHC, whichmay pointeitherto thesame generally follow oflipidsand thedistribution ofthePAHThe variations concentrations 2004]. shelf[Nemirovskaya, of theSakhalin concentration was70ng/l and 73ng/linthenear-bottom waters; the particulate matterwere particulate the average PAH concentrationsinfiltered increased. For example, intheGulfofRiga, concentrations ofpolyarenes isusually areas harbor andcoastalzones,In the seawaters 2004]. (20ng/l)[Nemirovskaya, on average) washigherthanthatinopen 2006,thecontent oftotal PAHIn (43.7ng/l 2004]. [Nemirovskaya, products of biotransformed residues oflightoil are characteristic ofiso-compounds series shape ofthehumpandpresence ofthe andJeffrey,Kennicutt 1988]. The cogged compounds [BouloubassiandSaliot,1993; aut of which ischaracteristic =1.7(prystane/), i-C19/i-C20 =0.33,and =0.53,i-C20/n-C18 n-C17 theratiosi-C19/ that ofiso-compounds: ishigherthan The content ofn-alkanes the ratioΣ(С12+С22)/Σ(С23+С37)= 56 ng/l in the surface waters in thesurface in the surface in thesurface ochthonous 0.39. 006.06.2011 12:18:06 6 . 0 6 . 2 0 1 1

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3 6 a relatively lowC sediments containingshellsandalgae, with studied in2005are mainlypresented bysandy oftheCaspianSea part of thenorthern The bottom sedimentsofthecoastalwaters below 0.5)[Tolosa etal, 2004]. products, thevalueofFl/(Fl +Py) (with thesupplyofne point to theinfluenceofpyrogenous sources 9and12(respectively, stations 0.33and0.43)may 1993]. The lowvaluesoftheFl/(Fl +Py)ratioat place[Lipiatou etal, biosedimentation takes sedimentation, orbybioaccumulationand and matter bysorption into particulate of lightpolyarenes from dissolved forms We transformation assumethataselective (9.4) >An(7.5)>Chr(6.5)Bp(1.5)Pl (1.1). (34.4) >Fl (20.1)>N(10.8)BaAn(9.6)Py decrease ingeneralasthesequence(in%):Ph PAH matter inthearea studied inparticulate Because ofthis, thecontent ofprevailing environment. inthemarine their stability the sources oftheirformation butalsoon composition ofHCdependnotonlyon 1988]. [Rovinskii, Therefore, theamountand most unstablehydrocarbons place takes water temperatures, decompositionof summer, withtheincrease intheairand 1988; [Rovinskii, Tolosa late etal, 2004].In or underabiogenousnaturalsynthesis PAH are formed eitherinpyrolytic processes by phytoplankton, orbyoilpollution,and environmentmarine through theirsynthesis isbelieved thatAHCare suppliedtoIt the Volga moutharea, River r(C sediments from thecoastal waters ofthe layer ofthe data of2004,for thesurface by theirgrain-size According type. to our sediments moisture mainly isdetermined When passingfrom sandsto silts, theC onthedegreeextent, ofsedimentdispersion. organic compoundsdepends, to agreat increased to 1.199%. ofThe distribution from station5,inwhichC The exception isthesilty–clayey 2005), r(C area studied:r(C sediment dispersionandC 2004]. There wasacorrelation between value usually org –moisture) =0.96(in2009). The increases [Nemirovskaya, org org content (0.197–0.582%). –moisture) =0.92 (in wly-formed org concentrations org –moisture) = org combustion combustion inthe ratio is org

