Rare earth element geochemistry of groundwaters from coal bearing aquifer in Renlou coal mine, north

JOUNAL OFScience DirectRARE EARTIASELSEVIERJOURNAL OF RARE EARTHS, VoL 29, No. 2, Feb. 2011, P. 185www.rejournalcom/en/Rare earth element geochemistry of groundwaters from coal bearing aquifer inRenlou coal mine, northern Anhui Province, ChinaSUN Linhua(孙林华), GUI Herong(桂和荣, CHEN Song(陈松)Achool of Earth Sciences and Engineering. Suchow University, Suzhou 234000, China)Received 5 March 2010, revised 18 July 2010Abstract: Rare earth element(Ree)concentrations of two different types of groundwaters(high SO2 water-SW and high alkaline water-CW) from coal bearing aquifer (400--280 m)in Renlou coal mine, northen Anhui Province, China were measured. The results indicatedthat they had different REE characteristics: the total concentrations of REEs (tREe)of Sw were lower than those of Cw in general althoughthey all had heavy REEs enriched relative to light REEs. The dissolved REE inorganic species of Sw included Ln", LnCo,, LnSO4*,Ln(COh and Lo(SO4h, whereas the CW are Ln(CO,h and LncO, dominant, and the proportions of Ln(CO,h increased while other speciesdecreased with pH increasing. Combined with correlation analysis, the enrichment and fractionation of sw (low alkaline water)were considered tobe affected by alkaline concentrations via affecting the types and proportions of REE inorganic species. However, the effect of alkalineconcentra-the contribution from different rocks they flowed over, different degrees of water-rock interactions and/or REE solid-liquid partition coenen otions to the enrichment and fractionation of REEs of Cw(high alkaline water) was less important than total dissolved solids and pH, which refleKeywords: rare earth elements; inorganic speciation; enrichment and fractionation; coal bearing aquifer; groundwaterRare earth elements(REEs) have attracted many geolo- In this paper, the preliminary results of the REe concen-gists because of their unique characteristics", and thus have trations, distribution pattems, as well as inorganic speciationbeen used in tracing many geological processes: the magma modeling of two different types of groundwaters from thegeneration, crustal evolution, weathering process, prove- coal bearing aquifer in Renlou coal mine, northen Anhuiance of sedimentation and, water-rock interactions et al. 2. Province, China have been reported, and the effects of REEDuring the past two decades, geochemistry of REEs have concentration and fractionation by rEe inorganic complexabeen widely used in the studies of groundwater systems 0-8, tion are also discussed. It will provide additional informationand showed that REE abundances and their characteristics about the water-rock interactions in deep seated environment( Ce and Eu anomalies, fractionation of light and heavy rEes and, for building the foundation of water source discrimina-et al)in groundwater systems were mainly controlled by the tion by using REEs in the futurerocks through which they flowed over 2), pH, redox conditions, solution chemistry, organic andor inorganic complexa- 1 Geological and hydrological settingtion, colloidal and particulate matter transport. 9230)Although the ree studies about the underground waterThe Renlou coal mine is located southwest to Suzhou City,systems had been extensively carried out in different regions, northern Anhui Province, China(Fig. 1), which is belongingthe similar work related to the deep seated environment had to the northeastern part of the Huaibei mining area. Thenot been well documented because of the difficulty of sam- Renlou coal mine is separated by the north Jiegou Fault andpling. It is fortunately that the deep coal mining in northem south Xuting Fault from Suntuan and Xutuan coal mine inAnhui Province, China provides us opportunities for tracing north and south, respectively. The length of Renlou coalthe ree characteristics of such an environment. Addition. mine from north to south is 9.8-14 km, and the width fromally, because of the discrimination of water source is impor- east to west is 1. 