《全球变化科学》课程教学资源（讲义）05 Tracking fluvial sediment sources through the lanthanide traces. Experimental method applied on the Jiu river basin（Romania）

WuhanUniversityofTechnologyDepartmentofSpatial InformationandPlanningSchoolofResourcesandEnvironmentEngineeringTrackingfluvialsediment sourcesthroughthe lanthanide tracesExperimental methodappliedontheJiuriverbasin(Romania)GabrielaAdinaMOROSANU-MITOSERIUInstituteofGeographyoftheRomanianAcademy,Romaniagabriela.adina.m@gmail.com

Tracking fluvial sediment sources through the lanthanide traces. Experimental method applied on the Jiu river basin (Romania) Wuhan University of Technology Department of Spatial Information and Planning School of Resources and Environment Engineering Gabriela Adina MOROȘANU-MITOȘERIU Institute of Geography of the Romanian Academy, Romania gabriela.adina.m@gmail.com

→ContextVSediment sources analysis is a current scientific and practical concern, specificallyby river basin managers.This situationparticularly concerns thelatest implications in themanagement of European river basins,followingtheadoptionoftheWaterFrameworkDirective(WFD200o/6o/EC),whichpromotessourceareasassessmenttoexplainsedimentdynamicscontamination. Fine sediment sources analysis by means of geochemical tracing may ensure compliance with the Eu WaterDirective,particularly with its provisions concerning the prioritization and inclusion of measures for controlling themobilizationanddeliveryof riverinesedimentstotheDanubeRiver,akeyfluvialsystem in Europe.>ObjectivesofthestudyOverallaim:To identifythemostcontributing sub-catchmentsinterms of sediment sourceareas,byanalyzingcoalymatterfromthetwomaincoal basins(seeFigure1)andthe heavyminerals/rare earthscontent inthefinesediments ofthe JiuRiver.Specific objective relativeto thetoday'spresentation:Usethelanthanidesproportion inthefinesedimentsastracers

 Objectives of the study 2 Overall aim: To identify the most contributing sub-catchments in terms of sediment source areas, by analyzing coaly matter from the two main coal basins (see Figure 1) and the heavy minerals / rare earths content in the fine sediments of the Jiu River. Specific objective relative to the today’s presentation: Use the lanthanides proportion in the fine sediments as tracers.  Context  Sediment sources analysis is a current scientific and practical concern, specifically by river basin managers.  This situation particularly concerns the latest implications in the management of European river basins, following the adoption of the Water Framework Directive (WFD 2000/60/EC), which promotes source areas assessment to explain sediment dynamics contamination.  Fine sediment sources analysis by means of geochemical tracing may ensure compliance with the EU Water Directive, particularly with its provisions concerning the prioritization and inclusion of measures for controlling the mobilization and delivery of riverine sediments to the Danube River, a key fluvial system in Europe

StudyareaN.0.0.092519mcm23m2132071910'0010°00°E20°0/0°E30*010°E177UkraineLegend168tazn159HungaryRep.oflJiuRiverBasinMoldovavRiversAlluvialdepositsona116Sampling:fromsourcetoalluvialdepositspointbarofthemain99Podari hydrometric station (h.s.)river(Jiu).Riverbank92Sampling locationsvertical profileat70Coal extractionareasPodarireachSerbiaElevations (m)DanubeMax:2544Bulgaria0102040Km200Km050100Morosanu,2019,2020Min:0

Alluvial deposits on a point bar of the main river (Jiu). Riverbank vertical profile at Podari reach 213 207 191 177 168 159 116 99 92 70 0 cm Morosanu, 2019, 2020 3

METHODOLOGY1.Sampling protocol:.Finesedimentsfromtheriverbeds(sourceintermediateareas)Alluvial layers'samplingfromthedownstreamriverbank (accumulationarea)JiuRiversamples(Jiuriverbedfromupstreamtodownstream&→2typeof locationsforL.B.R.B.alluvialdepositsonJiuRiverbank)theenvironmental(sediments) samplesyTributarysamples(fromtheriverbedsof Jiurivermaintributariesofnaturalandhumancontrolsofthegeochemicalbackground)V24samplesfromtheriverbeds (Jiuriverand itstributaries)11 samplescollected fromthealluvial layers of Jiu riverbankatPodarih.s.,downstream all thepossiblegeochemical sources +1referencesamplefromthebaseof thealluvialprofile2.Laboratoryanalysis:.Performed in the Geochemistry Laboratory of the Faculty of Mining,Petrosani University.The fraction with a densitygreater than2.8g/l was considered to be of interest and was isolated byadjusting(increasing)thedensityof the samplesolutionwithbromoformThesampleswerefirstdried intheoven(forabout24hin105°C).Theresultingmaterialwasthencrushedand sievedtotakeoutparticleslargerthan1mm.Elemental analyses(forboththescopeof studyingthetracesofheavymineralsandrareearths)wereperformedbyX-rayfluorescence (XRF)spectrometry(SREN15309:2007)onthe subsequent>2.8g/lfraction4

