Geochemistry of rare earth elements in groundwater from deep seated limestone aquifer in Renlou Coal

J Cent. South Univ. Technol (2011)18: 1646-1653DOl:10.1007/s11771-011-08842Geochemistry of rare earth elements in groundwater fromdeep seated limestone aquifer in Renlou Coal Mine, Anhui Province, ChinaSUN Lin-hua(孙林华), GUI He-rong(桂和荣), CHEN LU-wang陈陆望), CHEN Song(陈松School of Earth Sciences and Engineering, Suzhou University, Suzhou 234000, China;2. School of Resources and Environmental Engineering, Hefei University of Technology, Hefei 230009, Chinao Central South University Press and Springer-Verlag Berlin Heidelberg 2011Abstract: Rare earth element(REE) concentrations were measured by ICP-Ms for groundwater collected from deep seated TaiyuanFm limestone aquifer(from -400 to -530 m)in Renlou Coal Mine, northern Anhui Province, China. It can be concluded that thegroundwater is warm (340-372C)Cl-Ca, Na type water with circum-neutral pH(7. 35-8.28)and high total dissolved solids(TDs1 746-2 849 mg/L). The groundwater exhibits heavy REEs enrichment relative to light REEs compared with Post Archean AverageShale(Paas), as well as their aquifer rocks(limestone). The enrichment of REEs is considered to be controlled by terrigeneousmaterials(e. g. zircon) in aquifer rocks, whereas the fractionation of REEs is controlled by marine derived materials( e.g. calcite), to aless extent, terrigeneous materials and inorganic complexation. The Ce anomalies normalized to PaAs and aquifer rocks are weak,which probably reflects the signature of the aquifer rock rather than redox conditions or pH. The similarities of rEe patterns betweengroundwater and aquifer rocks imply that aquifer rocks play important roles in controlling the ree characteristics of groundwateand then provide a probability for discrimination of groundwater sources by using rEEsKey words: rare earth elements; geochemistry; water-rock interaction; limestone aquifer; groundwaterthe similarity between groundwater and aquifer rockI IntroductionREE patterns. Indeed, many groundwater samplesexhibit REE pattems that closely resemble the REEBecause of their unique characteristics [1], rare patterns of the rocks through which they flow. However,earth elements(REEs)were highly interested by many for some of the groundwater samples, they have highlygeologists and thus had been used in studying many fractionated REE patterms compared with the aquifergeological processes: magma generation, crustal rocks [11]evolution, weathering process, provenance ofThe deep coal mining in northern Anhui Province,sedimentation and water-rock interactions etc [2-6]. China, provides us opportunities to trace REEHowever, for the ree study of water systems, much characteristics of groundwater in deep seatedattention had been paid towards the surface water environment. Additionally, because the discrimination ofgeochemistry of REEs, with less study focused on REEs water source is important in the safety of coal minein groundwater systems although the number of such production, a series of studies based on major ions,investigations is increasing [7-11. Especially, because isotopic and trace elements had been published inof the difficulty of sampling, the similar work related to previous literatures [12-15]. Heoweverthe methodthe deep seated environment is still far from related to REEs had not been reported yet, which mightunderstanding.be useful in water source discrimination because of 1)The previous work revealed that REE abundances the relative stability of REEs during water-rockand their characteristics (Ce and Eu anomalies, interactions, 2)the similarity of ree patterns betweenfractionation of light and heavy REEs etc)in groundwater and aquifer rock, and 3)different rockgroundwater systems were mainly controlled by the compositions of the aquifersrocks through which they flowed over, pH, redoxIn this work, the preliminary results of