G. Oaiaet al. - Environmenfalassessment of the RiverDanube between 1995 and 1997

ENVIRONMENTALASSESSMENT OF THE RIVERDANUBE BETWEEN I995 AND 1997

GheorgheORrel, gtefan SzoeorKAl, Adrian SrAHtcAl, Aurelia GRosul, Constantina Furce2, GicuOpnrRruuz, Gy0ngyi RuzsR3, Simona Pesrneea

tNationaffnstitute of MarineGeology and Geo-ecology- GEoEcoMAR, 23-25,D. OnciulStr., 70318 Bucharest, Romania 'zNationalfnstitute of MarineGeology and Geo-ecology - GEaEcoMAR, ConstantaBranch, 3M MamaiaBvd., 8700 Constanta, Romania 3Environmental Research and Engineering Institute, 294,Splaiul Independentei Str,, 77703 Bucharest, Romania 'GeologicalInstitute of Romania, 1 CaransebesStr., 78344 Bucharest, Romania

AbstracLThe EuropeanRiver-Ocean System, EROS - 2000Danube Project (PI-IARE Contracl No. 9!0339), aimedat assessing '1997. theenvironmental state of RiverDanube between 1995 - The studieswere canied out alongthe entire Romanian Danube watershed.In time, the natural flow regime of the Dunube River was disturbedby anthropicintervention (damming and embankment).The exist€nc€of numerousindustrial and agricultural obieclives in the Danube'sdrainage basin altered the qualityof the environment.In orderto assessthe anthropicimpact on the Danubeenvironmental quality, water and sedimentsarnples were collectedand analysed, The water samples analyses show the physical-chemicalparameters and heavy metals, nutrients, organic pollutantscontents. Grain size values,heavy minerals associations and heavymetals contents were performedon the collecied bottomsediment samples. Studies were also maderegarding the naturaland artificialradionuclides contents in bottomsediments. Studieswere made on diatomsassociations, used as salinityand pollutionmarkers. lt can be remarkedthat the general environmentalslate along the RomanianDanube wat€rshed improved from 1995 to 1997,unfurtunately due mainlyto the economicalrecession. Keywords: EROS2000, Danube River, environmental assessment, sediments, grain size, heavy metals, diatoms, radionuclides

INTRODUCTION surfacewater, the characteristicsof the biotopes, The EuropeanRiver-Ocean System,EROS - waterand sediment fluxes and naturaland artificial 2000 Danube Project,aimed at assessingthe radionuclidestypes and characteristicsin water environmentalstate of River Danubebetween andsediments samples. 1995and 1997. The longitudinalmonitoring was completedon The studieswere carried out in the framework cross-sectionson the Romaniancourse (km 1075- of the PHARE ContractNo. 95-0339 " Danube BlackSea) of the RiverDanube. The samestudy EROS - 2000 Research Programme sectionsfrom 1995were maintained for 1996and Romania"signed by the EuropeanCommunity 1997. Commission as "ContractingParty" and the Grainsize analyses for 1995- 1997period National Institute for Marine Geology and ln the Portile de Fier I reservoirtwo main Geoecology(GEOECOMAR) as'Contractor''. The depositionalenvironments were observed: the contractis placedunder the co-ordinationof the upstream area (Km 1072.4 - Km. 1010), DanubeProgramme Co-ordination Unit. characterizedby predominantsandy sediments For the completionof the specifictasks of the and fine sediments(silts) in the lacustrine'sensu project,the NationalInstitute for MarineGeology stricto"environment (Km. 1010 - Km. 943). and Geoecologyworked in co-operationwith BetweenPortile de Fier I (Km.943) and Portilede several Romanianresearch institutes(National Fier ll (Km. 864) barrages,the sedimentsare ResearchInstitute for EnvironmentalalProtection - constitutedmainly of sandsand gravel.Only close lGlM Bucharest,Geological Institute of Romania, to the Portilede Fier ll barragethere was founda "LowerDanube University" - Galati). thinlayer (2 cm) of finesediments. Between The presentpaper contains the comparisonof Portilede Fier ll banage(Km. 864) and Mile44, the measureddata and resultsfor 1995,1996 and the beginningof the DanubeDelta, the bottom 1997 cruises.The 1997 resultsare presented sedimentsare representedmainly by sands and separately,as the samples collection and seldomby gravel.The sedimentscollected from measurements cruise took place between the four main distributariesof the DanubeDelta Novemberand December,while the cruisesfrom (Chilia,Tulcea, Sulina and Sf. Gheorghe)are the previoustwo years had been held between mainly sands. Finer sediments (from fine to June and July. The main aspects are: the mediumgrained silts) are presentat the mouthsof assessmentof the qualityof bottomsediments and

