selenium in soils cuvardic

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Zbornik Matice srpske za prirodne nauke / Proceedings for Natural Sciences, Matica Srpska Novi Sad, ¥ 104, 23—37, 2003 UDC 631.416:546.23 Maja S. Åuvardiã Faculty of Agriculture, Trg Dositeja Obradoviãa 8, Novi Sad Institute of Field and Vegetable Crops, Maksima Gorkog 30, Novi Sad SELENIUM IN SOIL ABSTRACT: Selenium (Se) is an essential microelement, necessary for normal func- tioning of human and animal organisms. Its deficiency in food and feed causes a number of diseases. In high concentrations, selenium is toxic for humans, animals and plants. Soil pro- vision with selenium affects its level in food and feed via nutrition chain. However, seleni- um reactivity and bioavailability depends not only on its total content in soil but also on its chemical forms. Distribution of the different forms of selenium depends on soil properties such as reaction, aeration, contents of clay and organic matter and microbiological activity. KEY WORDS: selenium, total Se, water-soluble Se, soil INTRODUCTION The biological importance of selenium is reflected in the fact that it is es- sential for humans and animals on one side (R a y m a n, 2000), and toxic when in high concentration on the other. This controversial element was disco- vered by Berzelius, a Swedish scientist, in 1817, although it was Marco Polo during his travel to Asia, as early as the 13 th century, who observed toxic symptoms in animals feeding on plants that contained a high concentration of selenium. In the first half of the 20 th century, selenium was considered exclu- sively from the standpoint of its toxicity, until it was identified as a compo- nent of a preparation which prevented the necrosis of liver in rats (S c w a r z and F o l t z, 1957). Soon afterwards, selenium was found to play a key role in glutathione peroxidase, an enzyme that catalyzes the decomposition of hydro- gen peroxide thus protecting cells from oxidative damage. Selenium also plays an important anti-carcinogenic role and it neutralizes heavy metals toxicity. Soil provision with selenium affects its level in food and feed via nutri- tion chain (F i n l e y et al., 2000). However, selenium reactivity and bio- availability depends not only on its total content in soil but also on its chemi- cal form. Depending on oxidation state, selenium is present in soil as selenide (Se 2— ), elemental selenium (Se 0 ), selenite (SeO 3 2— ), selenate (SeO 4 2— ) and or- ganic selenium. The water-soluble selenium fraction is considered to be most available to plants. Its content in normal tilled soil does not exceed 50 ppb 23

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ZbornikMaticesrpskezaprirodnenauke / Proceedings for Natural Sciences, Matica SrpskaNovi Sad, 104, 2337, 2003UDC631.416:546.23M a j a S . u v a r d i Facultyof Agriculture, TrgDositejaObradovia8, Novi SadInstituteof FieldandVegetableCrops, MaksimaGorkog30, Novi SadSELENIUMINSOILABSTRACT:Selenium(Se)isanessentialmicroelement, necessaryfornormalfunc-tioningofhumanandanimalorganisms.Itsdeficiencyinfoodandfeedcausesanumberofdiseases.Inhighconcentrations,seleniumistoxicforhumans,animalsandplants.Soilpro-visionwithseleniumaffectsitslevelinfoodandfeedvianutritionchain. However, seleni-umreactivityandbioavailabilitydependsnotonlyonitstotalcontentinsoilbutalsoonitschemical