2-3.5 km with a total area of 43 km. Thetant in the safety of coal mine production, a series of study depth of basement rock in the mine increased from north tobased on major ions, isotopic and trace elements had been south significantly, about -200 m and-280 m below the sur-published in Refs. [21-24], whereas the method related to face, respectively. The basement of Renlou coal mine isREEs had not been reported yet, which might be useful in composed of Archean and early to middle Proterozoicwater source discrimination because of their relative stability metamorphic rocks, with cover strata are stable sedimenta-during water-rock interactions.tion b中国煤化工 mian. The total thickFoundation item: Project supported by the National Natural Science Foundation of ChinalCNMH Gcientific and technologicalCorrespondingauthor:SUNLinhua(E-mail:sunlinh@hotmail.com:Tel:+86-557-2871038DoI:10.1ol6s100240721(10)604280186JOURNAL OF RARE EARTHS, VoL 29. No. 2. Feb 2011YelloZHengzhouBanqiao100kmMengchengFig. 1 Location of the study areaess is near 3 000 m with lacking of sedimentation betweenlate-Ordovician to TriassicTable 1 Hydrological characteristics of the aquifers in renlouThe underground water system in the region is subdividedcoal mineinto four aquifers from shallow to deep: the Quatemary aqquiverThickness/ Depth/ Water tyTuifer, the Coal bearing aquifer(Meixi aquifer in previoustudyl), the Taiyuan Fm aquifer and the Ordovician lime-2057220280CL,SO4Camudstone, sandstone andstone aquifer, characteristics of each aquifer synthesized ac-conglomeratecording to previous work 2 are listed in Table 1. Hydrody. Coal bear. Mudstone, siltstone, sand- 37-128 280-400 sO.namic conditions of these four aquifers are different based ing aquifer stone and coal seams, and aon carbon and oxygen isotopic study/2). Due to shallowsmall amount of limestonedepth and coal mining, Quatemary aquifer is an"open,"sys- aquifer siltstone, and thin coal seamHCO,-Na530-680HCO2-Nasmall amount of groundwaters in it can be recharged by thelimestone limestoneupper Quaternary and lower Taiyuan Fm Aquifer(Fig. 2);aquiferthe limestone aquifers(including Taiyuan Fm and the Ordo- . The characteristics are synthesized from Gui and Chenavician limestone aquifer) are also closed systems, whereasthe groundwaters in them flow quicklyaquifer, samples were collected via drainage holes in the al-ley. The depth of sample location was between -280 and2 Sample collection and analysis-400 m. Water temperature(n), pH and total dissolved solids(TDS) were measured in the field with a portable pH and2.1 Sample collectionTDS meter after 5 min of water tum on. Water samples werefiltered through 0.45 um pore-size membrane and collectedOur study focused on the groundwaters from coal bearing into acid-cleaned polyethylene bottles that were rinsed threey。业times with sample water. 2.5 L waters(two bottles, the 2.0L。·。·ofor analysis of major ions, and the 0.5 L for REE analysis)had been collected for each sample. The samples for REEanalysis were immediately acidified to less than pH=2 usinghigh-purity HNO, and all samples were stored at less than 4'CMajor ions were analyzed in the department of geologyK and Nasorption Spectrometry, SO4 and Cr were analyzed by lonp2巴3國4 Chromatoand Me*were analyzed by EDTA Ti-中国煤化工 id-base TitrationFig. 