a novel extraction chromatography and mc-icp-ms technique for

Chemical Geology 291 (2012) 3854

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Chemical Geology

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Research paper

A novel extraction chromatography and MC-ICP-MS technique for rapid analysis ofREE, Sc and Y: Revising CI-chondrite and Post-Archean Australian Shale(PAAS) abundances

Ali Pourmand a,b,, Nicolas Dauphas a, Thomas J. Ireland a

a Origins Laboratory, Department of the Geophysical Sciences and Enrico Fermi Institute, The University of Chicago, 5734 South Ellis Avenue, Chicago IL 60637, USAb Neptune Isotope Laboratory, Division of Marine Geology and Geophysics, The University of Miami, RSMAS, 4600 Rickenbacker Causeway, Miami, FL 33149, USA

Corresponding author. Tel.: +1 305 421 4384; fax:E-mail address: [email protected] (A. P

0009-2541/$ see front matter 2011 Elsevier B.V. Alldoi:10.1016/j.chemgeo.2011.08.011

a b s t r a c t
a r t i c l e i n f o
Article history:Received 2 March 2011Received in revised form 14 August 2011Accepted 24 August 2011Available online 30 August 2011

Edited by: K. Mezger

Keywords:CI-chondriteRare earth elementsLiBO2 flux fusionTODGA extraction chromatographyMC-ICP-MSPost-Archean Australian Shale (PAAS)

A new analytical protocol is introduced for rapid measurement of rare-earth elements (REE), Sc and Y in mete-oritic and geological materials bymulti-collection inductively coupled plasmamass spectrometry (MC-ICP-MS).A simple purification step was devised to reduce REE, Sc and Y abundances in commercial lithium metaborate(LiBO2) for low-blank flux fusion. Separation of the analytes from the rockmatrix was achieved by using a singleTODGA extraction chromatography step. A dynamicmulti-collector cup configurationwas developed tomeasureREE, Sc and Y using a desolvating nebulizer and standard-sample bracketing technique. To test the accuracy ofthis analytical protocol, we analyzed aliquots of USGS geological reference materials BHVO-1, BIR-1, BCR-2,PCC-1, W-2, G-2 and G-3, specifically selected to encompass a wide range of REE, Sc and Y concentrations andmineral compositions. Elemental abundances in reference materials are indistinguishable within analytical un-certainties from compilations of literature values analyzed by various ICP-MS techniques. The average externalreproducibility on REE, Sc and Y concentrations (reported as RSD=100standard deviation/average) was~2% based on replicates of G-3. With the exception of PCC-1, which has low REE concentrations, adjustmentsfor poly-atomic interferences and procedural blanks in the reference materials were negligible.In order to re-visit the terrestrial and cosmic abundances of REE, Sc and Y, aliquots of nine Post Archean Austra-lian Shales (PAAS), Allende (CV-3), Tagish Lake (C2-ungrouped), Alais (CI1), Orgueil (CI1) and Ivuna (CI1) me-teorites were measured using our new analytical procedure. The REE patterns of PAAS, normalized to the meanof CI-chondrites from this study, are smoother and show less dispersion compared with literature measure-ments. Eu/Eu*, LREE/HREE, and La/Sc ratios remain constant in these samples. The recommended PAAScomposition based on these new measurements is (in g g1): Sc=15.89, Y=27.31, La=44.56, Ce=88.25,Pr=10.15, Nd=37.32, Sm=6.884, Eu=1.215, Gd=6.043, Tb=0.8914, Dy=5.325, Ho=1.052, Er=3.075,Tm=0.4510, Yb=3.012 and Lu=0.4386. The REE pattern in Allende is similar to group II-type CaAl-richinclusions (CAIs) that typically show enrichment in light REE (LREE), depletion in heavy REE (HREE), andnegative and positive anomalies for Eu and Tm, respectively. The REE in Tagish Lake and Alais do not showsignificant fractionations and closely resemble the relatively flat pattern observed in Orgueil. Based on eighthigh-precision multi-collection ICP-MS measurements of Orgueil (n=5), Ivuna (n=2) and Alais (n=1), werecommend a new CI-composition for REE, Sc and Y normalization and refine the cosmic abundances of theseelements (in g g1): Sc=5.493, Y=1.395, La=0.2469, Ce=0.6321, Pr=0.0959, Nd=0.4854, Sm=0.1556,Eu=0.0599, Gd=0.2093, Tb=0.0378, Dy=0.2577, Ho=0.0554, Er=0.1667, Tm=0.0261, Yb=0.1694 andLu=0.0256.