forms. Distributionof thedifferent formsof seleniumdependsonsoil propertiessuch as reaction, aeration, contents of clay and organic matter and microbiological activity.KEYWORDS: selenium, total Se, water-solubleSe, soilINTRODUCTIONThe biological importance of selenium is reflected in the fact that it is es-sential for humans and animals on one side (R a y m a n, 2000), and toxicwhen in high concentration on the other. This controversial element was disco-veredbyBerzelius, aSwedishscientist, in1817, althoughit wasMarcoPoloduringhis travel toAsia, as earlyas the 13thcentury, whoobservedtoxicsymptomsinanimalsfeedingonplantsthat containedahighconcentrationofselenium. Inthefirst halfofthe20thcentury, seleniumwasconsideredexclu-sivelyfromthestandpoint of itstoxicity, until it wasidentifiedasacompo-nentofapreparationwhichpreventedthenecrosisofliverinrats(S c w a r zand F o l t z, 1957). Soon afterwards, selenium was found to play a key role inglutathioneperoxidase, anenzymethat catalyzesthedecompositionofhydro-genperoxidethusprotectingcellsfromoxidativedamage.Seleniumalsoplaysanimportant anti-carcinogenicroleandit neutralizesheavymetalstoxicity.Soil provisionwithseleniumaffectsitslevel infoodandfeedvianutri-tion chain (F i n l e y et al., 2000). However, seleniumreactivity and bio-availabilitydependsnotonlyonitstotalcontentinsoilbutalsoonitschemi-calform. Dependingonoxidationstate, seleniumispresentinsoilasselenide(Se2), elemental selenium(Se0), selenite(SeO32), selenate(SeO42)andor-ganicselenium. Thewater-solubleseleniumfractionisconsideredtobemostavailabletoplants. Its content innormal tilledsoil does not exceed50ppb23(W o r k m a n and S o l t a n p o u r,1980).Althoughseleniumisnotessentialfor plants, theytakeupseleniumandincorporateit intheir aminoacidsandproteins (S h r i f t, 1973). The level of seleniumaccumulationinplants de-pendsontheamount of availableSe, pHvalueandredoxpotential, contentsof sesquioxide, clay and organic matter and the microbiological activity of soil(J u m p and S a b e y, 1989).GEOGRAPHICDISTRIBUTIONOFSELENIUMSeleniumisabundant indifferent partsoftheworldbut itslevel insoilvaries withnative substrate, climatic conditions andvegetationcover (M c -N e a l and B a l i s t r i e r i,1989).IncentralUS,forexample,thereareregi-ons inwhichplants containSe levels 10times higher thanthe toxic level,whileSelevelsinplantsineasternandwesternUSarelow(K u b o t a etal.,1967). IneasternCanada, Seconcentrationsinplant drymatteraremuchbe-low0.1ppm(W i n t e r and G u p t a, 1979), whiletheyare10timeshigherinwesternCanada. SeleniumdeficiencywasobservedinsomepartsofSouthAmerica, seleniumtoxicityinothers(J a f f e, 1973). SeleniumdeficiencywasnotedinwesternandsouthernpartsofAustraliaandinNewZealand(W e l s het al., 1981).SevereseleniumdeficiencyregisteredinsoutheasternChinahasbeenas-sociatedwithKeshandisease, adiseasethatoccursalmostexclusivelyinchil-dren.InIndia,toxicitywasobservedintheregionofHarayanaanddeficiencyintheotherpartsofthecountry(D h i l l o n and D h i l l o n ,1991).TotalSecontent isslightlyincreasedinJapanesesoilsascomparedwiththecontentsestablished in other countries (K a n g, 1990). However, because these soils ha-veanacidreactionandbecauseofthehumidclimateofJapan, theconcentra-tionofwater-solubleSeislow, makingonly2.33.85%ofthetotal