Color profile: Disabled Composite 150 lpi at 45 degrees ActaBot.Croat.66(2),177–195,2007 CODEN:ABCRA25 ISSN0365–0588 Flora of heavy metal-rich soils in NW Iran and some potential hyper-accumulator and accumulator species ROGHIEHHAJIBOLAND*,MIRH.MANAFI PlantScienceDepartment,UniversityofTabriz,51666Tabriz,Iran InthenorthwesternpartofIran(Azerbaijanprovince),therearenumerous,activemining areaswithheavymetal-richsoils.Theplantvegetationgrowingonthesesoilscouldrepre- sentaspecificflorahavingpotentialhyperaccumulators,accumulatorsandexcluderspe- cies.Inthiswork,soilsrichinNi,Zn,CuandMnandplantswereidentifiedduringApril toSeptemberin2002–2003.Plantspeciesbelongingto39familieswerecollectedandthe heavymetalsintheabove-groundpartsofspecimenswereanalyzed.Forthemajorityof species,thoughmetalconcentrationswereordersofmagnitudehigherthanplantsgrow- ingonsoilswithoutmineralization,theconcentrationswerebelowthethresholddefining hyper-accumulation.TheNi,Zn,CuandMnexcluderspeciesthatgrowonmetalrich soilsbutrestrictmetalabsorptionand/ortransportintoshootswerealsoidentified.These speciesaresuitablefortherehabilitationandstabilizationofcontaminatedlandsaround miningareasaswellastheremediationofagriculturalsoilsaffectedbywastewatersof metalsmeltersinminingsitesofNWIran. Keywords:flora,accumulatorspecies,heavymetal,Iran Introduction Thepresenceofhighlevelsofmetalsinsoilsexertsapressureonplantspeciesleading totheselectionofaspecificflora.Plantsgrowingonmetal-loadedsoilsrespondbyexclu- sion,indicationoraccumulationofmetals(BAKER1981).Anumberofplantspeciesen- demic to metalliferous soils accumulate metals to extraordinarily high levels (> 1%) as comparedtothenormalconcentrationsinplants(SHALLARIetal.1998). Ahyperaccumulator is defined as a plant with a concentration of heavy metal in its abovegroundparts,10–500timeshigherthaninusualplants(SHENandLIU1998). Theexistenceofmetal-accumulatingplantshasattractedtheattentionofplantscien- tistsformanyyears.Theseplantsarestrictlyconfinedintheirdistributiontosoilsenriched inheavymetals,eithernaturallythroughmineralizationorasaresultoftheextractionand smeltingofmatalliferousresources(VAZQUEZetal.1992).Approximately45familiescon- taining metal-accumulating species and more than 400 hyperaccumulator species have beenreported.Inadditiontotaxonomicapplications,somehyperaccumulatorspeciesare usedasgeobotanicindicatorsinmineralexploration(BROOKS1998a). * Correspondingauthor,e-mail:[email protected] ACTABOT.CROAT.66(2),2007 177 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:31 Color profile: Disabled Composite 150 lpi at 45 degrees HAJIBOLANDR.,MANAFIM.H. Ni-richsoilsmainlybelongtotheserpentinetype.Serpentinesoilsareconsiderablydif- ferentfromnormalsoils,beingveryrichinNiandcontaininghighamountsofchromium, cobalt,ironandmagnesium(BROOKS1987).Serpentineflorasarethemostextremeexam- plesofchangesoccurringinplantvegetationbecauseofthesubstrate,sothatgeological boundariesarereadilyobservableduetodifferentiationintheflora(BROOKS1998a).Itwas suggestedthatnickelistheelementresponsibleforserpentinevegetation.Thetotalnumber of Ni hyper accumulator plants exceeded 400 (ROBINSON et al. 1997). The Ni hyper- accumulation threshold level has been set at 5000 (BROOKS 1983) or 1000 mg g–1 dry weight(BAKERetal.2000;POLLARDetal.2002). PlantcommunitiesgrowingoverZndepositshaveacertainsimilaritywithserpentine flora.InarecentreportontheZnhyperaccumulators,16hyperaccumulatorswereintro- duced which accumulated up to 1% Zn in dry weight (BROOKSet al. 1995). The hyper- accumulation threshold level for Zn has been set