2 Cartoon illustration showing the cross section of the Renlouafter pre-concentra-tion bCNMH--Ealyzed by inductively1-Quatermary sediments: 2-Coal bearing strata; 3-Carbonaticplasma mass spectrometry(ICP-MS, POEMS IID) in(Taiyuan Fm and Ordovician); 4-Direction of undergroundthe State Key Laboratory of Geological Processes and Min-SUN Linhua al, Rare earth element geochemistry ofgroundwaters from Coal bearing aquifer in Renlou coal mine,l87eral Resources, China University of Geosciences(Wuhan). (Na+K)and TDS contents, 127-1 026 mg/L, 468-968andAnalytical process was following the method reported by 2 016-3 223 mg/L, respectively. They can be subdividedShabani et al. 124 and the principles of DZ/To223-2001 into SO4- enriched water(SW) and alkaline enriched water( China): Intermal standards(rh) were used to correct for in- ( CW) according to their relative concentrations of SO4 andstrumental drift and matrix suppression; the REe isotopes alkaline. The Sw are characterized by higher Ca"( 17. 2-324ILa, 4Ce,pr, 4Nd, 4Sm, SEu, SGd, 5Tb, Dy, mg/L), Mg*(5.10-86. 8 mg/L), SO4(594-1 844 mg/L)16 Ho, 6Er, 16 Tm, 7Yb and Lu were used to quantify contents, and lower alkaline(268-318 mg/L), pH valuesthe REEs in the groundwater samples. Although many of (7. 14-8. 20)than CW, who have Ca2*4.05-13.4 mg/these REE isotopes are free of isobaric interference, the Mg*=0.98-4.90 mg/L, SO42=3.6548.0 mg/L, alkalisobaric interference of Bao to Eu had not been well cor- 886-1 488 mg/L and pH=836-8. 78rected, leading to the useless of Eu among these REEs. Theanalytical precision for all REEs except for Eu was 10% 3. REE concentrations and fractionationrelative standard deviation(RSD)or betterREE concentrations of groundwaters from coal bearingaquifer, Renlou coal mine are listed in Table 3. As see in the2-3 Speciation modelingtable, REE concentrations and fractionation patterms are dif-Previous research demonstrated that rEEs exist in solu- ferent between Sw and cw. The total concentrations oftion primarily as complexes with the halides, sulphate, REEs(EREE)of Sw range from 0.0218 to 0.0373 ug/L,phosphate, hydroxides, carbonate, DOC or as the free ions"2. which is much lower than those of Cw(0. 1203-0.3158 ug/L)Phosphate complexes are only important if phosphorus lev- except for sample M-6(0.0286 Hg/L). Additionally, all of thels are high>6 which is considered always in eutrophic samples are light REEs(LREEs) depleted relative to heavwaters rather than waters in this study. Moreover, although REEs(HREEs)in PAAS( Post Archean Average Shalethe role of organic complexing may be important in wa- normalized diagrams(Fig 3), whereas the fractionation deers 327 the lack of data limited such a consideration. In thisstudy, only inorganic complexation of REEs modeled byTable 3 Rare earth element(Hp/L) compositions of the ground-modeling is similar to the report by Zhu et alled ofVisual Minteq (veersion 2.61(28小 is reported,thewater from coal bearing aquifer in Renlou coal mineElements M-1 M-2 M-3 M-4 M-5 M6 M-7 M-8Ronnback et al. 2. Equilibrium with calcite was assume00013000250001600017000000190022000330=p如山①(m000170003800011000360002100011000nplagioclase is one of the major phases in sandstones from Nd 0.00480.00470.00010.0032 0400-410.00320.0089 00071coal bearing strata, effects of Ca+, Mg?*, K*and Nato the SmREe speciation is considered simultaneously. Only species000680008900080003600590000340.150002400with proportions higher than 1%are collected in Fig. 6000310001500007000140003400010003600006000090001300038000120002400007Dy000670004400010000780013000010000623 Result00010000100001800017000160000800018000053. 