Secon-tent (K a n g, 1990).InEurope, toxiclevel was registeredinseveral locations inWales andIreland(F l e m i n g, 1962). SymptomsofSedeficiencywereobservedincat-tleinEnglandandScotland(R i m m e r etal.,1990).SuboptimalSecontentswere reported for northern Europe. In Finland, before Se fertilization became aregular practice, wheat contained only 1015 ppb Se (K o i v i s t o i n e n andV a r o, 1981). LowSelevelswereregisteredinPoland(meanvalue0.27mgg1) (B o r o w s k a, 1998) andHungary(G o n d i et al., 1992; H o r v a t het al., 1996).Inour country, preliminarystudiesof soil, cereal andanimal feedsam-ples (K r a j i n o v i , 1983) indicated the presence of low Se levels. Later stu-diesofSecontentingeologicalmaterials(J o v i etal., 1995; D a n g i etal., 1989), soil (J a k o v l j e v i et al., 1995; M a k s i m o v i et al., 1992; u v a r d i et al., 1997) andbiological materials (M a k s i m o v i et al.,1992) confirmedapronouncedSedeficiencyonthisterritory. PerilouslylowSe contents were found in blood serumand hair of two groups of maleexaminees, minersintheMajdanpekcoal stripmineandinhabitantsof are-gioninthevicinityof Belgrade(serum31ppband25ppb, respectively;hair76ppband73ppb, respectively). Accordingtotheseresults, theana-24lyzed populations were comparable to the inhabitants of the countries sufferingasevereSedeficiency, suchasChina, NewZealandandFinland(M a k s i -m o v i et al., 1992).SELENIUMINLITOSPHEREThe primary sources of Se in nature are volcanic rocks and metal sulfidesformedbyvolcanicactivity(NAS, 1974). Althoughsome50mineralscontainSe,itoccursmostfrequentlyinsulfidesofheavymetals(Ag,Cu,Pb,Hg,Ni,etc.),eitherintheformofselenideorsubstitutingthesulfurion(S)inthemi-nerals' crystal grid (A d r i a n o, 1986). Average Se content in the Earth'scrustisconsideredtovaryfrom0.05to0.09mgg1(L a k i n,1972).TotalSecontentvariesfrom0.1to2mgg1inmostsoils(S w a i n e,1955).Increasedamountsof Searefoundinthesoilsformedbythedecompositionof shale,mostlyinaridandsemiaridregions(R o s e n f e l d and B e a t h, 1964).Seleniumcontent inmagmaticrocksseldomexceeds0.05mgg1(K a -b a t a - P e n d i a s,1993).AnextremelylowSecontentwasfoundinmagma-ticrocksfromSerbia(meanvalue46ppbSe)(M a k s i m o v i etal.,1986).Intheserocks, Seis part of sulfides inwhichit substitutes sulphur. So, Secontent depends on the size of sulfide phase. In magmatic rocks, Se concentra-tiondecreasesfrombasicandultrabasictoacidandneutral rocks(D a n g i et al., 1989).In sedimentary rocks, Se is bound to the organic and clay fractions. Low-estSeconcentrationsarerecordedinsandstonesandlimestones(Table1).Se-lenium is most frequently found in phosphates, uranium ore, fossil coal and oilandinshalewithahighcontentoforganicmatter. Soilsformedonsuchsub-stratestypicallyhavehighortoxicSeconcentrations, unlikethesoilsformedonmagmaticrockswhichhavealowSecontent (F l e m i n g, 1980).ThemetamorphicrocksofSerbiahavealowerSecontentthanthemag-matic and sedimentary rocks. An analysis of 89 samples of metamorphic rocksfrom Serbia showed a low Se content of 28 ppb (J o v i et al., 1995), leadingtoaconclusionthat thehightemperatureandpressurepresent duringmeta-morphicprocessestendtoextrudeSefromtheserocks.Tab. 1SeleniuminmainrocktypesmgSeg1(K a b a t a - P e n d i a s, 1993)Igneousrocks mgSeg1Ultrabasic(dunit, peridotite, pyroxenite) 