reeconditions, solution chemistry, organic and/or inorganic concentrations, distribution patterns, as well as inorganiccomplexation, colloidal and particulate matter transport speciation modelling of the groundwater from limestone[9]. The most significant finding among these studiesaquifer (LW)d between -400 and -530 m in中国煤化工Foundation item: Project(40873015)supported by the NaNatural Science Foundation ofFive- year Scientific and Technologcal Program of Anhui Province, ChinaCNMHGed by the EleventhReceived date: 2010-07-28: Accepted date: 2010-11-26CorrespondingauthorSunLin-hua,Phd;Tel:+86-557-2871038;E-mail:sunlinh@126.comJ. Cent. South Univ. Technol. (2011)18: 1646-16531647Renlou Coal Mine Anhui Province, China, are reported, aquifer, the Coal bearing aquiferand the controlling factors for the REE concentration, previous study [12]),the Taiyuanmaquifer in thefractionation and Ce anomaly are discussed based on the Ordovician limestone aquifer. The characteristics of eachcomparison of REEs of groundwater, average shale and aquifer synthesized according to the previous work [12]aquifer rocks. It will provide additional information are listed in Table 1. Hydrodynamic conditions of theseabout the water-rock interactions in deep seated four aquifers are different based on carbon and oxygenenvironment,and provide new information for water isotopic study [13]. Due to shallow depth and coalsource discrimination by using REEsmining, Quatemary aquifer is an"open"system; Coalbearing aquifer is relatively "closed"with only small2 Hydrogeological settingamount of groundwater in it, which can be recharged bythe upper Quaternary and lower Taiyuan Fm AquiferThe Renlou Coal Mine is located southwest to ( Fig. 2); the limestone aquifers(including Taiyuan FmSuzhou City, northern Anhui Province, China(Fig. 1), and the Ordovician limestone aquifer)are also closedwhich belongs to the northeastern part of the Huaibei systems, whereas the groundwater in them flows quicklymining area. The Renlou Coal Mine is separated by thenorth Jiegou Fault and south Xuting Fault from Suntuan 3 Methodsand Xutuan coal mines in north and south, respectively.The length of Renlou Coal Mine from north to south isThe groundwater from Taiyuan Fm limestone9.8-14 km, and the width from east to west is 1. 2- aquifer was focused on; aquifer rocks were collected3.5 km with a total area of 43 km. The depth of from drilling cores; water samples were collected viabasement rock in the mine increases from north to south drainage holes in the alley. Water temperature(n), phsignificantly, about -200 m and -280 m below theand total dissolved solids(tDs)were measured in thesurface, respectively. The basement of Renlou Coal Mine field with a portable pH and TDS meter. Water samplesis composed of Archean and early to middle Proterozoic were filtered through 0.45 um pore-size membrane andmetamorphic rocks, with stable sedimentation between collected into polyethylene bottles that had been cleanedlate-Proterozoic and Permian. The total thickness is using trace element clean procedures. Two bottles ofnearly 3 000 m with lack of sedimentation betweenwater(2.0 L for analysis of major ions, and 0.5 L forlate-Ordovician to TriassicREE analysis) were collected for each sample. TheThe groundwater system in the region is subsamples for REE analysis were immediately acidifiedinto four aquifers from shallow to deep: the Quaternarto less than pH 2 using high-purity HNO3 and stored atYellow sea100 km(Mengcheng5 kmFig 1 Location map of study area( Renlou Coal Mine)in northern Anhui Province, ChinaTable 1 Hydrological characteristics of aquifers in Renlou Coal Mine[121Rock typesThickness/m Depth/m Water typeQuatermaryOrange-deep yellow mudstone, sandstone and conglomerate20-57220-280 CL, SO4-Ca, NaCoal bearingMudstone siltstone, sandstone and coal seams,37-128280-400SO4,HCO3-Nad a small amount of limestoneanyuanudstone. siltstone, and