high AHCcontent intheC (tree foliage) 2004]. to 0.01%[Nemirovskaya, The 0.048% decreasing inhigherterrestrial and inphytobenthos itisrespectively 0.14%and 2.0-101.4 μg/g, 03-33.8%ofC indicate the impact ofoilHC. indicate theimpact of theCaspianSeaand Volga may River also shelf the bottom sedimentsfrom thenorthern 24% ofC comprised in 2004,onecase, theAHCfraction thesedimentsfrom the In Volga channels River values in biological objects. In theplanktonic C values inbiological objects.In is usually1%orbelow, witheven lower average bottom sediments, marine theAHCfraction In 74.5% ofC and nearoilstorages, ofAHCreached thefraction River,the Severnaya Dvina flood thespring during 2008]. Onlyinthesedimentsofmoutharea of 70–4557 μg/g, 3.55–62.5%ofC sedimentandto theOMcomposition: to dry widelybothwithrespect Their valuesvaried substance. higher thanthoseinafine-grained sedimentsappeared to be coarse-grained the area studied, theAHCconcentrationsin for capability oilproducts. in Nevertheless, andillite have themaximumsorption Kaolin matter.the water mass containingparticulate compounds, includingthepollutantsfrom <0.1mmprevails) organic fraction easilyabsorb (Fig. sediments(especiallywhenthe 3).Silty bythegrain-sizedetermined ofsediments type ofHC,inmostcases,The distribution isalso 2008]. andBrekhovskikh, = 0.96[Nemirovskaya UCM) was also maximal at station 19: 194.7 UCM) wasalsomaximalatstation 19:194.7 compounds (unresolved complexmixture – andnaphthenic The content ofalkanes n =16). stations 18and19,aC Fig. thesamearea, atthecloselylocated 1).In was found inthesedimentsfrom station19(see 2005,themaximumofAHCconcentrations In of C a weak correlationthe distribution between HC to thebottom sediments. Therefore, only was probably causedbythelocalsupplyofoil the AHCcontent of26.6,which byafactor of1.5 corresponded toa factor achangein org and AHC was observed (r = 0.26, (r=0.26, andAHCwasobserved org org [Nemirovskaya and Brekhovskikh, andBrekhovskikh, [Nemirovskaya with the AHC content of 544 μg/g. withtheAHCcontent of544μg/g. org content change by content changeby org org , in 2009 (Table 1). 1). , in2009(Table composition of compositionof org , in 2005 and , in2005and 006.06.2011 12:18:07 6 . 0 6 org . 2 0

1 1

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to heavy homologues in the bottom sediments to homologuesinthebottom heavy sediments 1300–1500 μg/g. The valuesoftheratioslight humpwasashigh the naphthene–aromatic sediments within15−17μg/g, thecontent of concentrations inthe Baku, atthetotal n-alkane thisratiois>10[Tolosa etal, 2004]).Near alkanes, environmentthe marine (for transformed oil oftheHCtransformation in is characteristic ratioof44.2,which naphthene/n-alkane and 8597μg/g, respectively, withamaximum 3 7 and AHC in different grain-size types of sediments in 2009 in sediments of types grain-size different in AHC and Fig. 3. The distribution of moisture content, C biogenic HC: the CPI values varied within biogenic HC:theCPIvalues varied composition pointed to theprevalence of of amixed origin (Fig. 4). intheir The markers well asinthoseatstations17 and23,were inthesedimentsofstation19,as n-alkanes According ofhomologues, to thedistribution transformation. thedegreewhich alsoconfirms ofn-alkane of thisarea were quite low(within 0.19–0.69), org , 006.06.2011 12:18:07 6 . 0 6 . 2 0 1 1

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3 8

Table 1. Content of Corg , AHC and PAH in the surface layer of bottom sediments AHC, % of Station Location Sediment type Сorg, % Moisture,% AHC,μg/g PAH, ng/g Corg

1 Gorodez Gray silt1.660 65.92 121.4 0.59 32 2 Above N.Novgorod Sand 0.029 19.95 6.7 1.85 undefi ned. 3 Oka River mouth Sand 0.048 14.0 3.0 0.50 “ 4 Below Cheboksary Sand 0.009 4.9 4.36 “ 5 Kama River mouth Gray silt 1.690 50.9 46.8 0.28 33 6 Kama River mouth Gray silt 1.856 47.7 18.6 0.10 35 7 Confl uence of Kama and Volga Gray silt 2.133 47.29 34.9 0.16 33 8 Tolyatty outer harbour Gray silt 1.937 46.12 107.4 0.55 145 9 Below Syzran Sand with shells 2.46 51.18 50.9 0.22 undefi ned 10 Volynsk outer harbour Oxidized silt 1.789 49.5 71.3 0.40 “ 11 Above Balakovo Brown fi ne sand 0.016 19.29 10.6 5.30 16 12 B.Irgiz Brown fi ne sand 0.031 32.83 4.02 1.03 26 13 Above Saratov Brown fi ne sand 0.012 19.33 21.7 14.47 57 14 Kamishin Gray silt 1.789 49.5 71.3 0.40 85 15 Confl uence of Kamishinka and Volga Gray silt 3.899 50.24 485.4 1.24 178 16 Below Volgograd Sand with pebble 0.136 16.55 2.40 0.14 13 17 Zagan-Aman village Sand with black inclusions 0.036 17.43 4.50 1.00 21 3У Akhtuba channel Silty sand with shells 0.245 23.2 33.1 1.08 12 7У Starobelinsky channel Silty sand 0.359 27.0 20.2 0.44 2 6У Joltaya stream (3 km from Starobelinsky channel) Black ooze 0.499 33.5 2.0 0.03 undefi ned 9У Belinsky channel (to the left from waterway) Dark silty sand 0.029 20.9 2.0 0.55 “ 11У Kamyziak channel (Tabola) Fine light sand with shell fragments 0.012 18.7 16.1 10.71 “ 12У Kamyziak channel (Verkhnekalinoovsky village) Sandy silt with clay 0.15 26.8 9.8 0.52 “ 14У Ryty channel Fine clean sand 0.018 17.8 2.0 0.89 “ 15У 3 km above station 14 Dark silty sand 0.091 25.6 9.7 0.85 “ 16У Staraya Volga channel Fine clean sand 0.011 18.9 2.1 1.45 “ 19У Gandurinsky channel Clay with fi ne sand 0.006 19.7 25.3 33.81 “ 20У To the right from station 19 (in macrophyte thicket) Sand 0.155 28.1 19.0 1.00 29 21У The same (in open water) Muddy sand 1.348 54.5 43.0 0.26 24 22У To the left from station 19 (in a bay) Muddy sand 1.192 44.1 28.1 0.19 252 006.06.2011 12:18:09 6