0.020.05Basic(basalt, gabbro) 0.010.05Intermediate(syenite) 0.020.05Intermediatetoacidic(rhyolite, trachyte, dacite) 0.020.05Acidic(granite, gneiss) 0.010.05SedimentaryrocksShale 0.400.60Sandstone 0.050.08Limestone, dolomite 0.030.1025SELENIUMINWATERANDAIRBesideslitosphere, atmosphericprecipitationisanother sourceof seleni-uminsoil. Seleniumisreleasedintotheatmospherefromnatural depositsorduetoanthropogenicinfluences(burningofcoal andotherfuels, releasesformines, oil refineriesandother industries). Soils, plants, microorganisms, ani-malsandvolcanoesreleaseupto0.04ngm3Se(EHC, 1987). Thetotal an-nual anthropogenicemissionofseleniumintheUSAwasestimatedat 4670t( H e r r i n g, 1991). The atmospheric precipitation in Norway and Swedenbringsannually0.51.0gSeha1. Under natural conditions, Secontentsinairandwaterarequitelowlessthan10ngm3inairandafewmgl1ofwater (EHC, 1987). Secontentsinrainandsnowsamplesgatheredindiffe-rent partsof theworldrangedfrom0.03to0.3mgl1(C u t t e r, 1989). Seconcentrationinatmospheric precipitationinSwedenwas below0.1 mgl1( J o h n s s o n, 1991).SELENIUMINSOILSeleniumcontentinsoilishighlyvariable. Itvariesfrom0.1to2mgSeg1in most soils, but it is most frequently between 0.2 and 0.4 mg g1( M c N e a l and B a l i s t r i e r i, 1989). Some soils are lowin selenium,from0.03to0.08mgg1(NAS,1976).Toxicconcentrationsoccurinaridandsemiaridparts of China, inHawaii, Mexico, Columbiaandwesternparts oftheUSAandCanada(M c N e a l and B a l i s t r i e r i, 1989). Soilscontain-inglessthan0.5mgg1oftotalSeareconsideredasdeficientinthiselement(M a y l a n d et al., 1989).Seleniumconcentrationinsoil isdeterminedbyseleniumcontent insoilnativesubstrate, climate, reliefandage(M a y l a n d etal., 1989). Thesefac-torsmaycontributeeithertoseleniumaccumulationduringsoilformingoritsremoval duringor after soil forming. Thesoilsformedonsedimentaryrocksthat containhighamountsoforganicmattertypicallyhavehightotoxicsele-niumconcentrations. Thesoilsformedonmagmaticrocks, whicharepoorinSe, usuallyhavealowSecontent (F l e m i n g, 1980).Besidesnativesubstrate,amountofrainfallplaysanimportantroleinde-terminingseleniumcontent insoil (F l e m i n g, 1980). Inregions withlessthan 500 mm of rain, the soil formed from rocks with a high Se content conta-ins potentially toxic Se concentrations. The same kind of soil formed in humidregions typicallycontains highamounts of Se, but it is boundtoironinapoorlysolublecomplex. Whenthesubstrateislowinselenium, thesoilform-ingonit will havealowSeconcentrationregardlessof climate.SincethetotalSecontentinsoilispredominantlydeterminedbyitscon-tent inthenativesubstrate, it isunderstandablewhythesoilsincertainregi-onsofourcountryhaveverylowSeconcentrations. Forexample, thesoilsinnorthernPomoravlje have the Se contents from0.12to0.44ppm, withthemeanvalue of 0.24ppm(J a k o v l j e v i et al., 1995), inwesternSerbia119.570.5ppbSe(M a k s i m o v i et al., 1992), inthevalleyof theZeta26River from0.2to0.41ppmSe, withthemeanvalueof 0.28ppmSe(J a -k o v l j e v i et al., 1995)LowSeconcentrationshavealsobeenregisteredintheVojvodinaProv-ince.In46soilsamplesfromtheregionsofSremandBanat,takenfromplotsusedfor vegetableproduction, thecontents of Serangedfrom0.11to0.45ppm, with the mean value of 0.25 ppm Se ( u v a r d i et al., 1997). In sam-plesof