GEO-ECO-MAR[NA,3/1 998 89 NationalInstitute of MarineGeology and Geo-ecologyof Romania Prcc.lntem. Workshop on "ContinentalMargins and Sea Level Changes" in Tescani,Romania, Oct. 6 -12, 1997 'w€lul '&)d 'ZL- 'epewaa'ruscseJ puB pusuluo1, uo tutts>trol$ t66t g po u! ts^s78es sulanfi elue,aoap tr'aotme|oea"s6f,uri,tcpue Aaopee eupewp e,f,,$sulleualev 86618'VUHW'O9?€3o

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'p 'e essepy€tttuu!^u1 - p Eeo G. Oaieet al. - Environmenfalassessrnent of theRiver Danube befween 1995 and 1997

the distributaries(Hm. 72 - Sulina;km 1.3 - Sf.Gheorghe).The samplescollected from most Romaniantributaries, at the junctionswith the DanubeRiver, show distinctgrain size features. rulFs --..] The sedimentsare mainlysands in the following .rlJqnq$rlo 0o0r+9tqu I ] l rivers.Topolnita, Jiu, Arges,lalomita, Siret. Silts i arepredominant in Cerna,Olt, Vedea, Prut rivers. frtaur I Comparison of heaw_metals contentsfrom r''cur bottom sedimentscollected between 1995 and I i 't em{ 1996underlined the followingmain conclusions: f0o9 Cu - insignificantchanges in the MoldovaNoui area,(values of 3380ppm in 1995,3690 ppm in i-,,".,n I 1996),a slightlydecreasing trend between Mile 78 rz9r uy andthe BlackSea (Fig.1); Zn - the samemaximal I valuesin the MoldovaNouS section (1280 ppm in - lll uty 1995,1500 ppm in 1996);downstream Km 1040 -LJZUJy sectionthe valuesdecreased in comparisonwith - the previousyear; Pb the maximalvalues were .,, 'tocu)a measuredin thePortile de Fierldam lakein 1995 E (Km952 - 243 ppm,Km 947.2- 195ppm). These .F _ qJut g raaro€ l'tt r!)l values suffered an important decrease,H maintaininga relativelyconstant level till Mile78; E -gzt a)l Ni - muchlowercontents in 1996than in 1995,of E -9tt uty the maximalvalues; approximately constant values i - - betweenKm 866 Black Sea; Gd important5 - l8t ulx decreasesince 1995between Km 1072.4and Km 6 947 (Portilede Fier I lake);the valuesincreased ff l-919ux - betweenKm 866 and the BlackSea (Fig.2);Ct I ';E the same trends are maintainedeven by the fcrsux maximaland minimalvalues for the two studied'[f; years;Mn - in comparisonwith 1995,the maximal f r'*r," values moved downstreamthe Portilede Fier ll i j-'rasu,v I dam,reaching a peakof morethan 1400^ppmat p l Km866; between Km 684 and Mile33 + 1000,the i I Tta9 uy - I values remain relativelyconstant; V relativelyfi i constantvalues in 1996compared to 1995were - j f c'sorrx measuredin the reservoirs;a peakof 60 ppmwas .t I - -e.r8t rux measuredin 1996at Hm72 Sulinadistributary. -,P In 1996, in comparisonwith 1995, the 1998 u)l situationis generallyimproved, exception being !!)| the Cd contents(for the Portilede Fierll barrage- f z'ltg Mile 44 section). For the main Romanian tributaries,the measuredvalues for 1996generally havea decreasingtrend in comparisonwith 1995 T9'09C uI for the Cerna,Topolnita, Olt, Arges, lalomita, Siret I and Prut rivers,The situationbecame worse only fg'cseu:n for Jiu and Vedeatributaries, as mostof the heavy I metalscontents increased very much as follows: Fgoaurx Jiu River:Cu, Pb, Ni, Cd, Cr, Mn, As;Vedea River: I Cu,Zn, Ni, Cd, Mn,V, ArgesRiver maintains the iotol u)l same high pollutionlevel for both years,even though there was observeda decreasefor the =_r I foflowing contents: Cu, Zn, Cd, Cr, Mn, As. Pband -t?l0!ruy oo Ni (Fig.3)were found here in the highestcontents 0 in comparisonwith allthe other presented rivers. o The water saqrplesfrom the Danubeand its main Romaniantributaries were analyzedfor: dissolved 02 concentrationand O2 saturation,