1 Major ions and other characteristicsTm0005000090000Major ions and other characteristics (T, pH and TDS) of Yo 0.0032 0.0032 0.0001000740002groundwaters from Coal bearing aquifer, Renlou coal m00013000000002000110001400019are presented in Table 2. As see in the Table, the water sam- EREE 0.0366 0.0366 0.0218 0.0373 0 1203 0.0286 02308 03158ples have temperature range between 30.1 and 314C with Nds Bon 0. 120.120.080.140050.090.07030neutral to slightly alkaline pH (.. 78), and high Cr,"SN means PAAS normalizationTable 2 Major ions of the groundwater from Coal bearing aq-ons ML M2 M-3M4 M.. M87738686275.102524.90098252Na+K+468564857949710860755968lX10-15%453818441780中国煤化工Alkaline298318268289-42亠M3M426702806322331802219201624353055CNMHO46→M7Tb Dy Ho Er Tm Yb LuT301313305314306305312.M-I to 4 are sW, M-5 to 8 are CW, the unit for major ions and T are mg/L andig. 3 PAAS normalized REE pattems of the groundwater from"C, respectively. Alkaline means HCO,(pH<8.3)or C0,(pH>8.3)coal bearing aquifer in Renlou coal mineI88JOURNAL OF RARE EARTHS, VoL 29, No 2, Feb 2011grees expressed by NdsN/YbN ratios(SN means PAAS TDS and NdsN/Bsn ratios(R 0.80, 0.90 and 0.89, respecnormalization)of SW and CW are different, 0.08-0.14 and tively). The relationships between EREE and SO4, alkaline0.0S-0.30, respectivelypH and TDS are shown in Fig. 5, no obvious relationshippH versus SO4, alkaline, TDS and NdsN/YbsN are between them are observed for SW, which might be due topresented in Fig 4. The pH values of Sw are well correlated their limit variations of EREE. However, significant correlawith SO4-and TDS(R0.87 and 0.90, respectively). More- tions between ZREE, pH and TDS, and a weak correlationer, the pH values of Cw are well correlated with alkaline, between EREE and alkaline for CW are presented.(a)(b)2000R087H35000.283000R=0890.12000Fig 4 pH versus SO4(a), alkaline(b), TDS (c)and NdsNYbsN( d)of the groundwater from coal bearing aquifer in Renlou coal mineOpen diamaons-Sw: filled square-CW6001000500F80304∑REE∑REER=0.74R=0.902000中国煤化工CNMHG3 0.4∑REE∑REEFig. 5 REE versus SO4(a), alkaline( b), pH(c)and TDS(d) of the groundwater from coal bearing aquifer in Renlou coal mine(symbols asSUN Linhua et al, Rare earth element geochemistry of groundwaters from Coal bearing aquifer in Renlou coal mine,3.3 REE inorganic speciesThere are many processes likely control REE concentra-tion and fractionation of groundwaters: (I)release of REEsResults of REE inorganic speciation modelingin Fig. 6 for groundwaters from Coal bearing aquifepfrom host rocks; (2)solution complexation with organiccoal mine. Fig. 6 indicates that thenic solution com-andor inorganic ligands and surface adsorption or desorpplexation of REEs in the aquifer istion and (3) precipitation of REE phosphate minerals n1ve reve(which is considered to be related to major ions, especially the release of REEs from host rocks to waters during wa-SO4 and alkaline in Fig. 4)The dissolved REE inorganic species of sw include Ln ter-rock interaction played important role in controlling theREE concentrations and fractionations of groundwaters(Fig.Ln(SO), LnSOA, Ln(COj) and LnCo, Ln Ln(SOa)2, 7). However, with the complexity of rock types of the coalLnSO4 are only important for LREEs, whereas Ln(Co3hand LnCO, are predominant for M- and HREEs. Moreover,bearing strata (Table 1), such a consideration cannot bequantitatively discussed at the moment. Moreover, as men-with increasing pH values, the proportions of Ln", tioned above, the phosphate complexes are only important ifLn(SOA), LnsO4 and LncO, are predicted to decrease,phosphorus levels are high 2526), which is considered alwayswhereas Ln(Co3) is predicted to increasein eutrophic waters rather than waters in this study. Addi-pHtionally, although the role of organic complexing may be7147377908208368428.528.78important in waters3, the lack of data limited such a