at 10,000 mg g–1 dry weight (BROOKS 1983). There are only few regions in the world where a true copper flora exists (BROOKS 1998a). The presence of 50 species endemic to copper/cobalt deposits was reported (BROOKSetal.1995)and24copperhyperaccumulatorswereidentified(BROOKS1998a). ThehyperaccumulationthresholdlevelforCuhasbeensetat5000(BROOKS1983)or1000 mgg–1dryweight(BAKERetal.2000;POLLARDetal.2002). IncontrasttoNi,ZnandCu,theoccurrenceandgeobotanyofMnhyperaccumulators hasnotbeenfullystudied.ThisisbecauseverylittleisknownabouttheuptakeofMnby plantsanditisnotacommonpollutant.However,11Mnhyperaccumulators fromthree familieswerereported(BROOKS1998a)andtheMnhyperaccumulationthresholdlevelhas beensetat10,000mgg–1dryweight(BROOKS1983). Hyperaccumulatorplantsrepresentapotentialfortheremediationofsoilspollutedby heavymetals(BAKERetal.2000).Hence,itisnecessarytoobtainmoreinformationabout thefloraexistingonmetal-enrichedsoilsinordertodeterminetheirpotentialfortheman- agementofpollutedsoilsandparticularlyformetalextraction(SHALLARIetal.1998). Newhyperaccumulatorswillbeidentifiedbymorestudiesonmetal-enrichedenviron- ments.ThereareabundantmetalresourcesinAzerbaijanprovince,NWIran,andtheprov- inceischaracterizedbyahighdensityofminesandmetalsmelters.Thesemetalresources include Cr-Ni, Pb-Zn, Cu and Mn. From the geological point of view, Azerbaijan is the mostcomplexpartoftheIranPlateauandischaracterizedbynumeroussitesofmetaland non-metalelement-richdeposits(CALAGARI,2003).Depositionofmetalstookplaceduring variousmetallogenicperiodsandheavymetalrichsoilswereformedbythedestruction, movementandsedimentationofthesedeposits. Thisworkwasundertakentoacquireinformationaboutthefloraofheavymetal-rich sitesinAzerbaijanprovincewithaspecialemphasisonmetalaccumulationbyplants. Materialsandmethods StudieswereundertakenduringtwosuccessivegrowingseasonsincludingApril–Sep- tember2002and2003.AzerbaijanislocatedintheNWIran(Fig.1),withanaveragealti- tudeof1500m,anannualprecipitationof257.5mmandannualaveragetemperatureof 178 ACTABOT.CROAT.66(2),2007 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:31 Color profile: Disabled Composite 150 lpi at 45 degrees FLORAINHEAVYMETAL-RICHSOILSINIRAN 12.3°C.Themeantemperatureinsummeris26.4°Candinwinteris-1.3°C.Thisprovince canbeclassifiedbioclimaticallyasMediterranean. Metalrichsitesweredescribedinthisworkaccordingtorecentresearchonthegeology ofNWIran(CALAGARI2003,KHALATBARI-JAFARIetal.2005,MOAZZENandMODJARRAD 2005). Fig.1. MapofNWIranindicatingthestudiedsites. Soil samples were taken from the plant sampling location of the upper horizon at a depthofapproximately15cm.Sampleswereairdriedandsievedthrougha2-mmscreen. All plant species grown at each site were collected during two time intervals including April–MayandAugust–Septemberintwoyears(2002–2003).Foreachspecies5–6sam- plesweretakenateachsiteandtime;oneofthemwaspreparedfortaxonomicidentifica- tionandtheotherswereusedforelementalanalysis.Theidentificationofspecieswasreal- izedwiththeFloraIranica(RECHINGER2002)andFloraofTurkey(DAVIS1988). ACTABOT.CROAT.66(2),2007 179 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:34 Color profile: Disabled Composite 150 lpi at 45 degrees HAJIBOLANDR.,MANAFIM.H. SoilpHandECweredeterminedinthesaturatedsoilpastewithapHandEC-meter. Soiltexturewasdeterminedusingthehydrometermethod(GEEandBAUDER1986)andor- ganiccarbonwasanalyzedusingthemethodofWALKELYandBLACK(1934).Theconcen- trationofheavymetalsinawater-solubleandNH -acetate(AAc)extractablefractionin 4 soil(2h,5mLg–1soil)wasdeterminedaccordingtothemethoddescribedbyJIANGetal. (2004). Foranalysis