GEO.ECO.MARINA.Y1998 Nationallnstitute of MarineGeology and Geo-ecologyof Romania Proc.lntem. Workshop on'Continental Margins and Sea LevelChangos" in Tesani, Romania,OcL 6 -12, 1997 G. Oaie et al. - Environmenlalassessment of the River Danubebetween 1995and 1997

CAD,TDS, oH. Eh. susoended solids and nutrients disappeared;detergents - someof thehigh values (Not, No2', pOo&). Physical - chemical maintainedboth for 1995 and 1996 in the Olt (> 0.1 parametersshow important variations: DOe and Oz mg/l) and Arges (0.14 mg/l) rivers.New high have minimalvalues in the Portilede Fier ll valueswere measuredin 1996 on the Danube reservoirand on the Sulinadistributary; CAD and branchesat Mile44 P.22 mg/l)and at Km 1i5.2- TDS for 1996 are higherthan in 1995;forthe Chiliadistributary (0.14 mg/l); organo-chlorlnate suspendedsolids thereis a relativesimilarity for compounds- the highvalues measured in Cerna, bothyears; pH valuesvary between 7.50 - 8.20in Jiu, Olt, Vedea and lalomita rivers in 1ggs 1995 and 7.2A- 8.45 in 1996.Many variations decreasedto valuesless than 0.001 mg/l in 1996. were observedfor the mainRomanian tributaries: Heavv metals, in 1996 the CAD valueswere 1.700mS/cm for measuredon filtered water samplesshow the following variations: Arges and 1.250 mS/cm for Vedea rivers;the As andSe contents highestTDS valueswere measuredin the Arges oversteppedthe Romanianstandards in all the water and Vedearivers; the Oz (9 DO2(<1 samples,Cd and Zn contents %) and %) part concentrationsare verysmall in ArgesRiver, both oversteppedthe standardsin the upstream of the Portile Fier I in 1995and in 1996; the highestvalues were de reservoir;Hg contentsare higher Romanian measuredin Cernaand Vedea rivers; the maximal thanthe andE.U. standards. For the mainRomanian valuesfor the suspendedmatter in 1996 were tributaries:Hg contentswere higherthan the standardsin Olt andVedea rivers; measuredin SiretRive(320 mg/l) and Jiu River(> Gd 250mg/ l) rivers. contentshad the onlyabnormally high value in 1995at the mouthof ArgesRiver (3.4 ppb);Se As a result of the comparativestudy of the andAs contentsexceeded both the Romanianand measurednutrients concentrations-in the River E.U.standards in the watersamples collected in Danubeboth for 1995and for 1996the following 1995,while in 1996only in Jiu River(Se) and conclusionsemerged: NHa* contents is with- 0.2 Cernaand Olt rivers(As); Zn contentsin Arges, mg/l higherin 1996than in 1995.Along the river Siret and Prut rivers exceededthe Romanian the valuesare relativelyconstant; NO2-ranges standardsin 1995.For 1996, these standards were betweenthe samelimits for the bothyears (0.05 - oversteppedin the samplesfrom Cerna,Topolnita, 0.25mg/l). The maximalvalues measured in 1995 Jiu,Olt, Vedea, lalomita rivers. were observedin 1996 only at Mile 34; NOs' Theresults obtained during the 1997cruise are contentsshow two oeaks at Km 879 and Km presentedseparately because the cruisewas held 709.5;POr3- contents are with 0.400 mg/l higher in betweenOctober and December. 1996 than in 1995.Three maximalvalues were measuredat Km 1040,426and 167, in 1996;TOC Heavvmetals contents in bottom sediments: valueswere much higherin 1995than in 1996 the highestpollutants contents were foundin the betweenKm 1072.4and Km 596.3.Only one Portilede Fier I reservoir.The followingheavy peakwas spotted in 1996at Km 553.Between Km metals exceededthe standardvalues: FezOg, 515and the BlackSea the values range constantly MnO,Pb, Mn, Zn, Ni, Cr, V, Hg,Cu, Cd. The most between10 - 25 mg/lin bothyears. heavily pollutedmain Romaniantributaries in heavymetals were: (Fe2O3,TiO2, V) Alongthe RomanianRiver Danube section the Cerna Cd,Cr, and Vedea (MnO, Ni, Cu, Pb, Hg) rivers.The followingevolution trends of the most important highestmeasured value for As was found in organic pollutantswere: phenols presented lalomita maximalvalues only in 1995; detergentshave River. similarvalues both for 1995and 1996; organo- Heavv minerals in boftom.sediments:the chlorinatecompounds concentrations decreased only issuesthat allowedthe comparisonof the 10times in 1996compared to 1995. resultsfor the threeyears of study(1995 - 1997) arethe heavyminerals. Their associations are not For the main Romaniantributaries, both disturbedby the seasonalvariations, as they nutrients and the organic pollutants,suffer significantvariations: NHr" - significantlyhigh dependonly on thesource areas. About 40 distinct heavyminerals have identifiedin valueswere measured in bothyears for the Arges, been the fine the DanubeRiver. In lalomitaand Jiu rivers;NO2'maximal values were bottomarenytes of all the samplescollected during the three cruises,the measuredin 1996in theArges and Jiu rivers; NO3' heavyminerals associations were dominatedby highestvalues were measuredin the Jiu River; garnet by amphiboles P6ot-hadan abnormallyhigh value in ArgesRiver and occasionally and in 1996. opacites. The nutrientsand the organicpollutants from Variationof phvsical- chemicalparameters the same main Romaniantributaries suffered of watersamples: Because the 1997cruise was held in October- December,when the water significantalterings: phenols: the peaksobserved oC in Cerna, Jiu, Olt and Arqes riversin 1995 temperaturedecreased from 16.7 in Octoberto