. 23У The same (in the stream) Sand 0.38 32.7 23.0 0.47 120 0 6

. 24У 7 km below station 19 (in the channel) Dark clay 0.807 35.4 29.2 0.29 24 2 0 1 1

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[Bouloubassi andSaliot,1993]. in thelow-molecularrange compounds natural terrigenous range, andbythetransformation oil supplyinthehigh-molecular UCM iscausedbythepermanent by gaschromatography, the within 10–35.2.Beingunresolved ratiovaried naphthene/alkane 14, and18,where CPI≈1andthe sediments from stations8,11,13, ofthebottom the n-alkanes the closestto oilHCwere According to themarkers, substances. together withterrigenous sediments, oilHCprecipitate 2006]. Onshoals, withinsandy Grichyk, Saliot, 1993;Sokolova, higher plants[Bouloubassiand ofwaxesto thecontribution of whichisusuallyrelatedalkanes, odd the rangeofn-C29–C31 in the maximawere observed several cases,composition. In allochthonous processes ontheir and indicate theinfluenceofauto- may andn-C25 maxima atn-C19 >1).Moreover,phytane (i-C19/i-C20 the prevailed over3.05–6.97, andprystane 3 from the bottom sediments in 2005 at stations: 9 Fig. 4. Composition of the alkanes separated separated alkanes the of Composition 4. Fig. (stations’ 1) atFig. positions 1—18, 2—19, and3—8 station 8 - Tolyatty outer harbor; stationstation 14 harbor; 8-Tolyatty outer –Kamishin; station 3y–Akhtuba Fig. 5. Composition of the alkanes separated from the bottom bottom the from separated alkanes the of 5.Composition Fig. channel; station 7y–Starobelinsky channel; station 19y –Gandurinsky channel; andstation 21y water) channel(in open –Gandurinsky may pointto ahighdegree ofthe Tyulenii + Chr)ratiowasmaximalatstation8,which 0.36. Atthesametime, the(Py+Bp)/(Ph + minimal valueofFl/(Fl +Py)ratio, equalto the the sedimentsofthisstationconfirmed pyrogenous compositionofpolyarenes in as high382ng/g(12.2%ofΣPAH). The the polyarenes identified)atthisstationwas content of Bp(themostcarcinogenic among found inthesandysedimentof sediment, andthemaximalvalueswere also was independentofthegrain-size of type ofPAH,The distribution aswell asthatofAHC, to thestandard deviation(σ−951.2ng/g). average value(948.6ng/g)wascomparable wide(4–4800ng/g, see so Table. 3)thatthe concentrations inthebottom sedimentswas 2005,thedispersionofPAHIn origin ofAHC(Fig. 5). alsopointsto oil the compositionn-alkane 2009,inspite oflower concentrations,In sediments in 2009: in sediments station 19. The 006.06.2011 12:18:09 6 . 0 6 . 2 0 1 1