con-sideration. Thus, in this study, we focused on only the effectsLa(so,of inorganic complexation over the REE concentration andfractionation of groundwatersAdsorption of REEs onto solid phases could removeLacoREEs from groundwaters and thus decrease their dissolvedconcentrations).In contrast, solution complexation ofM-2M.3 M4 M-5 M6 M-7 M-8REEs with inorganic ligands can result in the formation ofweakly or non-adsorbing aqucous complexes of REEs andthen keeping the REEs in solution ) Based on these ideas,0000■Sm(SO)2Johannesson and Hendry 4 suggested that the carbonate ion■SmsoSm(co)concentrations, and thus ph, exert important controls onaqueous(high carbonate ion concentrations, pH=7-8)REEconcentrations via different proportions of Ln(CO3) andM,1M2M3M-4M.5M-6M.7M8LnCO,, and Zhao et al. 35)suggested that the concentrationsofSo4 control the concentrations of REE in AMD samples(high SO4 concentrations, pH=3.5-3. 8) with LnsO4 spe-■Yb(S)cles■YbsOIn present study, the EREE of Cw is positively correlatedYb(cO,)with alkaline concentrations(Fig. 5). However, as see in Fig5. the eREE of Sw are rather constant, and show no obvious0..2M-3M.4M-5M-6 M-7 M&correlation with SO and/or alkaline concentrations, is itFig. 6 REE(La, Sm and Yb)speciation distribution of the groundreally different with Cw? For better understanding of suchwaters from Coal bearing aquifer in Renlou coal mine. Num. consideration, correlation coefficient calculation has beenrs at the top horizon are ph valucs for each sampleBeing different from SW, the dissolved REEs of Cw is 2LW/Limestonepredominantly composed of Ln(CO,) and LnCO,, espe- 5Ix10cially the Ln(CO,), which can account for more than 80%of the dissolved LREEs, and more than 90% of the M- andHREES, and the proportions of Ln(CO, h and LnCo,'are 5 1x1dpositively and negatively correlated with pH values, respec-tively.It is worth noting that although the CT in water samplesre high (Table 2), the REE-chloride complexes that was中国煤化工 yY Ho Er Tm Yb Luconsidered to be important in low pH conditions 2.)are ex- FigCNMHGgoundwaters(Y is in-tremely low in this study (<1%)ters from limestone and sandstone aquifer, respectively(Ourunpublished data)IscussionJOURNAL OF RARE EARTHS, VoL 29, No 2, Feb 2011carried out. The results show that the ZREE is positively cor of groundwaters are higher than those of HREEs, then forrelated with alkaline concentrations for SW, whereas EREe the reason mentioned above, the groundwaters will exhibitof Cw is best correlated with TDS, to a lesser extent, the pH LREEs depletion. This consideration is consistent with theand alkaline(Table 4). Such results imply that the controlling observations in Table 3 that the NdsNYbsN ratios from M-1factors of REE concentrations of Sw and CW are different, to 4 increased with the increasing of negatively chargedbut at least, all of them are affected by alkaline concentra- cies except for M-3.tions, which might reflect the effect of carbonate/bicarbonate As to the CW, because more than 80%(most of the REEsmore than 90%)of the dissolved REEs are complexed to beLn(CO3), with less have been complexed as LnCO3Table 4 Correlation analytical results of the groundwater fromcoal bearing aquifer in Renlou coal mine(<20%, and most of the HREEs less than 10%). For the samereason, it will not lead to significant fractionation of L- andHREEs. However, this conclusion is contrary with the truthERee Nds/YbsNΣ REE Ndo/Ybsythat samples from M-5 to 7 have very low NdsN/Bsn ratios(Table 3). Considering about the correlations in Table 4, theH03000pHNdsN/YbsN ratios of Cw are well correlated with TDS andAlkaline 0.65 0.80pH values, and moderately correlated with alkaline concen-0.57-026SO2-032trations. the different rocks of cw flowed