thin coal seam中国煤化工C,HCO3NaOrdovician limestoneThick layer of light gray limestoneCN MH GHCOj-Na, CaLimestone aquifer in this study1648Cent. South Univ. Technol. (2011)18: 1646-1653phosphate, hydroxides, and carbonate or as the free ions[18]. Phosphate complexes are only important ifphosphrous levels are high [19], which is alwaysconsidered in eutrophic water rather than water in thisstudy. Moreover, organic complexation of REEs ingroundwater is likely to be substantially less significantthan for surface water [11]. In this study, only inorganiccomplexation of REEs modeled by Visual Minteq(Version 2.61)is reported. The method of modelling issimilar to that used by ZHU et al [19] and RONNBACKp密2巴3國et al [20]Fig2 Cross section of Renlou Coal Mine: I-Quaternary 4 Resultssediments; 2--Coal bearing strata; 3--Carbonatic strata(Taiyuan Fm and Ordovician); 4--Direction of underground4.1 Major solute compositions of groundwaterwater rechargeConcentrations of the major ions of the LW arepresented in Table 2, along with pH, water temperatures4C before analysisand TDS. The groundwater can be classified as Cl-CaMajor ions were analyzed in the Department of Na water based on the relative distribution ofGeology, Renlou Coal Mine. REE concentrationssolutes(Fig 3), which is slightly different from thgroundwater were determined after pre-concentration by previous study [12]. Additionally, the groundwater is ofliquid-liquid extraction, and analyzed by inductively circum-neutral pH, with values ranging from 7.35 to 8.28coupled plasma mass spectrometry (ICP-MS, POEMS ID) and an average of 7.62, and is relatively warm within the State Key Laboratory of Geological Processes and temperatures ranging from 340C to 37. 2C and anMineral Resources, China University of Geosciences average of 357C. The groundwater is also high in TDS(Wuhan). Analytical process followed the method ranging from 1 746 to 2 849 mg/L with an average ofreported by SHABANI et al [16]. The isobaric 2 241 mg/Linterference of Bao to Eu had not been well corrected,leading to the useless Eu among these REEs [11]. The 4.2 REE of groundwateranalytical precision for all REEs except for Eu was 10%The Ree concentrations are slightly higher than( relative standard deviation) or better. REEs of rocks those reported for other groundwater of circum-neutralwere analyzed with PE Elan 6000 ICP-MS at the Key pH(see Table 3). For example, Nd concentrations of theLaboratory of Isotope Geochronology and Geochemistry, Lw range from 0.006 to 0.010 ug/L with average ofCAS. The relative derivations were less than 5%, and 0.008 ug/L (equivalent to 55.5 pmol/kg). In comparison,detailed analytical procedures were referred to LIU et al Nd concentration of the Lw is higher than the mean Nd[7]concentration of groundwater collected from theThe previous study demonstrated that REEs exist in Battleford aquitard (pH=7.54 with mean Ndsolution primarily as complexes with halides, sulphate, concentration of 22 pmol/kg)[21]. On the other handTable 2 Major solute compositions, PH, temperature and total dissolved solids(TDS)of groundwater from limestone aquiferLW-ILW-2LW-3LW-5Lw-67.7273673535.634.737.035.5P(K*+Na(mg L-)375380p( Ca"(mg L-)210P(Mg)(mg L-)p(CI)(mg L610P(sO4(mg L)441324p(Alkaline)(mg L")539中国煤化工202TDS/(mg L-)2849CNMHG 1746Alkaline-HCO)J Cent. South Univ. Technol (2011)18: 1646-16531649Fig- 3 Temary plots of major ion concentrations of groundwater from limestone aquiferTable 3 Rare earth element concentrations of groundwater from limestone aquifer(ug/L)LW-1LW-2LW-3LW-4LW-6Average135541181317148193531385310529143750.0660.0430.0580.055003800140.00710007700l10.0079000960.0240.01100150.01800170012001630.00290.00l6000230.0016000180.0021Nd00060000780.00750.00820.008000048000280.0011000330.00510.0021000620.0110.004200.00300.00090.0020000180.00350.00220.00040.00030.00040.00040.00040.00040.0004000130.0014000l80.00150.00120.00230.0016000050.00040.00050.00050.00040.00030.00040.00130.00l50.0010000150.00l10.00010.00040.00040.0000.00040.0002000030.00200.00270.00210.00140.0019Lu0.00050.0002000090.00020.00040.00080.0005∑REE0.0710.0370.0540.0510.05800526NdSN/Bsn0.430.300240.30038Ce/Ce"sN0.060.110.100.140.080790.710.94133NORNYbRN0.460.320.53Ce/Ce*RN0030.120.75670.900.55130sN