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4 0 [Lisitsyn, 1995]), the principal changes take changestake [Lisitsyn, 1995]),theprincipal (marginal filters At theriver–sea boundary to fuelcombustioninthenavigable areas. 3.1), whichmay berelated to theirsupplydue sediments ofstation20(8.1atanaverage of value ofthePy/Pl ratiowasfound inthe therefore,the share ofperylene; themaximal supply ofpyrogenous polyarenes decreases studied, itscontent was6.3%onaverage. The PAH thesediments [Tolosa etal, 2004].In isover 10%ofthetotal ofperylene fraction Ross, 2004]. With thediagenetic origin, the Saliot, 1993;Lipiatou etal, 1993;Oros and 2004;Bouloubassiand matter [Nemirovskaya, withterrigenous sediments enriched amounts ofitare usuallypresent inthe polyarenes, thatsignificant despite thefact doesnotbelongtoPerylene theprevailing (r=0.61,n16). parameters wasobserved and asignificant correlationthese between bottom sedimentsoccursinthesameareas, of pyrogenous andoilpolyarenes to the area. According thesupply to themarkers, polyarenes inthebottom sedimentsofthis indicate thehighdegree oftransformation of the Ph/An ratiowasashigh21.7,whichmay from themainnavigable waterways, farthest is below10.Onlyatstation22,whichthe mostofthesamples, al, thisvalue 2004].In the Ph/An ratio isusuallyover 10[Tolosa et of great amountsoffresh oilcompounds, diagenetic processes andwiththesupply 2004]. Undertheintense transformation in oil origin ofthepolyarenes [Tolosa etal., of theApsheron Peninsula andrelated to in thebottom sedimentsfrom theshoals processes. accumulationwasnoted earlier Its decomposable inthecourseofnatural studied, becausethisvolatile arene iseasily inthesedimentsofarea unexpected etal, 1988]appeared 2007; Rovinskii to be offresh oilproducts[AMAP,characteristic ratherhighconcentrationsofnaphthalene The (2.2 onaverage). ratio inthebottom sedimentswasover 1 Caspian Sea,because(Py+Bp)/(Ph +Chr) ofthe part in otherareas ofthenorthern of pyrogenous polyarenes wasalsotraced pyrolysis oforganic raw materials. The effect Island area pollutionwiththeproductsof light homologues – PH and NA prevail in the light homologues–PHandNA prevail inthe contrast to AHC, inthePAHIn composition,the AHC to thebottom may beregistered. final step ofsedimentation,thesupplyoil (including finesilt)are precipitated, atthe matter ofparticulate Only asallthefractions compared to low-molecularcompounds. as matter interface the water–particulate great for capability hydrophobic bindingat plants prevail (seeFig. 2). These HCshow of thecoastalmacrophytes andgrassy high-molecular homologuescharacteristic matter,in allthesamplesofparticulate is negligible 2009]. [Kravchishina, Therefore, content (bymass)oftheclayey fraction andJeffrey,[Kennicutt 1981],becausethe origin with somecomponentsofmarine this isahighmolecularanthropogenic group autochthonous AHCrarely prevail; mostly, matter, filtered2004]. In particulate the waters [AMAP, 2007;Nemirovskaya, processes, especiallyfastinthesurface degraded through physical andbiochemical become their composition.Oilalkanes matter butalsochangesin in particulate only anincrease intheHCconcentrations anthropogenic compoundscausesnot OMrepresentedSea, theterrigenous by oftheCaspian part thenorthern 2009]. In natureof aterrigenous [Kravchishina, OMisusually waters, riverine particulate In matter.HC concentrationsinparticulate areasin harbor promotes theincrease inthe studied. Evidently, intensification ofnavigation ofthesea fromcollected thewestern part matter samples compounds inparticulate resulted inrelatively highcontents oforganic [Shiganova etal, 2003]. This probably delta, withthelatter beingmore powerful from andwestern theeastern channelsofthe isexpressedRiver inthespread oftheflows Caspian Seastudied, theeffect ofthe Volga ofthe part thearea ofthenorthern 2004]. In [Nemirovskaya, amounts suppliedbytherivers sedimentation may reach 80%from their matter decreases of10. byafactor The AHC narrow zone, in avery thefluxofriverine the substancessuppliedbyrivers. Here, place inthecontents andcompositionsof 006.06.2011 12:18:10 6 . 0 6 . 2 0 1 1