METHODOLOGY 4 1. Sampling protocol: • Fine sediments from the riverbeds (source intermediate areas) • Alluvial layers’ sampling from the downstream riverbank (accumulation area) → L.B. R.B. 2 type of locations for the environmental (sediments) samples  24 samples from the riverbeds (Jiu river and its tributaries)  11 samples collected from the alluvial layers of Jiu riverbank at Podari h.s., downstream all the possible geochemical sources + 1 reference sample from the base of the alluvial profile Jiu River samples (Jiu riverbed from upstream to downstream & alluvial deposits on Jiu Riverbank) Tributary samples (from the riverbeds of Jiu river main tributaries of natural and human controls of the geochemical background) 2. Laboratory analysis: • Performed in the Geochemistry Laboratory of the Faculty of Mining, Petroșani University. The fraction with a density greater than 2.8 g/l was considered to be of interest and was isolated by adjusting (increasing) the density of the sample solution with bromoform. • The samples were first dried in the oven (for about 24 h in 105°C). The resulting material was then crushed and sieved to take out particles larger than 1 mm. • Elemental analyses (for both the scope of studying the traces of heavy minerals and rare earths) were performed by X-ray fluorescence (XRF) spectrometry (SR EN 15309: 2007) on the subsequent >2.8 g/l fraction

HowdoesXRFwork?METHODOLOGY1-IncidentX-ray3-CharacteristicX-ray2-EjectedelectronMZn,KA'SPb,LAs'Pb.LBCu.KAobscrrN,KA025101Fe,KAi,KBh,KA43U9TKBrVAastFeBa,LAnCa KB6.57.87.518.8 18.511.e11.512.8 12.513.8 13.5.85.56.89.88.59.5Energy (keV)

METHODOLOGY Energy (keV) Occurrence / second

Tableauperiodiquedeselements chimiquesMETHODOLOGY品0N15#心134AL三P00222324427303332628298vGr5#8小1一Mn0808GeAS京百#5214445如24346NbTCPa2cdeeMoRURh国一新S广中酒72ena上欢足75北谷#PE·旦皖A1-7100电104ACR1兰8三兰兴OETs.中品be58中国3#5山#70718摄YD三"LANTHANIDES二90品福102103ThNOUtActinidesEtat:NonmetauElements d'origineHGaseousAutresmetauxNaPrimordialNon dassesBrPoDisintegration d'autres elementsLiquideHalogensMtsiSolideGasnoblesAmEtat inconnuSynthetiqueMetalloidesMetauxMorosanu,2019Metaux deMetauxAlcalinsLanthanidesActinidertransitiorPauvreAlcakno-terreuQu'est-ce qu'on a etudie?Elements quiforment les metaux/ mineraux lourds厦Lanthanides ou terres rares

METHODOLOGY Morosanu, 2019

METHODOLOGY3.ElementsanalyzedI.HeavymineralscontentinthefinesedimentsNa20,Mg0,Al203,Si02,K20,Ca0,TiO2,V205,Cr203,MnO,Fe203,Co203,NiO,CuO,ZnO,Ga203,Ge02,As203Se02,SrO,Zr02,Nb205,Mo03,Ba0,Hf02,WO3,Pt02,Au20,Tl203,Pb0,Bi203,Th02,U308Laterselectedtheindicatorswiththemostoccurrence inthesourceareas,asratiobetweenassociatedmineralsinthepredominantrocksinthesediments'sourceareas.Examples:Rare minerals identifed inChemicalLithologic andInassociationNameXRF analysis possiblyformulawithmineralogiccontentassociated with the rocksCaoSilicaLimestoneCacO,impurities of clayClayFeoFe203siltSandKAISi,Og NaAISigOs-clay minerals (lliteCaoFeldsparCaAl2SizOs Baand kaolinite)celsian BaAl,Si,OsCaoK20BariumFeldsparshyalophane (K,Ba)(Al,Si)OsK20Na20albite NaAISi,O,Na20Baoplagioclasefeldsparsoligoclase (Na,Ca)(Al,Si)AISi;OsAI203andesineNaAlSi;O,CaAl,Si,Ossio

METHODOLOGY 3. Elements analyzed I. Heavy minerals content in the fine sediments - Na2O, MgO, Al2O3, SiO2, K2O, CaO, TiO2, V2O5, Cr2O3, MnO, Fe2O3, Co2O3, NiO, CuO, ZnO, Ga2O3, GeO2, As2O3, SeO2, SrO, ZrO2, Nb2O5, MoO3, BaO, HfO2, WO3, PtO2, Au2O, Tl2O3, PbO, Bi2O3, ThO2, U3O8 - Later selected the indicators with the most occurrence in the source areas, as ratio between associated minerals in the predominant rocks in the sediments’ source areas. Examples: Name Chemical formula Lithologic and mineralogic content In association with Rare minerals identifed in XRF analysis possibly associated with the rocks Limestone CaCO3 Silica impurities of clay CaO Clay FeO Fe2O3 Silt Sand Feldspar KAlSi3O8 – NaAlSi3O8 – CaAl2Si2O8 Ba clay minerals (illite and kaolinite) CaO Barium Feldspars celsian BaAl2Si2O8 CaO K2O hyalophane (K,Ba)(Al,Si)4O8 K2O Na2O plagioclase feldspars albite NaAlSi3O8 Na2O BaO oligoclase (Na,Ca)(Al,Si)AlSi2O8 Al2O3 andesine NaAlSi3O8—CaAl2Si2O8 SiO2