chernozem, districcambisol, humogley, humofluvisol, arenosol, solo-netzandsolonchaktakenintheVojvodinaProvince, Secontentsinthesurfa-cesoil layer rangedfrom0.024to0.194mgSeg1( u v a r d i , 2000).SELENIUMDISTRIBUTIONALONGSOILPROFILESeleniumcontent insoil typicallydecreaseswithdepthbecauseit bindswithproteins, fulvicacidsandotherorganiccompoundsthatcontentnitrogen.As organic matter decreases along soil profile, so does total selenium (A b r a m setal.,1990; A l e m i etal.,1991; G u s t a f s s o n and J o h n s s o n,1992).Selenium fixation may also be due to microbiological incorporation into aminoacids and other Se-containing organic compounds (M a o, 1999). In addition tohumusdistribution,SedistributionalongsoilprofileresemblesthoseofFe,Aland clay (L e v e s q u e, 1974; G o n d i et al., 1992; u v a r d i , 2000). Se-leniumbindswithclayandarrangesitselfalongtheprofile.TotalSeincreaseswiththeincreaseofsmallfractionsinthesoil( u v a r d i ,2000).Themostimportant characteristicsofthefinesoil fractionarethelargetotal areaofitsparticles andspecific mineralogical compositionwhichdistinguishes it fromthe coarse fractions. Secondary minerals predominate in the finest fraction,clay, whilethecoarsest fractioniscomposedmainlyof quartz(J a k o v l j e -v i and P a n t o v i ,1991).Forthatreason,thefractionsofcoarseandfinesandhavealowadsorptioncapacity. IonsofAloctahedrallayer, whosesidesarebare, maybeconsideredaspositivelychargedsitesonthesurfaceofclayminerals.IonsoftheAloctahedrallayerofcaolinite,which,incontrasttothemineralsfromthemontmorillonitegroup, arenot coveredwiththetetrahedralsheet, maybepositivelychargednot onlyat thesitesofcrystal fracturesbutalsotheir planesmaybecharged, attractingHSeO3asasubstitutefor OH( B a r - Y o s e f and M e e k, 1987).FACTORSAFFECTINGSELENIUMSOLUBILITYANDAVAILABILITYTOPLANTSOrganicandmineralformsofseleniumarepresentinthesoil(C a r y andA l l a w a y,1969).TheorganicformsofSeresultfrompartialdecompositionof selenium-loving vegetation. Mineral Se occurs as a selenide of metals(Se2), elementary Se (Se0), selenite (HSeO3) and selenate (SeO42). Se parti-tioningis affectedbysoil pHandredoxpotential, content of sesquioxides,clay, organicmatter andmicrobiological activity(E l r a s h i d i et al., 1987;J a y a w e e r a and B i g g a r, 1996).27SesolubilityandavailabilitytoplantsispredominantlyaffectedbypH--valueandredoxpotential(G e e r i n g etal.,1968).Accordingtope+pHdia-gram(Figure1) (E l r a s h i d i et al., 1987), selenideandelementarySearefavored in a reducing environment (pe+pH < 7.5), selenite in a slightly oxidiz-ingenvironment(pe+pH7.515.0), andselenateinanoxidizingenvironment(pe+pH>15.0).Inhumidregionsandacidsoils,theprevailingformisseleni-te, whichisfirmlyadsorbedonsesquioxidesandclaymineralsandthusnotreadilyavailabletoplants.HighannualprecipitationandlowtemperaturetendtoreduceSecontent inplants. Thisisduetoreducingconditionsinthesoiland reduction of selenate (SeO42) into less available forms: selenite (SeO32);elementaryseleniumor selenids (Se2) (G e e r i n g et al., 1968). IncreasedleachingofavailableSeformsalsoleadstoreductioninuptake(J o h n s s o n,1991). Underwell-aeratedconditionsinthealkalinesoilsofsemiaridregions,seleniumis present intheformof selenatewhichis not adsorbed, does notforminsolublesaltsandisreadilyavailabletoplants(C a r y et al., 1967).Although soil reaction plays a major role in