over. differentdegrees of water-rock interactions and/or REe solid-liquidNegatively charged bicarbonate complexes (e.g. partition coefficients probably played important roles for theLn(CO3h)will be stabilized in waters than positively REE fractionation of cwll3, rather than the concentrationscharged carbonate complexes (e.g. LnCO,, because the of alkaline.positively charged carbonate complexes can be easily ab- In general, our study demonstrated that in neutrsorbed to the negatively charged particle surface, and then slightly alkaline groundwaters, REE species play importantleaving the water with REE depletion n. REE speciation role in affecting the REE concentration and fractionation ofindicates that the proportions of negatively low alkaline waters(sW), but not the key factor controllingcharged REE species of CW are higher than Sw in general the high alkaline waters( CW). This result is different with(Fig. 6), which will lead to higher EREE of CW than SW, Johannesson and Hendry/ s4 and Zhao et al 351.Howeverthis is consistent with the truth that EREE of Cw are higher because of only limited data had been analyzed in this paperthan those of Sw except for M-6. However, because of the the understanding needs further study to confirm.different compositions (e.g. major ions in Table 2)of Cwand Sw, they might have different sources that they cannot cOnclusionsbe directly compared, but should be discussed separately. Asto the sw, from M-I to 4, with the increasing of proportions (1)Groundwaters from coal bearing aquifer in Renlouof Ln(COjh, the ZREE increased except for M-3, which is coal mine could be subdivided into SO 4 enriched (SW)andalso consistent with the above conclusion. A similar conclu- alkaline enriched water(Cw) according to their relative con-sion can be obtained for CW that the EREE increased with centrations of So4- and alkaline, and they had different REEthe increasing of Ln(CO3) proportions except for M-6characteristics: the tree of Sw were lower than those ofJohannesson and Lyons) attributed the large HREEs en- Cw in general, and all of them were HREEs enriched relarichments of waters from Mono Lake in eastern Carliforlia, tive to LREEs with variable NdsN/YbsN ratiosUSA to the predominance of ree bicarbonate complexes(2)The dissolved REEs inorganic species of Sw includedBecause in low CO, waters, the bicarbonate species pref- Ln, LnCO,, LnSO4, Ln(CO,h and Ln(SO4h, whereaserentially complex the HREEs, then leave the LREEs to be Cw were Ln(CO3) and LnCO, dominant Proportions offree ions, sulphate species, or carbonate species. Then the Ln(CO,)h increased while other species decreased with in-positively charged species(LnCO,, LnSO, and Ln")can creasing phbe easily removed by negatively charged particle surface,(3)Alkaline concentrations played an important role inand then the lrees of the water is depletedcontrolling the enrichment and fractionation of REEs of SwThis model can well explain the LREEs depletion of the (low alkaline water) via affecting the types and proposw with low alkaline from Coal bearing aquifer, Renlou of REE inorganic species. However, the role of alkaline con-coal mine. As see in Fig 3, the Sw samples in this study ex- centrations to the enrichment and fractionation of REEs ofhibit enrichment of HREEs relative to LREEs, and thus Cw(high alkaline water)was less important than TDS andsmall NdsN/YbsN ratios(0.08-0. 14)of the groundwater. Be- pH vacause of the relatively low concentrations of alkaline of Sw, the中国煤化工 contnbutionthe LREE species tend to be Lnco3, LnSO4 and Ln(e.g. greesCNMH GEE solid-liquid par-La of M-1, 87.9% in total), whereas the proportions of same tition coefficientsspecies of HREEs are low(e.g. Lu of M-1, 51. 