GEA-ECA.MARINA,V1998 National lnstituteof Marine Geology and Geo-ecologyof Romania Proc. lntem. Wotkshop on'Continental Margins and Sea Level Changes"in Tescani, Romania, Oct. 6 -12, 1997 ^L- G. Qaieet al. - Envircnrnenfalassessment of the RiverDanubo between 1995 and 1997 lues oC 5.7 in December,dissolved oxygen increased measurementof heavymetals concentrations (Hg, 0.1 from upstream 5.54 mg/l (watertemperature - Cd, Pb, Zn, Cu, Cr, Fe, Mn, As, Se). lt can be high 6.9 to downstream(7.17 mg/l at a temperatureobservedthat the Danube "C)oC), Deltaretains the Zn and ube of 16.7 ptt valuesincreased from upstream to Cu cationsas oligoelementsduring the biologic i.2- downstream,from 7.53(Km. 999 profile)to 8.7 on processesor by bioaccumulationin the deltaic rate the Km. 3 - Chiliadistributary profile. The water faunaand flora. These high concentrations are due rna, alkalinitymight be also due to the massesof probablyto the washoutsfrom the waste dumps 995 pollutedwaters brought by the main Romanian connected to Tulcea industry, being 16. town's tributaries.The nutrients contents (NHr*,NOg-, afterwardsadsorbed by the suspendedsediments. NO2-,PO4&) respect the maximalvalues specified !!er Diatomsassociations: the observationsmade by the Romanianand E.U. standards.The Se markersallow the measured organic pollutants (detergents, on the diatoms,as salinity ;in conclusion that no salinity variations were pesticides,phenols, CN-, S-, TOC) concentrations rnts observedfrom one cruiseto another.Most of the arewell belowthe maximalstandard values. tof observed species, from the studied samples are The mainheavy metals measured on thewater collectedin all the cruises,are alcaphyle,these For of the River Danubeand its main Romanian being accompaniedby species that prefer a ere tributarieswater samples were: Cu, Pb, Zn, Fe, neutralpH. The comparativestudy of the diatoms )rs; Mn, Hg, As, Se, Cr and Cd: Fe was found in associationsas markersfor the riverpollution level rin concentrationshigher than the standards in showsthe existenceof areaswith various pollution Se severalprofiles from the Portilede FierI reservoir; levels. The constant presence of Fragilaria rnd Se and Hg werefound in abnormalconcentrations crotonensis(pollution-intolerant species) shows in nd 3S, an )re Flg { Malnpollubnt hotcpob dong the ta, RomanlanDanubs WHenhed rre rld 1 9: 1e /0 ty J.s 13, : st l in : L /) 1 ra n I tr-* o Giurgiu e Moldovo Noud Brdilo e o o Goloti ) Portilede FierI Donr o )t o Heovilypolluted v o TurnuMogurele \ Romqniontributories .+ o Zimniceo ; l generallydownstream the industrial towns. the existenceof a lesspolluted environment in the I Bazias- Portilede Fier I barragesection. The I A specialcase is representedby the Danube Delta.The deltaicsystem acts like a bufferzone speciesthat tolerate a highpollution level (Diatoma vulgare,Achnanthes minutissima, Nitzschia palea) for the Danubewater. The followinq-ttO-gconclusions can be presented:POla, NH'a an^d ionsare are constantlypresent in a high percentagein the retentionedby the deltaicflora. PO*a accumulation samplescollected during all the cruisesin the is a cause for the lakes' eutrophication.The following areas: Jiu and lalomita rivers and Danubewater samples were analyzed also for the DanubeDelta area. This shows the constant