determining Se solubility andavailability, itsinfluencelessensasthecontentsofclayandorganicmatterinthesoil increase(J o h n s s o n, 1991). BecauseofSeaffinityforclayminer-als, thesoilshavingincreasedclaycontent aretypicallybetter providedwithSethansandysoils(G i s s e l - N i e l s e n, 1975). Asdescribedintheprevio-uschapter, SebindswiththepositivelychargedionsofAL-octahedralsheets,which occur on the edges of clay minerals, primarily caolinite (B a r - Y o s e f,1987). G i s s e l - N i e l s e n (1971) studiedtheeffect of pHvalueandtex-tureonSeuptakefromloamyandsandysoils.InthefirsttwocuttingsofLo-28Fig. 1Theeffect of redoxonSespeciesinsolution(E l r a s h i d i et al., 1987)liummultiflorumgrownonaslightlyacidsoil,Seuptakedroppedwithincrea-seinclaycontent. Insubsequent cuttings, however, theeffect of soil acidityevidentlyweakenedbecauseSebecamemoreandmoreavailable. Whenthesoil pHexceeded7, theeffect of claydisappearedaltogether. Seadsorptionoccursalsooniron(Fe), aluminium(Al)andmanganese(Mn)oxidesandhy-droxides in acid environments, when these particles become positively charged(B a l i s t r i e r i and C h a o,1990).Namely,aspecificcharacteristicoftheseoxidesisthattheychangetheirelectricchargewithachangeofambientreac-tion. Thechargeisnegativeunderalkalineconditionsandpositiveunderacidconditions.Seleniumalsobindswellwithorganicmatterinacidsoils(C h r i s t e n -s e n et al., 1989; G u s t a f s s o n and J o h n s s o n, 1992). Because of ahighcontent oforganicmatterintopsoil, higherseleniumcontent maybeex-pectedtherethanindeepersoil layers(L e v e s q u e, 1974). Whenintheor-ganicfraction,seleniumeitherformscomplexeswithorganiccompoundsorisbuiltinaminoacidsandproteinsbymicroorganismsandplants(C a r y etal.,1967; H a m d y and G i s s e l - N i e l s e n, 1976). Sefractionationfromthreeprofiles of Swedish podzols showed that considerable amounts of Se were pre-sent inthesoil organicmatter, especiallyintheBshorizonwhichhasahighcapacityfor adsorptionof anions(G u s t a f f s o n and J o h n s s o n, 1992).Microorganismsplayanimportant roleinSetransformationsinthesoil.Theyarecapableof transformingtheabsorbedseleniteintoorganiccompo-undsorinot selenate(D o r a n, 1982). It wasalsofoundthat microorganismstakepartinthetransformationofselenateintolessmobileforms,especiallyinsoilsrichincarbon(A l e m i etal., 1991). Productsofmicrobiologicalactiv-ityarealsovolatileSeorganiccompounds, primarilydimethyl selenide. Thisis a way for seleniumdepletion fromthe soil (F r a n k e n b e r g e r andK a r l s o n, 1989). H a m d y and G i s s e l - N i e l s e n (1976) measured thevolatilizationofaddedseleniteunderlaboratoryconditions. Thevolatilizationwashigherfromasandysoil (about 8%oftheaddedSe)thanfromahumicsoil (about 5%of addedSe).Seavailabilitytoplantsdependsalsooncompetingions,especiallyphos-phates andsulfates. Interactionbetweenseleniumandphosphorus (P) inthesoil has beenobservedbyseveral researchers, but its mechanisms have notbeenfullyrevealed.Inagreenhousetest, S i n g h (1979)examinedtheeffectofaddedSeandPondrymattermassandchemical compositionofBrassicajunceaCos. Inthevariant without Pandwith10ppmSe, theseleniumcon-tentintheplantwas100timeshigherthaninthecontrol. Theincreaseswere258- and336-foldwith50and100ppmP. Similar resultswereobtainedbyS i n g h and M a l h o t r a (1976) whofoundthat