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as well HCandC asbetween the grain-size compositionofthesediments, and correlation theHCdistribution between is precipitated. Becauseofthis, there isno flocculation andcoagulation,thebulkofHC [Lisitsyn, 1995].Here, theprocesses during of ofthemarginalthe physicochemical filter part avalanche sedimentationzone, whichincludes the area studiedin2005isassociated withthe shelf oftheCaspianSea(see Table 2).Evidently, onthenorthern time ofthestudiesperformed appeared to bethehighestover theentire The HCcontent inthebottom sediments matter isofmixed origin. particulate et al, 1988].Hence, thePAH compositionin because FLfeatures [Rovinskii highstability a distantairtransfer 2004], [Nemirovskaya, transformation ofthePAH compositionduring andbythe both byanthropogenic impact The highconcentrationsofFLmay becaused belong to thearenes prevailing inoilproducts. origin ofaeolicmatter. NAanditshomologues well theland astheAHCcompositionconfirm matter as a highcontent ofitinparticulate et al, 1988; 1987]and Venkatesan andKaplan, formed insoilsfrom [Rovinskii buried composition ofPAH matter. ofparticulate PHis 100 μg/g, thesiltsediments are saidto μg/g). Even atthe AHC concentrationsof the background level insiltsediments(50 The average valueof895.9μg/gexceeded etal,Nemirovskaya 2007; Tolosa etal, 2004]. aquaticareas 2004; harbor [Nemirovskaya, concentrations registered inthemostpolluted grained sedimentswascomparableto the 10, 17,19(1940–4558μg/g)incoarse- 2005,thecontent ofAHCatstations In (r=0.72). observed time acorrelationC between conformed to weathered oilHC; atthesame flood,the spring thecompositionofn-alkanes River,mouth oftheSevernaya Dvina during main source ofPAH [Culotta the etal, 2006].In considered thepyrolytical processes to bethe althoughtheauthors Lagoon(Italy), of Marsalla PAH concentrationsinthecoastalsediments a correlation wasfound theOMand between even intheareas to oilpollution. subject Thus, inthebottom sediments, usually observed 4 1 org and AHC was andAHCwas org , which is , whichis polyarenes decreased in the order (in%):Py 19. Therefore, of individual thefractions 1000 ng/g, andover 4000ng/g, atstation 17, and23,thecontent ofPAH wasover the studiessince2003.Atstations10,11, theentireto of bethehighestduring period 948.6 ng/g),aswell asthoseofAHC, appeared sediments sampledin2005(onaverage, The concentrationsofPAH inthebottom 2006]. respectively [Jeng, CPI valueswere 4.08and1.70onaverage, samplesnear the marine Taiwan Island, the origin. Thus, sedimentsandin intheriverine oftheir may beusedasamarker n-alkanes the CPIvalue, therefore, thechainlengthof coast in2005.SupplyofoilHCdecreases at station23whichistheclosestto the HC,wasfoundterrigenous inthesediments value ofCPI=6.97,i.e., themaximalvalueof than thatfor siltsubstances. The maximal grained sedimentsappeared to behigher degree ofanthropogenic pollutionofcoarse- increase 2004]. [Nemirovskaya, Therefore, the their content insandysedimentsmay AHC inwater, even dueto passive sorption, increased concentrationsofanthropogenic matter inthemoutharea ofthe Volga River. At ofthesandy–silt be explainedbypoorsorting matterAHC together may withterrigenous Moreover, theaccumulationofanthropogenic alsopointsto oilorigin AHC(Fig.n-alkane 5). of lower concentrations, thecompositionof in theshallow-water zone. 2009,inspite In bulk ofanthropogenic compoundsprecipitate matter,different ofparticulate fractions andthe degrees, to ischaracteristic, various alkanes of HC. Hydrophobic bindingofhigh-molecular is truefor oilproductsmainlyconsistingof anthropogenic AHC accumulation. This Probably, there isalimitto thedegree of bottom sediments wasofamixed genesis. 2005,thecompositionofAHCin In etal,108 μg/g[Nemirovskaya 2007]. aquatic areas didtheircontent increase to and onlyinthesandy–siltmatter ofharbor background level was20μg/gorbelow, theAHC sediments oftheGulfRiga, be polluted sandy [Tolosa etal, 2004].In 006.06.2011 12:18:11 6 . 0 6 . 2 0 1 1