15% in total),of lreesAbbreviations: REEs: rare earth elements, also Ln in theSUN Linhua ef al, Rare earth element geochemistry ofgroundwaters from Coal bearing aquifer in Renlou coal mine,text and figures; HREEs: heavy rare earth elements; LREEsrare earth elements in an alluvial aquifer affected by acid mineight rare earth elements; TDS: total dissolved solids; PAAS:drainage: the Guadiamar aquifer(Sw Spain). Emvironmentalpost archean average shale; SW: SO4 enriched groundwater;CW: alkaline enriched ground[16] Sanada T, Takamatsu N, Yoshiike Y. Geochemical interpretation of long-term variations in rare earth elements concentra-Acknowledgements: Thanks are given to Dr. Zi J w from the Uni-tions in acidic hot spring waters from the Tamagawa geotherversity of Westem Australia for his help in manuscript preparatimal area, Japan. Geothermics, 2006, 35: 141[17 Biddau R, Bensimon M, Cidu R, Parriaux A. Rare earth ele-References:nents in groundwater from different Alpine aquifers. Chemieder Erde Geochemistry, 2009, 69(4): 327[] Henderson P. Rare Earth Element Geochemistry. Edited by [18] Choi H S, Yun ST, Koh Y K, Mayer B, Park SS, Hutcheon L.Henderson P. New York: Elsevier, 1984. 1.Geochemical behavior of rare earth elements during the evolu-[2] Hanson G N. Rare earth elements in petrogenetic studies oftion of COr-rich groundwater: A study from the Kangwon dis-trict, South Korea. Chemical Geology, 2009, 262: 318[3] Taylor SR, McLennan S M. The Continental Crust: Its Com- [19) Tricca A, Stille P, Steinmann M, Kiefel B, Samuel 3, Eiken-position and Evolution. Oxford: Blackwell Scientific Publica-tions of dissolved and suspended loads from small river sys-[4] Banner J L, Wasserburg J, Dobson P F, Carpenter A B,tems in the vosges Mountains(france), the river Rhine andMoore C H. Isotopic and trace element constraints on the ori-groundwater Chemical Geology, 1999, 160: 139gin and eve[20]Nelson B J, Wood S A, Osiensky J L Partitioning of ree be-Geochimica et Cosmochimica Acta, 1989. 53: 383.tween solution and particulate matter in natural waters: a filtra-tion study. Journal of Solid State Chemistry, 2003, 171: 51Cerium anomalies in lateritic profiles. Geochimica et Cosmo- [21] Chen Hongjiang, Li Xibing, Liu Aihua, Peng Shuquan. Identichimica acta. 1990. 54: 781fying of mine water inrush sources by fisher discriminant[6Bau M. Rare-earth element mobility during hydrothermal andanalysis method. Journal of Central South University(Scieetarmorphic fluid-rock interaction and the significance of theand technology)(in Chin. ) 2009, 40(4): 1114A Oxidation state of europium. Chemical Geology, 1991, 93: 219. 22]Gui Herong, Chen Luwang. Hydrogeochemistric Evolution andLeybourne M L, Goodfellow W D, Boyle D R, Hall G M.Discrimination of Groundwater in Mining District. Edited bypid development of negative Ce anomalies in surface watersGui HR Chen L w(in Chin. Beijing: Geological Publishingand contrasting rEE pattens in groundwaters associated withHouse. 2007.Zn-Pb massive sulphide deposits. Applied Geochemistry, 2000, (23) Chen Luwang, Gu Herong. Yin Xiaoxi. Composing charac-teristic and evolution law of carbon and oxygen stable isotopes[8] Niu Manlan, Liu Guosheng, Zhu Guang, Song CZ, Wang DXin groundwater dissolved carbonate. Journal of China Coalf mechanism of formation of Cenozoic basaltsocery( in Chin.),2008,335):537along Shandong-Anhui part of Tan-Lu Fault Zone by using [24] Shabani M B, Akagi T, Shimizu H, Masuda A. Determinationare earths. Journal of the Chinese Rare Earth Societyof trace lanthanides and yttrium in seawater by inductivelyChin,205,23(3):363coupled plasma mass spectrometry after preconcentration with[9] Tan Lugu, Zhou Taofa, Yuan Feng, Fan Y, Yue S C. Mecha-olwen extraction and