and RN mean PAAS and rock(average limestone)normalization, respectively: Ce/Ce"alog (2*Cea/(Laa+Pra)), Ew/Eualog(2"Eua/(Sma+Gda),whereaSN or RNgroundwater from the Carnmenellis region of England PAAS normalization) range from 0.24 to 0.49 with(pH=5.82) has remarkably high Nd concentrations average of 0. 38(Table 3). In addition, all kinds of theranging from 3 500 to as high as 478 000 pmol/kg[7]groundwater samples show weak or no negative CePAAS(Post Archean Average Shale [3])noanomalies( Fig 4). The PAAS-normalized Cethe groundwater are characterized.g.4. All kinds of range fromEE patterms of Lw are presented in Fi-0.08. Another中国煤化hment of remarkable chHREEs compared with LREEs when normalized toSTHCNMHGation analysisPAAS, and the normalized ndsn/bsn ratios(Sn means indicates that the Zr concentrations of groundwater are1650J. Cent. South Univ. Technol.(2011)18: 1646-1653LREEs(NdsN/YbsN060-0 88). However, other twosamples(LR-4 and 6) have NdsN/YbsN=1.03 and 1.11respectively. Moreover, these limestones show almost nonegative Ce anomalies, with Ce/Ce*sN ranging from-0.07 to =0.01 with an average of -0.02. Suchcharacteristics suggest that these limestones are notpure"limestones, but have been affected by terrigenousmaterials ("pure"marine derived limestones arecharacterized by significant negative Ce anomalies and104low NdsN/YbsN ratios [22-23DZr and Sr are always considered to representterrigenous and marine materials, respectively. The Zr82品弓日占占目3concentrations of limestones are well correlated withREEEREE (R=0.96), whereas the R value between Sr andFig 4 PAAS normalized REe pattems of groundwater fromREE is 0limestone aquiferAlthough it is instructive to normalize REEconcentrations of the groundwater in this study to PAASwell correlated with 2REE (R=0.76), whereas the R for purposes of comparison with earlier studies, it isvalue between Sr and 2REE is 0.22.more appropriate to normalize these groundwater to theREE concentrations of the limestones in this study4.3 REE of limestones and limestone-normalized because aquifer rocks are thought to be the chief sourcepatterns of groundwaterof REEs to groundwater [7]. Figure 6 shows a plot ofThe REE concentrations of limestones are listed in REE concentrations of Lw-normalized to the averageTable 4, and the PAAS-normalized REE patterns are limestones from Table 4. The average limestonepresented in Fig. 5. Some of these limestones exhibit normalized groundwater patterns are similar to the PaasPAAS-normalized REE patterns similar to the oceanic normalized patterns with little differences. For examplelimestones [22-23] with HREEs enriched relative to the groundwater also exhibits HREEs enrichmentTable 4 Rare earth element concentrations(10 )of limestonesREELR-ILR-2LR-3LR-4LR-5LR-6108110641042104697610564.8312.03.609.7894317213.486.695.762593.0003014.62.562461,272.840.512.190.260.570.130.120.52031262.872.361.350.420080340.501.910.301.26H0.540.070.331.050.210700.680.20.031.380.850.180.540.580.220.130.030.080.09∑REE80.817.014.36347.7638436.950.740.86H中国煤化工0.870.07001CNMHG-002Ew/Eun0.030.030.040.050.03J Cent. South Univ Technol (2011)18: 1646-1653165110ag10LW-1(.72)Wwwww6(828)10218占烹月品弓日占占目旦8占易品弓日卤目REEREEFig5 PAAS-normalized ree pattens of limestones1-LW-1(7.72)2一LW2(7363-LW-3(7.354-LW4(7.50)5-LW-(753)LW6(8.28)1028占烹息岛宫白古自REE旦8占2月品弓日品占目Fig 7 Results of speciation model for groundwater fromREElimestone aquifer:(a)Ln(CO3);(b)LncO,Fig 6 Rock(average limestone)normalized groundwater fromlimestone aquiferLW-1 are 24.5% and 81.4%, respectively. In addition, therelative proporticf Ln( cO3)2relative to LREEs with NdRN/YbRN0. 