ofplant specimens, theleaves ofeachplant were separated andwashed withdouble-distilledwater,blottedonfilterpaperanddriedat70°Cfor2daysfordetermi- nationofdryweight.Thedryweight(DW)ofsamplesvariedbetween0.5and2.0g.Four replicates consisting of leaves of four plants were analyzed for each plant species and heavymetal.FordeterminationofZn,CuandMn,sampleswereashedinamufflefurnace at550°Cfor8handforNi,samplesweredigestedwith1:1perchloricacid/nitricacidmix- ture(1:8W/W)onaheatingplate(200°C)for5h.Thereafter,samplesweresuspendedin2 ml10%HClandmadeuptovolume(25mL)withdouble-distilledwater.Metalconcentra- tionsweredeterminedbyatomicabsorptionspectroscopy(Shimadzu,AA6500)using232, 213.9,324.8and279.5nmforNi,Zn,CuandMndeterminationrespectivelyprovidedby metal-specificlamps.Referencestandardsolutions(Merck)wereusedafterproperdilution for calibration of the instrument. All collected plant specimens were analyzed, but only thosebelongingtospecieswiththehighestandlowestaccumulationarereported. Investigatedarea Ni-richsites Geshlagh: This site is located near the city of Khoy, 190 km from Tabriz (45°38’E, 38°22’N)atanelevationof1750m.Thesitecoversanareaof500m2.Annualaverage temperatureis13°Cwithaprecipitationof294mmandrealtranspirationof283mm.This site can be classified bioclimatologically as temperate semi-humid with dry and warm summers. The main geological units in this site include metamorphic (amphibolite and greenschist),mafic,ultramaficandserpentinerocks.Themajorityofultramaficrocksare lherzolite.Theserocksaresuitablesubstratesfortheaccumulationofheavymetalssuchas CrandNi.ThetotalreservoirofNiis10,000tons. AnamaghandMahboob-Abad:ThissiteislocatedinnorthofMishoudagh,nearthe cityofMarand,65kmsouthofTabriz(45°38’E,38°22’N)atanelevationof1850m.The sitecoversanareaof2km2.Annualaveragetemperatureis11°C,annualprecipitationis 426mm,andrealtranspirationis370mm.Thissitecanbeclassifiedastemperatehumid withdryandwarmsummers.Maficrockssuchasdiabasicandgabbroicrocksarepresent inthisarea. Zn-richsites Gebchagh:Thissiteislocated75kmfromTabriz(46°58’E,37°43’N),atanelevation of1960m.Theareacoveredbythesiteis1000m2.Annualaveragetemperatureis8°C,an- nualprecipitationis268mmandrealtranspirationis250mm.Thissitecanbeclassifiedas coldandhumidwithdryandcoldsummers.Sulphur-siliconmineralizationtookplacein thisareaandsilicabandslowinFeandrichinZn,Cd,PbandMncouldbefound.Thetotal reservoirofZnis50,000tons. 180 ACTABOT.CROAT.66(2),2007 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:34 Color profile: Disabled Composite 150 lpi at 45 degrees FLORAINHEAVYMETAL-RICHSOILSINIRAN Cu-richsites CopperminesaredominantinthemininginAzerbaijan,forthetotalreservoirsofCu minesinthisprovincecometo160milliontons. Hiagh:LocatedeastofthecityofHiagh,120kmfromTabriz(45°15’E,37°12’N)atan elevationof2450m.Theareacoveredbythesiteis3km2.Thissitelocalizedneartheintru- sive mass of quartz monzonite. Aporphyry type of Cu mineralization took place and at marginalareastherearenumerousbandsofCu,PbandZn. ZandAbadandMazra-eh:Bothoftheseareasarelocatednorthwestofthecityof Ahar,120kmfromTabriz(47°5’E,38°37’N)atanelevationof2010m.Theareacovered is500km2.ThissiteissituatedatthemarginalareaofagranitoidmassinShivar-Dagh.A skarntypeofmineralization(Fe-Cuskarn)tookplaceandthemajorityofCudepositsare localizedinexo-skarn. Annualaveragetemperatureforthesetwositesis10°C,annualprecipitationis314mm andrealtranspirationis283mm.Bothofthesesitescanbeclassifiedastemperatesemi-hu- midwithdryandcoldsummers. AliAlamdar:ThissiteislocatednortheastofTassoudj,75kmfromTabriz(45°30’E, 