back-extraction. Analytical Chemistrynism of formation of the permian volcanic rocks in Sawuer1990,62:2709area, Xinjiang: constrains from rare earth elements. Joumal of (25] Lewis A J, Komninou A, Yardley B WD, Palmer M R. Rarethe Chinese Rare Earth Society(in Chin. ) 2007, 25(1): 95earth element speciation in geothermal fluids from Yellow[10] Smedley P L. The geochemistry of rare earth elements instone National Park, Wyoming, USA Geochimica et Cosmo-groundwater from the Carmmenellis area, southwest Englandchimica acta,1998,62(4):657Geochimica et Cosmochimica acta, 1991. 55: 2767[26] Zhu Zhaozhou, Liu Congqiang, Wang Zhongliang, Li Jun, Zhou[11]Johannesson K H, Stetzenbach K J, Hodge V F, Lyons WBZhihua. Inorganic speciation of rare earth elements in ChaohuRare earth element complexation behavior in circumneutral pHLake and Longganhu Lake, East China. Journal of the Chinesegroundwaters: Assessing the role of carbonate and pgosphateRare earth Society(in Chin. ) 2006, 24(1): 110ions, earth Planet Science Letters, 1996. 139: 305.[27] Tosiani T, loubet M, Viers J, Valladon M, Tapid J, Marrero s,[12] Johannesson K H, Stetzenbach K J, Hodge V F, Kreamer K,Yanes C, Ramirez A, Dupre B. Major and trace elements inZhou X P. delineation of groundwater flow system in theriver-bome materials from the Cuyuni basin(southen Vene-southem Great Basin using aqueous rare earth element distri-zela): evidence for organic -colloidal corbutions, ground Water, 1997. 35: 807.load and element redistribution between the suspended and[13]Johannesson K H, Tang J, Daniels J M, Bounds wJ, Burdigedissolved load. Chemical Geology, 2004, 211: 305D J. Rare earth element concentrations and speciation in or- [28]Gustafsson J P, Pechova P,Berggren D. Visual Minteq versionganic-rich blackwater of the Great Dismal Swamp, virginia,中国煤化工 /OurSoftware/minteq/USA Chemical Geology, 2004, 209: 27112010.14]WoodS A, Shannon W M Rare-earth elements in geothermal 129)CNMHGaters from Oregon, Nevada, and Califorlia. Journal of Solidavior of rare earth elements in surface waters. overburdeState Chemistry, 2003, 171: 246.groundwaters and bedrock groundwaters in two granitoid[15]Olias M, Ceron J C, Femdndez L, Rosa JD L. Distribution ofsettings, Eastern Sweden. Applied Geochemistry, 2008, 23(7)JOURNAL OF RARE EARTHS, VoL 29, No 2, Feb 2011along a groundwater flow path within a shallow, basin-fill aq30 Haas J R, Shock E L, Sassani D C. Rare earth elements inuifer, southern Nevada, USA. Geochimica et Cosmochimicahydrothermal systems: estimates of standard partial molalActa,1999,63:269thermodynamic properties of aqueous complexes of the rare [34]Johannesson K H, Hendry MJ. Rare earth element geochemis-earth elements at high pressures and temperatures. geochimicatry of groundwaters from a thick till and clay-rich aquitard se-et Cosmochimica Acta, 1995, 59: 4329quence, Saskatchewan, Canada. Geochemica et Cosmochimica[l] Tang Jw, Johannesson KJ. Controls on the geochemistry ofca,2000,64:1493rare earth elements along a groundwater flow path in the Car- [35] Zhao F H, Cong Z Y, Sun H F, Ren D Y. The geochemistry ofnzo Sand aquifer Texas, USA, Chemical Geology, 2006, 225rare earth elements(REE)in acid mine drainage from the Sitai156.coal mine. Shanxi Province, North China. International Jour.[32]Zhou X P, Stetzenbach K J, Yu Z G, Yu Z B, Johannesson Knal of Coal Geology, 2007, 70: 184H Rare earth elements in Groundwater Flow Systems. Edited [36] Johannesson K H, Lyons W B. The rare earth element geo-by Johannesson KJ5.1chemistry of Mono Lake water and the importance of carbon-33Johannnesson K H, Famham I M, Guo C, Stetzenbach KJ.ate complexing. Limnology and Oceanography, 1994, 39Rare earth element fractionation and concentration1141中国煤化工CNMHG