+1 305 421 4632.ourmand).

rights reserved.

2011 Elsevier B.V. All rights reserved.

1. Introduction

Over the past two decades, inductively coupled plasma mass spec-trometry (ICP-MS) has increasingly become the preferred method fordetermination of REE, Sc and Y abundances in meteoritic and geolog-ical materials (Balaram, 1996; Eggins et al., 1997; Pin and Joannon,

1997; Potts, 1997; Jarvis, 1988; Robinson et al., 1999; Yu et al.,2001; Bayon et al., 2009). While most ICP techniques have utilizedsingle collector, sector-field or quadrupole mass spectrometers,multi-collector ICP-MS in conjunction with isotope dilution massspectrometry (IDMS) has only been recently explored for REE mea-surements (Baker et al., 2002; Kent et al., 2004). The ability to simul-taneously measure multiple isotopes with MC-ICP-MS allowstechniques such as isotope dilution and standard-sample bracketingto achieve more precise and accurate elemental concentrations. Con-current measurement of multiple isotopes minimizes the influence of

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39A. Pourmand et al. / Chemical Geology 291 (2012) 3854

fluctuations inherent in the plasma source and sample introductionsystems that otherwise limit precision and accuracy of the analysiswith single collector ICP-MS.

In order to improve the accuracy and precision of REE, Sc and Ymeasurements by MC-ICPMS, the following conditions must be ful-filled: 1) complete digestion of refractory phases and minerals inthe samples; 2) low procedural blanks; 3) separation of interferingmatrix, and 4) elimination of molecular (i.e., oxides and hydrides)and direct isobaric interferences on the mass of the analytes of inter-est. In the following contribution, we introduce a novel analytical pro-tocol to reduce REE, Sc and Y concentrations in commercial LiBO2 flux,which facilitates processing small aliquots (~1550 mg) of sampleswith concentrations as low as 10 ng g1. A novel extraction chroma-tography was also developed using a resin from Eichrom Inc. for REE,Sc and Y purification. The exceptional affinity of N,N,NN tetraoctyl-1,5-diglycolamide ligand (hereafter TODGA) for these elements hasmade this resin a preferred medium for separating the rock matrixthat interferes with REE, Sc and Y measurements during ICP-MS anal-ysis (Horwitz et al., 2005; Connelly et al., 2006; Sasaki et al., 2007;Pourmand and Dauphas, 2010). Our proposed procedure takes advan-tage of improved sample digestion with low-blank, high-temperatureLiBO2 fusion, a single TODGA extraction chromatography step forquantitative matrix separation, and a novel, dynamic multi-collectorcup configuration method that allows measurement of REE, Sc andY byMC-ICP-MS in a single sample solution. The entire analytical proce-dure, from sample fusion to MC-ICP-MS analysis, can be completed inless than a day. In order to examine the accuracy of our protocol, ele-mental concentrations and CI-normalized REE patterns for seven USGSreference materials are measured and compared with high-precisiondatameasured by various ICP-MS techniques from the literature. Finally,we present REE, Sc and Y abundances and REE fractionation patterns inaliquots of Post-Archean Australian Shales (PAAS), Allende (CV3), Tag-ish Lake (CI2-ungrouped), Orgueil (CI1), Alais (CI1) and Ivuna (CV1)meteorites with the aim to re-evaluate the terrestrial and cosmic abun-dances of these elements.