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4 2 the Italian coasts[Culotta etal, 2006].However,the Italian 48090 ng/g, andwithin72–18381 ng/g, off their concentrationsvar area coastsofFrance, ofthenorthwestern the Sea.In sediments oftheMediterranean to thoseofthemostpolluted bottom The concentrationsobtainedare comparable content for of8–19. (20ng/g)byfactors considered exceeded themaximalallowable of Bpinthebottom sedimentsofthearea the sedimentsbecometoxic. The content >1000 ng/g;at PAH inthebottom sedimentsare usually supply ofpollutants, theconcentrationsof theareaset al, ofapermanent 2004].In polyarenes below100ng/g[Tolosacyclic polluted atthecontent ofthesum3–6- The sedimentsare considered aslow- received resultsAblia,2007]. [Sokolova, biogenic HC(Fig. 6),thatagrees withearlier and pyrogenous withasmallinclusion of pointed to amixed origin ofpolyarenes (oil of theavalanche sedimentationmainly inthePAHmarkers compositionofthezone ng/g and13-178ng/g, respectively. The 2-25 between bottom sedimentsvaried River, theconcentrationsofPAH inthe 2009inthe In Volga andthe Delta Volga (6.0) >Bp(5.6)>An(5.3)Chr(4.2). (21.1) >Fl (20.1)>NA(19.2)Pl (6.3)>Bpl 1, 2, 3,4—stations: 1—station 7, oftheKama confluence andtheVolga; harbor; Tolyatty outer 2—station 8, 3 —station 22у, channel(in thebay); Gandurinsky an Fig. 6. Composition of PAH separated from the bottom sediments in 2009: in sediments bottom the from PAH of separated Composition 6. Fig. the values over 4000 ng/g, the valuesover 4000ng/g, ied within6900– here to 3–17ng/g. The (Py +Bp)/(Ph +Chr) of PAH in sandysedimentsalsodecreased prevailed intheircomposition. The content oflandvegetationdecrease, andthealkanes concentrations inthebottom sediments through themarginal filter, didtheAHC passing in 2004),after studies performed shelf oftheCaspianSea(according to the etal,sources 1988].Onlyonthe [Rovinskii Bp supplyfrom naturalandanthropogenic about 400t/year, i.e., about8%ofthetotal seawater is inthesurface Bp destruction a depthof30cm(5.6%). The microbial and, to aconsiderablylower degree, at layer ofthewater (53%/h) in thesurface ofBpmainlyproceedsthe destruction simulation experiments, itwasshownthat oxidation ofnonaromatic HCofoil. In is comparableto thatofmicrobiological rate ofPAH photochemical transformation Even for themore stablepolyarenes, the plant,andanimalorganisms.by micro-, transformations, aswell asto biodegradation chemical (oxidation andphoto-oxidation) physical (weatheringanderosion) and all naturalobjects,HCareto various subject that,in This may beexplainedbythefact mixed origin (anthropogenic andbiogenic). within theircompositionpointed to their of theavalanche sedimentation,themarkers despite thehighHCconcentrationsinarea d 4—station 23у, channel (in thestream) Gandurinsky 006.06.2011 12:18:11 6 . 0 6 . 2 0 1 1

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which included the river channels;the which includedtheriver were examined. The gravitational area, ShelfoftheCaspianSea –Northern River areas ofthemarginal filters ofthe Volga 2003 to 2009,the Volga andallthree River ofthestudiesfrom Thus, theperiod during anthropogenic HCfrom the Volga River. asafilter preventingshelf acts theinputof ofthe mixing. Barrier Volga River–Caspian waterthe area andriverine ofthemarine due to theprecipitation ofPandBPin ratio decreased from 0.6–11.5to 0.3–0.5 4 Table 2. Content of AHC (μg/g of dry weight) in the surface layer of the bottom sediments of the Caspian Sea Caspian the of sediments bottom the of layer surface the in weight) dry (μg/g of AHC of Content 2. Table Table 3. Content of PAH (ng/g of dry weight) in the surface layer of bottom sediments of the Caspian Sea Caspian the of sediments bottom of layer surface the in PAH weight) of Table (ng/g Content 3. dry of 3 og et 0924 « Thisstudy « « 2004 Nemirovskaya, 2–43 3–121.4 « and Nemirovskaya 70–4558 « 12–210 94–136 2009 20–142 2009 59–3881 2–14* Tolosa etal, 2004* 2001,2003 2005 14–113 2004 Note: *total alkanes. backgroundAntarctica, 39–1515 2003 2004 Volga Delta 2001 Volga River shelf Northern 2001 shelf Northern Volga channels River 2000 shelf Northern shelf Kazakhstan aquatic area) (Russian part Northern shelf Iranian shelf Azerbaijan Delta Volga 2009 2–43(Σ10 PAH) 2–43(Σ10 PAH) 3–121.4(Σ10 4–4800(Σ10PAH) 6–76(Σ8PAH) 2009 2009 3–17(Σ8PAH) 8–154(Σ8PAH) Winkels, etal, 1998 2005 7–294(Σ15PAH) 2004 94–1789(Σ15PAH) 2003 2004 Volga Delta 40 338–2988(Σ15PAH) 2001 Volga River shelf Northern 2001 shelf Northern Volga channels River 2000 shelf Northern 1993 shelf Kazakhstan aquatic area) (Russian part Northern shelf Iranian shelf Azerbaijan Volga mouth River einYa H Reference AHC Year Region einYa A Reference PAH Year Region 0014*« 1–42* 2000 006–345(Σ15PAH) 2000 [Lisitsyn, 1995].Here, theprocesses during of ofthemarginal physicochemical filter part sedimentation zone, whichincludesthe treated in2005isassociated to theavalanche E 2,3). the CaspianSea(Tables shelfof onthenorthern performed the surveys appeared to bethehighestover allthetimeof 2005,theHCcontent inthebottom sediments In natural origin ofHCinthebottom sediments. point,to thehighestdegree,the markers to a concentrations; andthebiological area, where avalanche sedimentationwiththehighestHC physicochemical area, orthezone ofthe Brekhovskikh, 2008 Brekhovskikh, Nemirovskaya and Nemirovskaya Tolosa etal, 2004* Brehovskikh, 2008 Brehovskikh, vidently, thearea This study 006.06.2011 12:18:13 6 . 0 6 . 2 0 1 1