38°37’N),atanelevationof2300m.withanannualaveragetemperatureof9°C,annual precipitationof323mmandrealtranspirationof294mmandtheareacoveredis200km2. Thissitecanbeclassifiedastemperatehumidwithdryandcoldsummers.Themineralde- positsarelens-shapedtobandform.BaritecommonlyoccursinCuandPbveinsinlime- stones. Mn-richsites ManganeseminesaretheseconddominantminesinAzerbaijan,andthetotalreservoirs ofMnare400,000tonsinthisprovince.Theannualaveragetemperatureofthesesitesis 11.8°C,annualprecipitationis323mm,andrealtranspirationis294mm. Tikmeh-DashandBostanAbad:BothofthesesitesaresituatednearTabriz(50km) atanelevationof1895m(47°56’N,37°44’N).Theareacoveredis20,000m2.Thissitecan beclassifiedastemperatehumidwithdryandcoldsummers.TheMnskarnhaveathick- nessof2km,traceamountsofCumineralizationcouldbefound.InBostanAbad,Mn,Zn andPbmineralizationalsotookplace. Khorasanak: This site is located near the city of Hashtroud, 115 km from Tabriz (47°10’E, 37°20’N) at an elevation of 1850 m. The area covered is 500 km2. Manga- nese-richbandsarelocalizedwithinthegypsumdeposits. Choghanlou: This site is located near the city of Hashtroud, 150 km from Tabriz (46°50’E,37°43’N)atanelevationof2200m.Theareacoveredis10,000m2.Mnisasso- ciatedwithFe(Hematite)andsedimentaryrocks(Travertine). Results During two growing seasons, 254 specimens were collected from 11 sites and deter- mined.Thesespeciesbelongto39families.ThefamilyAsteraceaewasthemostabundant plantfamilygrowingonheavymetal-richsoils,Cupressaceae,Fumariaceae,Onagraceae, ACTABOT.CROAT.66(2),2007 181 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:35 Color profile: Disabled Composite 150 lpi at 45 degrees HAJIBOLANDR.,MANAFIM.H. Paronochiaceae,Polygalaceae,Ranunculaceae,ThymelaceaeandUrticaceae,eachhaving only one species among collected specimens, were the least frequent plant families occurringinthesesites(Tab.1). Tab. 1. Flora of Ni, Zn, Cu and Mn-rich soils in Northwest of Iran. 1 – Geshlagh (Khoy), 2 – AnamaghandMahboobAbad,3–Gepchagh,4–Hiagh,5–Zand-Abad,6–Mazra-eh,7– Ali-Alamdar,8–Tikmedash,9–Bostan-Abad,10–Khorasanak,11–Choghanlou. Heavymetal-enrichedsoils Ni Zn Cu Mn Sitecode 1 2 3 4 5 6 7 8 9 10 11 Apiaceae DaucusorientalisL. + EryngiumcaeruleumBieb. + + + + + Ferulasp. + Peucedanumsp. + + ScandixibericaBieb. + ZozimaabsinthifoliaVent. + Asteraceae Achilleasp. + + + AchilleamillefolliumL. + + AchilleasantolionaL. + + AchilleavermicularisTrin. + + AnthemistinctoriaL. + CartamusoxycanthaM.B. + CentaureavirgataLam. + + + + + + + + + Chrysanthemumsp. + + CichoriumintybusL. + + + + + Circiumsp. + + + + + + + CirsiumlanceotatumL. + Cousiniasp. + + CousiniacalocephalaJaub. + Crepissp. + CrepisrigidaWaldst.Kit. + Echinopssp. + EchinopspersicumStev. + EchinopspungensTrautv. + + HelychrisumargenteumL. + HelychrisumarmeniumD.C. + HelychrisumpallasiiSprengel. + + + + Lactucasp. + Onopordonsp. + + Scabiosasp. + + ScabiosaargenteaL. + 182 ACTABOT.CROAT.66(2),2007 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:35 Color profile: Disabled Composite 150 lpi at 45 degrees FLORAINHEAVYMETAL-RICHSOILSINIRAN Tab.1.