2. Method development

2.1. Materials

Concentrated, certified ACS Plus hydrochloric (HCl) and nitric(HNO3) acids from Fisher Scientific were distilled twice in sub-boilingquartz and PTFE Teflon stills. The working acid solutions were titratedwith calibrated sodium hydroxide solutions before use. High-puritywater from a Millipore Milli-Q system (resistivityN18 M cm1)was used for rinsing labware, extraction chromatography and acid di-lutions. Savillex PFA Teflon vials and beakers used for purification ofalkali flux and chromatography elutions were first cleaned in 50%HNO3 at 70 C, followed by boiling in aqua regia (HCl:HNO3 at 3:1).Platinum evaporation dishes were cleaned in a boiling, 4 mol L1

HCl solution. Pre-packed, 2-mL TODGA cartridges (resin mesh size:50100 m), connectors and a Plexiglas vacuum chamber are avail-able from Eichrom Inc. Polypropylene columns from Bio-rad wereused as loading reservoirs for cartridge chromatography. High-purity,8-mL graphite crucibles, LiBr non-wetting agent (Pure grade) and cer-tified multi-element REE, Sc and Y standard solutions were obtainedfrom SPEX CertiPrep. Commercially manufactured Puratronic lithiummetaborate powder (99.997% metals basis, cat# 10739) was pur-chased from Alfa Aesar.

2.2. Sample digestion

2.2.1. Purification of lithium metaborate fluxComplete dissolution of refractory minerals (such as garnet and

zircon) is a prerequisite for accurate and precise isotopic and elemen-tal analysis of terrestrial and meteoritic materials with solution-based

ICP-MS. Conventional methods that use hotplate or high-pressureParr Bombs and a mixture of HNO3HFHCLO4 (e.g., Eggins et al.,1997; Baker et al., 2002; Mahlen et al., 2008) are effective but cantake days to achieve complete dissolution of samples that containhighly refractory phases. High-temperature alkali flux fusion offers afaster and more efficient alternative to acid digestion, and the result-ing solution can be readily used for matrix separation by extraction orion-exchange chromatography (Bizzarro et al., 2003; Le Fevre andPin, 2005; Connelly, 2006; Pourmand and Dauphas, 2010; Dauphasand Pourmand 2011). Flux fusion also eliminates the need for multi-ple evaporation and acid conversion steps, which are commonly re-quired in acid dissolution protocols and can potentially result insample loss, contamination or elevated blank levels. In practice, how-ever, fewer studies have chosen flux fusion over acid dissolution be-cause of relatively higher blank levels associated with commerciallymanufactured flux material and incomplete recovery of the melt. Ina recent study, for example, Bayon et al. (2009) reported very highprocedural blanks (e.g., CeN2.7 ng) when using a Na2O2NaOH fluxmelting technique. Pourmand and Dauphas (2010) also found highlevels of actinides and high-field strength elements in three commer-cially available flux materials. While high blank levels are inconse-quential for the analysis of most terrestrial materials that have highREE, Sc and Y abundances, significant blank corrections in bulk mete-orites and some terrestrial rocks (such as peridotites), with concen-trations in a few parts per trillion, can lead to inaccurate results. Ifalkali flux fusion is to be successfully utilized with samples thathave low levels of REE, Sc and Y, the flux must be further purified toreduce blank contributions.

In order to address this need, a simple and highly efficient methodwas developed to remove these elements from commercially avail-able alkali flux materials using TODGA extraction chromatography.Approximately 60 g of Puratronic LiBO2 powder from Alfa Aesar wasdissolved at room temperature in 2 L of 3 mol L1 HNO3 stocked ina PFA Teflon bottle. Adding higher amounts of the flux will result inincomplete dissolution and precipitation of the flux on the resin.Three 2-mL Eichrom TODGA cartridges were stacked in tandem onthe vacuum chamber and 10-mL polypropylene columns were usedas loading reservoirs. The cartridge assembly was preconditionedwith 60 mL of 0.05 mol L1 HCl to remove residual REE, Sc and Y onthe resin, followed by 20 mL of MQ water and 20 mL of 3 mol L1

HNO3 to convert the resin to the loading acid concentration. The lith-ium metaborate flux solution was subsequently loaded to the car-tridge array and the eluent was collected in precleaned PFA Teflonbottles at elution rates of 34 mL min1. A total of five TODGA car-tridge arrays were used for 400 mL of flux solution per each array toavoid elution of REE, Sc and Y from the resin due to high load volume.