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4 4 7. Jeng W-L. (2006) Jeng W-L. Higher Plant n-Alkane Average Chain Length an Indicator As 7. of Efimov I. OilThe (2000) Gasand Resource Base oftheCaspian Region // J. of 6. 5. Dumont Sediments Surface of PAH Composition The (2006) al. et Gianguzza, A. Stefano, De C. Culotta, H. 4. J. (1998) Caspian Bouloubassi Saliot I.and A. (1993) Investigation ofAnthropogenic and Natural Organic3. Lake: AMAP (Arctic Monitoring and Assessment Programme) History, (2007). Chapter 4. Sources, Inputs 2. Agatova B.Kirpichev, I., K. Lapina, A. N.M. etal. (2005) Organic Matter in theCaspian Biota, Sea / 1. Structure, and Function //Limnol. increased role ofHCinC the influenceofnaturalprocesses. However, parameters studiedundergo changesunder that indicate insignificant oilpollution. The corresponded to theirbackground levels waters andsediments of HCinthesurface Volga anditsinflows. River The concentration play leading role attheconfluenceof level ofthe Volga River. Diffusionanddilution ofsummersteady lowwater characteristic waters are substances inthesurface The lowconcentrationsofsuspended is precipitated. flocculation andcoagulation,thebulkofHC particulate matter andthebottom sediments.particulate inthecompositionoffiltered were observed mass. Therefore, pronounced distinctions bottom becauseofthedissolutioninwater matter donotreach the biogenic particulate the bottom sediments, andthegrains of Particulate matter isconsiderablyfinerthan both anthropogenic andnaturalcompounds. due to thetransformation andprecipitation of undergoesVolga regular changes estuary River and thebottom sedimentsinthearea ofthe matter The compositionofHCinparticulate to theinfluenceofpollutingoilcompounds. sediments ofthe Volga probably Delta were due REFERENCES CONCLUSIONS No 3–4. pp. 242–251.No 3–4. PetrogenicScience Hydrocarbons Eng. Vol. 28. pp. 157–159. Oceanogr. Vol. 43. pp. 44–52. Contaminationfrom Stagnone Coastal Marsalla Lagoon, (Italy) // Mar. Chem. Vol. 99No1–7. pp. 117–127. in Marine Vol.Acta. 16. pp. 145–161. SedimentsInputs in Estuarine Sediments Using Hydrocarbon Markers (NAN, PAH) LAB, // Oceanol. //other Contaminants. Mar. Oslo: AMAP. 310 p. Chem.and Concentrations ofPetroleum Hydrocarbons, Polycyclic Aromatic Hydrocarbons, and Vol.102.Okeanologiya. Vol. 45. No. 6.pp. 841–850. org in arenaceous inarenaceous for basicresearch); projectno. 10-05-10084-а. Russian Academy ofSciences)(Program no. 21 Foundation for BasicResearch (Presidium ofthe bytheRussian This studywassupported et al, 2004]. polluted areas oftheCaspianSea[Tolosa shelfisoneoftheleast the northern amount ofanthropogenic compounds, despite the Volga supplyingagreat River is possible thatbecauseofthisand It thesea. entering filter preventing theanthropogenic HCfrom of the Volga asa shelfacts River–Caspian 2009 showed thatthegeochemicalbarrier The synthesisofthedataobtainedin2003– bottom sediments. content and thegrain-size compositionofthe theHC between no correlation wasobserved to 4800ng/gfor thetotal PAH). Becauseofthis, place(upto 4557.9μg/gfortakes AHCandup the HCaccumulationinbottom sediments avalanche sedimentation,thehighestdegree of ofthemarginal filter,part inthearea ofthe processes. As aresult, inthephysicochemical gravitational, physicochemical, andbiological substancesareOM withmarine causedby The deviationsfrom asimpledilutionofriverine ACKNOWLEDGMENTS 006.06.2011 12:18:13 6 . 0 6  . 2