–continued Heavymetal-enrichedsoils Ni Zn Cu Mn Sitecode 1 2 3 4 5 6 7 8 9 10 11 Scariolasp. + + + ScariolaorientalisBoiss. + ScariolaleucocladaRech.Tulsl. + + Seneciosp. + + SeneciovulgarisL. + Tanacetumsp. + + + + TanacetumkotschyiBois. + TanacetummyriophyllumWilld. + Asteraceae TaraxacummicrocephaloidesV.S. + Thevenotiasp. + TussilagofarfaraL. + + XeranthemumsquarrosaBoiss. + Xeranthemumsp. + Brassicaceae Alyssumsp. + + AlyssumdasycarpusSteph. + AlyssumalpestreL. + AlyssumcampestreL. + AlyssumdesertorumStapf. + + + AlyssumlanigerumDC. + AlyssumMuraleWalast. + + AlyssumstrigosumSchrad. + AlyssumszowitsianumFish. + Erysimumsp. + + + + GoldbachialaevigataL. + Lepidiumsp. + MalcolmiaAfricanaL. + NoneapersicaBoiss. + lEuclidiumsyriacumL. + Borraginaceae Alkannasp. + AlkannaorientalisL. + + MoltkiacaerulaWilld. + Myosotissp. + MyosotissparsifloraMikan. + NoneapersicaBoiss. + OnosmamicrocarpusDC. + OnosmapachypodumBoiss. + ACTABOT.CROAT.66(2),2007 183 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:35 Color profile: Disabled Composite 150 lpi at 45 degrees HAJIBOLANDR.,MANAFIM.H. Tab.1.–continued Heavymetal-enrichedsoils Ni Zn Cu Mn Sitecode 1 2 3 4 5 6 7 8 9 10 11 OnosmabulbotrichumDC. + Caryophyllaceae AcanthophyllumgracileBge. + Cevastiumsp. + Dianthussp. + + + Dianthusta + Herniariasp. + Holosteumsp. + Silenesp. + + + SileneaucherianaBoiss. + Chenopodiaceae Chenopodiumsp. + + + Convulvulaceae + Convulvulussp. + Cupressaceae JuniperuscommunisRech. + Cyperaceae Carexsp. + Crassulaceae Sedumsp. + Dipsaceae Cephalariasp. + ScabiosaargenteaL. + Equisetaceae EquisetumravensL. + + Euphorbiaceae Euphorbiasp. + EuphorbiagerardianaJacq. + + + + + + + + Fabaceae Astragalussp. + + + + + + + + + + AstragalushohenackeriBoiss. + HedysarumibericumM.Bieb. + LotuscorniculatusL. + + MedicagosativaL. + + + MelilotusofficinalisL. + + Fumariaceae FumariavaillantiiLoise. + + Geraniaceae GeraniumtuberosumL. + 184 ACTABOT.CROAT.66(2),2007 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:35 Color profile: Disabled Composite 150 lpi at 45 degrees FLORAINHEAVYMETAL-RICHSOILSINIRAN Tab.1.–continued Heavymetal-enrichedsoils Ni Zn Cu Mn Sitecode 1 2 3 4 5 6 7 8 9 10 11 Hypericaceae Hypericumsp. + HypericumperforatumL. + + + Iridaceae GladiolusatroviolaceusBoiss. + IrisacutilobaC.A.Mey. + Lamiaceae Ajugasp. + Calaminthasp. + + MarrubiumpariviflorumFishMey + + + Menthealongifolia(L.)Hudson + + + Nepetasp. + + + PhlomiscaucasicaRech.Fil + + + + PhlomispungensWilld + Salviasp. + + + + Stachyssp. + StachysinflataBentham. + StachyslavandulifoliaBoiss. + + + + Teucriumsp. + + Lamiaceae Thymussp. + ThymuskotschyanusBoiss. + + + + + ZiziphoraclinopodioidesLam. + Liliaceae Alliumsp. + Muscarisp. + Ornithogalumsp. + Linaceae LinumperenneL. + Onagraceae EpilobiumminutiflorumHe. + + Papaveraceae GlauciumcorniculatumL. + + HypecoumpendulumL. + Papaversp. + + + + PapaverdubiumL. + Paronochiaceae Herniariasp. + ACTABOT.CROAT.66(2),2007 185 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:35 Color profile: Disabled Composite 150 lpi at 45 degrees HAJIBOLANDR.,MANAFIM.H. Tab.1.–continued Heavymetal-enrichedsoils Ni Zn Cu Mn Sitecode 1 2 3 4 5 6 7 8 9 10 11 Plantaginaceae PlantagolanceolataL. + Plumbaginaceae Acantholimonsp. + Acantholimonhohenackeri + + + (JaubSpach)Boiss Poaceae Airasp. + Agropyromsp. + + + + + AgropyrumrepensL + AgropyrumorientaleL. + Agropyrumcristatum + (Schreb)Gaertn. Agrostisasp. + AvenafatuaL. + Boissierapumilio(Trin.)E.Hack + Bromussp. + + BromusmacrostachysDesf. + BromustectorumL. + + + BromustomentellusBoiss. + Cynodondactylon(L)Pers. + CynosorusechinatusL. + DactylisglomerataL. + + + + + + Eragrostissp. + EremopoaarundinaceaeL.Rosh. + Poaceae Eremopyrumsp. + Festucasp. + + + MelicacupaniGuss. + + PoabulbosaL. + + + + PoapratensisL. + PoatrivialisL. + SecalemontanumGuss. + StipabarbataDesf. + + + + + + Polygalaceae Polygalasp. + Polygonaceae AtraphaxisspinosaL. + 186 ACTABOT.CROAT.66(2),2007 U:\ACTA BOTANICA\Acta-Botan 2-07\Hajiboland.vp 3. listopad 2007 16:36:35