GEO-ECO^MAR|NA, 3/1 998 93 Nationallnstitute of Maine Geologyand Geo-ecologyof Romania Proc.Intem. Workshop on "ContinentalMargins and SeaLavel Changes" in Te*ani, Romania,Oct. 6 -12, 1997 G. Qaieet al. - Enviroruental assossment of the RiverDanube between 1995 and 1997 presencein these areas of a highly polluted sewage waters), or affected by accidents environment. (e.9.Chernobyl nuclear power plant) (Fig.4). Natural and artificial radionuclides:the The main polluted tributaries(Jiu, Arges, sedimentsamples were analyzedusing the high lalomita),represent important "hot spots"for the resolutiongamma spectrometrymethod for the River Danube, but their effects are limited in naturaland artificialradionuclides contents. Cs- space. 137 has a major contributionin the studied The annualmonitoring of the pollutionlevels samples.Cs-137 presence in the sampleshas as anddistribution for RiverDanube and its tributaries main causesthe nuclearopen air testsand the broughtto the conclusionthat the main pollution Chernobylaccident (May, 1986).The Chernobyl sourcescould be dividedin twocategories: momentwas used as markerfor the computation l.natural:- geologicalsource areas rich in ores; of the sedimentationrates. The maximumcontents sedimentation conditions that allow the in Cs-137were consideredas correspondingfor gravitationaldeposition (e.9. lakes, meanders); fine 1986. By the use the Cs-134/Cs-137isotopic grained bottom sediments than adsorb the fractions,considering a constant sedimentationpollutantson theirsurfaces. rate, sedimentationrates of 1.6-2.3cm/year were computedin the Portilede Fier I reservoir(results 2.anthropic:untreated waste and sewagewater obtainedin 1995). spills;mining, drilling, oil extraction,agricultural and industrialactivities; washout by meteoric coNcLusloNs watersof chemicalelements and compoundsfrom In time, the naturalflow regimeof the River the .waste dumps of ores, barren and ashes; Danubewas disturbedby anthropicinterventions. regional or local accidents (e.9. Chernobyl The damming broke the bed load flux and accidentfrom 1986). introduce disbalancesin the Black Sea littoral The self regeneratingcapacity of the River sedimentbudget. The reseruoirsPortile de Fier I Danubeand the filteringrole of the Danube Delta and ll representtraps for sedmenfsand pollutants are factorsfor improvingthe quali$ of the river (nutrients, organic matter, heavy metals) by waterand, only a multLannualmonitoring study deposition in the lacustrine environment, representsthe way for a better protectionof the adsorptionof pollutantson the surfaceof the fine RiverDanube. sedimentsand a significantsedimentation rate The main conclusionof the EROS 2000 - (1.2 5.8cm/y). Programmeis thanthe environmentalstate of the The highestvalues for pollutantscontents (e.9. RiverDanube is betterin 1997in comparisonwith Cu, Pb, Zn, Cd) are in the areas with lnfense 1995 and 1996, the principalcause being anthropic activities (mining and oil extractive unfortunately,the generaleconomical recession of industries;chemical and thermoelectrical.power South-EasternEuropean countries. plants;siderurgy and metallurgy;urban sources of

GEO-ECO-MARINA,311 998 Nationallnstitute of Maine Geologyand Geo-ecologyof Romania Prcc.lntern. Wotkshop on "ContinentalMargins and Sea Level Changes" in Tescani,Romania, Oct. 6 -12, 1997