26-0.53(average correlated with ph values, whereas the proportions ofof 0.40, RN means rock normalized), and shows weak to LnCo, are negatively correlated with pH values(Fig. 7)no Ce anomalies( Ce/Ce *RN-0.12-0.03 with average of For example, La(CO3) accounts for only 8.02% of-0.06). Additionally, the Eu/Eu*RN ranges from 0.55 to Lw-2 (pH-7.36)and 43.6% for LW-6(pH=8. 28),1.30 with average of 0.85. It is worth noting that thewhereas Lu(CO3)2 accounts for 9. 42% of Lw-6 andfractionation of REEs of groundwater normalized to 37. 6% ofLW-2PAAS and average limestone are different (e.g. thefractionation of La-Nd relative to Gd-Er is more obvious 5 Discussionin PAAS normalized REe pattems than averagelimestone normalized, with average NdsN/GdsN of 0.56 5.1 REE enrichment and fractionation of groundwaterwhereas NdRN/GdRN of 0. 78)Figure 6 demonstrates that Lw samples showsimilar REE patterns with their aquifer rocks (limestones)4.4 Solution complexationamong La-Nd and Gd-Er. However, Fig4 indicates thatThe results of inorganic solution complexation REe distribution patterns of the groundwater differ frommodelling for LW are shown in Fig.7. Only Ln(CO3) PAAS. Inspection of Fig4 reveals that the groundwaterand LnCo3(Ln means any lanthanide) had been samples have PAAS normalized REe patterns that arecollected because they were predicted to dominategrossly similar to those of seawater [22-23] except forgroundwater in this study(64.5%-998% of Ln can be Ce and Eu anomaliesexplained by these two species). It is observed that theMany中国煤化工 quifer materialproportions of Ln(CO3)2 increase from La to Lu, as the primarwhereas the proportions of LnCO3 decrease, forBecauseILCNMHintimate contactexample, the proportions of La(CO3)2 and Lu(CO3)2 in with limestones, the weathering or solid-liquid exchange1652J. Cent. South Univ. Technol (2011)18: 1646-1653reactions between groundwater and limestones represent more stable in low pH conditions [7, ll], and it will leadthe most likely source of REEs to the groundwater. It can to more negative Ce anomaly with pH increasing. In fact,be seen in Fig. 6 that the REe patterns of groundwater although the highest pH groundwater (Lw-6) has theand limestones are similar between La-Nd and Gd-Er, lowest Ce/Ce*sN value, the correlation between ph andindicating that the limestones play important roles in Ce/Ce*sN is not obvious(R=-0.38)controlling the ree patterns of groundwaterAlternatively, they may reflect a signature inheritedIn addition, the dramatic fractionationfrom the aquifer rock [7]. For example, groundwaterheavy REEs(Tm-Lu)indicates that other procsamples from aquifers composed of marine derivedengged (e.g. chemical reactionscarbonate rocks tend to obtain negative Ce anomaliesgroundwater and HREE-enriched minerals). The [22-23]. We had demonstrated that calcite playscorrelation analysis shows that Zr concentrations of important roles in controlling the fractionation of REesgroundwater are well correlated with 2REE(R=0.76) of groundwater, and then they might be also important inthan Sr concentrations (R=0. 22), indicating that controlling the Ce anomalies. The correlationterrigenous materials such as zircon play more important coefficients of Sr and Zr versus Ce/Ce"sN are 0.82 androles in controlling the REE concentrations of 0.63, respectively, indicating that either marine derivedgroundwater.However, for the correlation analysis of Sr, materials or terrigenous materials are important inZr versus NdsN/YbsN, they have R=0.60 and 0.48,controlling the Ce anomalies, although the former playsrespectively. Such results indicate that although the ree more important rolesconcentrations of groundwater can be controlled byterrigenous materials in the limestones, the Sr enriched 5.3 Application to water source discriminationminerals (e.g. calcite in limestone) play the mostThis study demonstrates that aquifer rocks, as wellimportant