METHODOLOGY3.ElementsanalyzedIl.Lanthanides·The initial proportionsofeach of the14 rareearths (La, Ce, Pr, Nd, Sm, Eu, Gd,Tb, Dy, Ho, Er, Tm, Yb, Lu)werenormalizedwiththeknownproportionofchondrites.Therelationshipbetweenthedistributionof lanthanidesinsedimentsfromupstreamsourceareas(riverbedsamples)andthatof samplesfromdownstreamalluvial deposit layers (atPodari reach)was analyzedthroughgraphs ofstandardizeddistributionoflanthanides

METHODOLOGY 3. Elements analyzed II. Lanthanides • The initial proportions of each of the 14 rare earths (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were normalized with the known proportion of chondrites. • The relationship between the distribution of lanthanides in sediments from upstream source areas (river bed samples) and that of samples from downstream alluvial deposit layers (at Podari reach) was analyzed through graphs of standardized distribution of lanthanides

METHODOLOGYTospatializethemainareasoforiginforthealluvial sedimentswithintheJiuRiverBasin,wegroupedthesamplesoftheupstreamsourceareasaccordingtothecommongeologicalandhydrological characteristicsinto6categories,eachonewithitsowncoloronthegraphs:1.EasternJiu (yellow);2. Western Jiu green);3.TheJiuGorgesector-Rovinari peach-lightbrown);4.The Jiuwatershed between Rovinariand theconfluence withtheMotruRiver,includingGilort and Amaradiatributarieswatershedswiththesamecharacteristicsasthis areaof the JiuRiverregardingtheoccurrenceof lanthanides(pink);5.the JiuValleydownstream oftheconfluencewiththeMotruRiver (violet);SOURCE中6.theJilt-Motruwatersheds (lightgreen),nTheinterpretationofthedistributionof lanthanidesconsistsofanattributionofthepossiblesedimentsourcesfromageneralperspective(atthelevelofthe6sourceareas)toafinerspatialscale(eachsampleindividually).Thedifference inlanthanidesabundancepatternwasanalyzedatafinerscaleaswell:RBLegend1-EasternJiuVBycomparingthedistributioncurvesofthelanthanidesaltogetherbetweensource2-Western Jiu3-Jiu Gorge-Rovinar-confluenceMotnuareasandPodarialluvialriverbankprofilesamplesDEPOSITIONS-Jilt-Motruwatershedsdwtreamonf.Motru9VBycomparingtheratiobetween lightandheavy lanthanidesverticalorofil

METHODOLOGY 9 • To spatialize the main areas of origin for the alluvial sediments within the Jiu River Basin, we grouped the samples of the upstream source areas according to the common geological and hydrological characteristics into 6 categories, each one with its own color on the graphs: 1. Eastern Jiu (yellow); 2. Western Jiu (green); 3. The Jiu Gorge sector – Rovinari (peach – light brown); 4. The Jiu watershed between Rovinari and the confluence with the Motru River, including Gilort and Amaradia tributaries, watersheds with the same characteristics as this area of ​the Jiu River regarding the occurrence of lanthanides (pink); 5. the Jiu Valley downstream of the confluence with the Motru River (violet); 6. the Jilț - Motru watersheds (light green). • The interpretation of the distribution of lanthanides consists of an attribution of the possible sediment sources from a general perspective (at the level of the 6 source areas) to a finer spatial scale (each sample individually). • The difference in lanthanides abundance pattern was analyzed at a finer scale as well: By comparing the distribution curves of the lanthanides altogether between source areas and Podari alluvial riverbank profile samples By comparing the ratio between light and heavy lanthanides from a general perspective (at the level of the 6 source areas) to a finer spatial scale (the samples L.B . R.B . SOURCE DEPOSITION

ASELECTIONOfRESULTSUpper:layerPodarip11Podari P10Podarip9Podari P8PodariP7Podari P6Podari P5Podari p4Podari P3Podari P2A-TiFeB-ZrFeC-P/CaPodariP1*Orangeareas-CoalbasinsPo-Reference bottom0%20%40%60%80%100%SomeexamplesforthedistributionofheavyZr/FeTi/FemineralscompositionassedimentsourcesVariationwithdepthoftheZr&TienrichmentsmineralsalongthePodari vertical profile(content [%]10

A SELECTION of RESULTS 10 Some examples for the distribution of heavy minerals composition as sediment sources Variation with depth of the Zr & Ti enrichments minerals along the Podari vertical profile (content [%]