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24. Winkels H.J., Y. S.B.Kroonenberg, M. Lychagin, etal. (1998) ofPriority Geochronology 23. Venkatesan Kaplan (1987) J. and I.R. M. ofAntarctic Marine Lipid The etal.Tolosa (2004) Sheikholeslami Aliphatic R. M.R. I., S.MoraM. and Aromatic Hydrocarbons 22. 21. (2007) AbliaSokolova E.A. M.N. Investigation in organic matter ofbottom 20. GrichykSokolova D.V. M.N. (2006) Investigation sediments ofpollution ofbottom ofthe 19. Shiganova T. V. A., V. Sapozhnikov, E.I.Musaeva, etal. (2003) Factors Determining the 18. Rovinskii F.17. Oros D. R. and Ya., J. M. Ross (2004) Polycyclic Aromatic T. Hydrocarbons A. in Estuary sediments Teplitskaya, // Nemirovskaya A.P. IA., 16. Lisitzin and V.P. Shevchenko (2007) Distribution and Composition of and T. A. Alekseeva (1988)15.Nemirovskaya I. Background A and V. F. Brekhovskikh (2008)14. Origin Monitoring of Hydrocarbons in theNemirovskaya Particulate of Methods for Studying Organic13. Matter in theOcean (1980) Romankevich Ed.by E.A. Nauka, 12. Guidelines.Methodic (1996) I. Determination ofPollutants in theSamples ofBottom A. Lisitsyn, A.P. (1995)11. Marginal The filter (2004) oftheOcean // Oceanology.Vol. 34, No. 5, pp. 671–682. Hydrocarbons10. Lipiatou, Saliot. J. and Marty, A. (1993) Sediment Trap Fluxes and Transport ofPolycyclic Kravchishina D. M. (2009) Suspended Particulate Matter in theWhite Sea Grain-Size and its 9. in the (1981) Jeffrey M. C.and L. M. Kennicutt Chemical and GC-MS Characterization ofMarine 8. Ocean (Snow–Ice–Water–Particulate 4 5 Rhone Delta //Rhone Delta Vol. Applied Geochem. 13. pp. 581–591. Pollutants in Sedimentation Zones oftheVolga and Danube in Delta Comparison withthe Sediments: Bransfield Strait // Mar. Chem. Vol. 21. pp. 347–375. in Coastal Caspian Sea Sediments //Mar. Pollut. Bull. Vol. pp. 44–60. 48. Russian]. and Middlesediments Caspian oftheNorth Sea // Vestnik MGU, №2, pp. 49-57 [in CaspianNorth Sea withorganic compounds //Vestnik MGU, №6, pp. 16-23. Russian]. [in Caspianleidyi in theNorth // Okeanologiya. Vol. 43 No5, pp. 716–733. Conditions ofDistribution and Quantitative Characteristics oftheCtenophore Mnemiopsis Polycyclic Aromatic Hydrocarbons. Gidrometeoizdat, Leningrad. 224 p. Russian]. [in Mar. Chem. Vol. 86.pp.169-184. of theTenth International Symposium onRiver Sedimentation. Moscow. V.4. P.175-184. Hydrocarbons in Bottom Sediments at theRiver-Sea Geochemical Barrier // Proceedings No. 1,48, pp. 43–53. Matter and Bottom Shelf Sediments oftheCaspian oftheNorthern Sea // Oceanology, Vol. Matter–Bottom Sediments) (Nauchn. Mir, Moscow. 328 p. [in Russian]. Moscow. 343 p. [in Russian]. Sediments. RD52.10.556-95 Gidrometeoizdat, Moscow. P. 18-26 [in Russian]. Aromatic Hydrocarbons in theMediterranean Sea //Mar. Chem. Vol. pp. 43–54. 44. Distribution. Nauchn. Mir, Moscow. 263 p. Russian]. [in Dissolved Lipids // Mar. Chem. No. 10, pp. 367–387. InnaA.Nemirovskaya and two books. regions. andAntarctic Arctic Author of190scientificworks inmany expeditions including thosetoShe took part hydro-, bio-, lithosphere inthe cryo-, atmo-, World Ocean. anthropogenesis hydrocarbons spheres: inallexternal qualitative distributionofvariousclassesnaturaland The focus ofresearch: mechanismof quantitative and Oceanology, RussianAcademy ofSciences, DSc. inGeology. oftheP.Analytical Laboratory P. Shirshov of Institute University Faculty ofChemistry. Now sheistheHeadof graduated from theMoscow State 006.06.2011 12:18:13 6 . 0 6 . 2 0 1 1

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