role in controlling the REE fractionation of as their mineral compositions, play important roles ingroundwater.controlling the REe characteristics of groundwaterThe fractionation of REEs of groundwater can also Because of the differences between aquifers( Table 1),be affected by solution and surface complexation the groundwater in each aquifer should be differentreactions [9, 24]. Speciation modeling shows that theTake Renlou Coal Mine in this study as an exampleHREEs of groundwater are predominantly complexed as The Quaternary aquifer is composed of mixed rocksLn(CO3)2, whereas LREEs are LnCO, dominant, and (including limestones, sandstones, etc), the coal-bearingthe proportions of Ln(CO, )2 increase with increasing the aquifer is mainly composed of sandstones(with minorrelative atomic mass(Fig.7). Because in neutral to limestones), whereas the Taiyuan Fm and Ordovicianslightly alkaline conditions, the particle or aquifer rock limestone aquifers are mainly composed of limestonessurface is negatively charged, the positively charged Considering the similarity of REE characteristicsLnCO3 species will be removed from the groundwater between aquifer rocks and groundwater, the groundwater[9]. Because HREEs are predominantly complexed as from Taiyuan Fm and Ordovician aquifers tend to inheritLn(CO3)2, they will be stabilized in groundwater, the marine derived signatures, and they will have theleading to the fractionation of L- and HREEs. In this lowest NdsN/YbsN(<0.5)and highest Y/Ho ratios(35)study, the highest concentration of Ln(CO3)2 sample [23]. Comparatively, the coal-bearing groundwater will(LW-6 with pH=8.28)having the highest NdsN/Ybsn show the highest positive Eu anomalies(Ew/Eu*sN>1)ratio might be an expressionbecause of the enrichment of plagioclase [5].Moreoverthey will be expected to have chondritic Y/Ho ratios (27)5.2 Ce anomalies[23]. Although groundwater from the Quaternary aquiferThe lW exhibits weak negative Ce anomalies when probably shows chondritic Y/Ho ratios(27-35), the lackormalized to Paas as well as average limestone ( table of obvious positive Eu anomalies(Ew/Eu*sN<1)can be3, Figs4 and 6). These negative Ce anomalies maycriminated from the coal-bearing groundwater.reflect oxidative conditions of the aquifer, whereby Ce" However, groundwater from the lowest Taiyuan Fm andis oxidized to less soluble Ce- [6]. However, field Ordovician aquifers are hard to be distinguished becausemeasurement indicates that the groundwater in the of their similarity of aquifer rocks and redox conditionsTaiyuan Fm limestone aquifer is in reducing condition so, other methods (e.g. major ions, isotopic and trace(En from -60 to-300 mV), which will lead Ce to be ce elements)are neededin groundwater, rather than leavingAnother possible explanation is that the Ce 6 Conclusionanomalies of groundwater reflect solubility differences中国煤化工of Ce redox species related to pH conditions in the1)TheCN MH Ge aquiaquifer system. The previous study revealed that Ce*is Renlou Coal Mine are CI-Ca Na water, withlfer InJ Cent. South Univ Technol (2011)18: 1646-16531653temperature(340-372C), circum-neutral pH (7.35[10] BIDDAU R BENSIMON M, CIDU R, PARRIAUX A Rare earth8. 28)and high TDs (1 746-2 849 mg/L);elements in groundwater from different Alpine aquifers []. Chemieder Erde Geochemistry, 2009, 69(4): 327-3392) The groundwater has higher REE concentrations (11 JOHANNESSON K H Rare earth elements in groundwater flow(P(Nd =0.006-0.010 ug/L) relative to groundwater withsystems[M]. Netherlands: Springer, 2005: 187-222circum-neutral pH, and shows HREEs enrichment [12] GUI He-rong. CHEN Lu-wang. Hydrogeochemistric evolution andrelative to LREEs and weak or no negative Ce anomaliesdiscrimination of groundwater in mining district [M]. Beijing:when normalized to PAAS. It has similar REE pattemsGeological Publishing House, 2007: 32-44. 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