theapplicationof 50and100ppmPpositivelyaffectedSeuptakebyTrifoliumalexandrinuminallva-riants of Se level, as well as in the experiment with residual Se. Effect of P onSe availabilitydepends onthe auxiliaryioninthe phosphorus fertilizer, Seformandthepresenceof other ions (K h a t t a k et al., 1991). F l e m i n g(1962)studiedtheeffectofPfromsuperphosphate, Ca(H2PO4)2, onSeuptakein an experiment in pots. All three doses of superphosphate reduced Se uptake,probablyduetotheinfluenceofsulfatethat wasacomponent ofthesuperp-29hosphate. Unlike superphosphate, dicalcium phosphate and monocalcium phos-phateincreasedSecontentingrasses(F l e m i n g,1965).Apossibleexplana-tionisthat P, ifincorporatedintothesoil togetherwithSe, substitutesSeinsomesorptionpoints,thusincreasingSemobilityanduptake(C a r t e r etal.,1972). Another possibleexplanationof thisinteractionisthat PincreasesSeuptakebystimulationcell divisioninplant root. Highcell divisionincreasesthecontact betweentheroot andsoil, whichincreasestheactiveroot surfaceandSeuptake(C a r t e r et al., 1972).Becauseof alargechemical similaritybetweensulfur (S) andseleniumandbecauseof thefact that most ScompoundshaveSeanalogues, it seemsreasonabletoexpect antagonisticinteractionduringuptakeof thesetwoele-ments.SeveralauthorsfoundthatSeconcentrationintheplantdecreasesafteraddingsulfatetothenutritivemedium(W a n etal.,1988; M i k k e l s e n andW a n,1990).Inanexperimentinpotsfilledwithpeatysoil, W i l l i a m s andT h o r n t o n (1972) examined the effects of different S compounds on Se up-take.AllScompoundstested(elementaryS,sulfateS,sulfiteS,sulfideSandmethionine) tended to reduce Se uptake. The situation was opposite in the caseofalkalinesoils,wheretheapplicationofsulfateincreasedSeuptake(C a r t e ret al., 1972).WATER-SOLUBLESELENIUMINSOILTotal Se content in the soil is not always in correlation with its content inplants because Se solubilityis affectedbyseveral factors: soil reaction, thecontentsofsesquioxides, clayandorganicmatter(E l r a s h i d i et al., 1987;J a y a w e e r a and B i g g a r,1996; P e z z a r o s s a,1999).Becauseofthat,when assessing soil provision with selenium, concentration of available Se andfactorsthataffectthedynamicsofSeinthesoilhavetobetakenintoaccountinadditiontothetotalSecontent.Thewater-solubleSefractionisconsidered30Fig. 2Contentsof total andwater-solubleSeintheprofilesof theexaminedsoilsintheVojvodinaProvince( u v a r d i , 2000)tobemostavailabletoplants(J u m p and S a b e y, 1989). Non-adsorbedSeandwater-solubleorganicSearereleasedfromthesoilbyextractionwithboi-lingwater(W a n g and S i p o l a, 1990; S e b y et al., 1997; K a n g et al.,1993).Innormal tilledsoils, theconcentrationof thewater-solubleSefractiontypicallydoesnotexceed0.050mgg1Se(W o r k m a n and S o l t a n p o u r,1980).Exceptionallylowconcentrationsofwater-solubleSe,rangingfromtra-cesto0.013mgg1, wereregisteredinthesoilsofSremandBanat usedforvegetableproduction( u v a r d i et al., 1997). Lowconcentrationsof wa-ter-soluble Se were found for seven different soil types in the Vojvodina Prov-ince( u v a r d i , 2000). Theseconcentrations rangedfromtraces to0.014mg Se g1of soil, or from 0.59% to 16.35% of the total Se (Figure 2). In Hun-gary, G o n d i et al. (1992)foundthat themobileSefractiondidnot exceed10%ofthetotal Seinmost ofthetestedsoils, withtheexceptionofseveralprofilesofalkalinesoilsinwhichthisfractionrangedbetween20%and35%of thetotal Se.SELENIUMUPTAKEPlants takeupSeintheformof selenateor selenite, or as organicSe( H a m i l t o n and B e a t h,1963,1964).Probablytheymayalsotakeupat-mospheric Se (A s h e r et al., 1967). Capacityfor Se uptake varies amongplantspecies(H u r d - K a r r e n, 1935). Still, differencesamongplantspeciesweresmallerregardingSeuptakefromlowSesoilsthanregardingSeuptakefromhighSesoils(E h l i g et al., 1968). Furthermore, therateofuptakede-pendsontheformofSeprevailinginthesoiloranutritivemedium(Z h a n get al., 1988). Generally, plants exhibit preference for selenate over selenite( B a n u e l o s and M e e k, 1990). This seems to be due to high adsorption ofselenitebyhydratedoxides, orselenitereductiontoelementarySeorselenide(C a r y et al., 1967; G i s s e l - N i e l s e n et al., 1984). Inanexperiment invegetation pots, G i s s e l - N i e l s e n (1973) found that the Se uptake bybarleywas40timeshigher fromselenatethanfromselenite.CONCLUSIONSeleniumisanessential microelement, necessaryfor normal functioningofhumanandanimal organisms, whosedeficiencyinfoodandfeedcausesanumberofdiseases. Inhighconcentrations, seleniumistoxicforhumans, ani-mals and plants. Soil provision with selenium affects its level in food and feedvianutritionchain. Seleniumbioavailabilitydependsnotonlyonitstotalcon-tent insoil but alsoonitschemical forms.Organic and mineral forms of Se are present in the soil. The organicformsofSeresultfrompartialdecompositionofseleniferousvegetation.Min-eral Se occurs as a selenide of metals (Se2), elementarySe (Se0), selenite(HSeO3)andselenate(SeO42).SepartitioningisaffectedbysoilpHandre-31doxpotential, content ofsesquioxides, clay, organicmatterandmicrobiologi-cal activity.Inhumidregionsandinacidsoils,seleniteisthepredominantform.Itisfirmlyadsorbedonsesquioxidesandclaymineralsandthusnotreadilyavaila-bletoplants. Inwell-aeratedalkalinesoil insemiaridregions, Seisfoundintheformofselenate, whichisnotadsorbed, doesnotforminsolublesaltsandisreadilyavailabletoplants.SinceSesolubilityandavailabilitytoplantsaregovernedbyseveralfac-tors, concentrationof availableSeandfactorsthat affect Sedynamicsinthesoil shouldbeconsideredinadditiontothetotal Secontent inthesoil whenestimatingsoil provisionwithselenium.REFERENCESA b r a m s,M.A., S h e n n a n,C., Z a s o s k i,R.J., B u r a u,R.G.(1990):Seleno-methionineuptakebywheat seedling, Agron. 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(1988):Growthandupta-keof seleniumbySwiss chardinacidandneutral soils, J. Environ. Qual., 17,314316.SELENUZEMQITUMajaS. uvardiPoqoprivrednifakultet, Trg dositejaObradovia8, 21000NoviSad,Institutzaratarstvoipovrtarstvo, MaksimaGorkog 30, 21000NoviSadRezimeSelenjeesencijalnimikroelemenat, neophodanzanormalnofunkcioni-saweorganizmaqudiiivotiwa, ijinedostatakuhranidovodidonizaobo-qewa. Uistovreme, uvisokimkoncentracijama, selen(Se)jetoksian, kakoza36qudeiivotiwe, takoizabiqke. Obezbeenostzemqitaseprekolancais-hrane odraava na nivoselena u hraniqudiiivotiwa, alireaktivnost ibiopristupanostselenanezavisisamoodwegovogukupnogsadraja,negoiodhemijskihformiukojimaseselennalaziuzemqitu. Nadistribucijuizmeupojedinihoblikaselenautiusvojstvazemqita, kaotosu: reakcijazemqi-ta, aeracija, sadraj glineiorganskematerijeimikrobiolokaaktivnost.37