The purified LiBO2 was recovered in two steps. The solution wasfirst evaporated to a thin slab in increments of 200 mL in precleaned,250 mL PFA Savillex beakers. The beakers were capped usingthreaded closers with portholes to minimize contamination. TheLiBO2 slabs (~5 cm in diameter) were subsequently heated in acapped, 100-mL platinum evaporation dish inside a Thermoline fur-nace at 720 C for 1 h. This temperature is safely below the meltingpoint of LiBO2 (845 C), yet it is sufficiently high to allow complete re-moval of residual HNO3 and water from the flux slabs. Subsequenttests have shown that high-purity quartz crucibles may also be usedas a substitute for expensive platinum evaporation dishes for thisstep. Approximately 57 g of purified flux was recovered from 60 g oforiginal LiBO2 powder. The flux purification and recovery proceduresare summarized in Fig. 1. The effectiveness of this procedure in re-moving REE, Sc and Y from the flux material is discussed inSection 3.1.

2.2.2. Alkali flux fusionApproximately 1550 mg of USGS reference materials, PAAS and

homogenized meteorite powders were fused with ~450 mg of

1) 60 mL 0.05 M HCl2) 20 mL MQ-Water3) 20 mL 3M HNO3

4) Flux loaded in 3M HNO3

5) Load solution: Purified FluxVacuum range: 0.66-0.79 atm. Flow rate: 3-4 mL min-1

I. Flux dissolution II. Purification III. Recovery

Furnace dry-down in

capped 100 mL Pt dishes at 720 C for

1 hr

TODGA

TODGA

TODGA

Hot-platedry-down in 250 mL PFA beakers at 220 C for

2-3 hr

~ 60 g LiBO2

dissolvedin 2L

3M HNO3

TODGA

TODGA

TODGA

TODGA

TODGA

TODGA

TODGA

TODGA

TODGA

TODGA

TODGA

TODGA

Cleaning and conditioning

Fig. 1. Schematic protocol for removal of REE, Sc and Y from commercial lithium metaborate flux using Eichrom TODGA extraction chromatography. About 60 g Puratronic LiBO2was dissolved in 2 L of 3 mol L1 HNO3. The flux solution was loaded onto an array of TODGA cartridges. About 57 g of purified flux powder was recovered by evaporating theelute in 250 mL PFA beakers at 220 C on a hotplate, followed by heating the residual flux slabs in Pt evaporation dishes at 720 C in a furnace.

40 A. Pourmand et al. / Chemical Geology 291 (2012) 3854

purified LiBO2 flux. Previous fusion experiments showed that a flux:sample ratio of 6 or higher is required for complete digestion of ter-restrial and meteoritic materials and successful dissolution of themelt in 3 mol L1 HNO3 (Pourmand and Dauphas, 2010). The geolog-ical reference materials were specifically selected to cover a widerange of REE, Sc and Y concentrations, spanning three orders of mag-nitude. Three chips of the Ivuna meteorite (200800 mg) were sawnfrom larger pieces and cleaned in an ultrasonic bath for ~10 s withhigh-purity ethanol. The chips were dried and powdered separatelyin a sand-cleaned agate mortar under class-100 clean air. Powderedaliquots of Orgueil, Alais and Tagish Lake were rinsed with ethanoland digested without further processing. Detailed information aboutthe terrestrial and meteoritic samples can be found in Table 1. In ad-dition to the samples, an aliquot of the multi-element standard solu-tion was also fused with the flux and processed through the TODGAresin to establish chemical yields for the REE, Sc and Y on this resin.

Approximately 450 mg of LiBO2 was weighted onto an 8-mL high-purity graphite crucible. The sample powder was then transferred to adepression at the center of the flux using clean weighing paper. Thenext crucial step was the addition of about 60150 mg of a high-puri-ty LiBr non-wetting solution (Spex Certiprep) to prevent adhesion ofthe fusion melt to the graphite crucible and facilitate its quantitativetransfer for dissolution. The crucible containing the flux, sample pow-der and the non-wetting agent was capped prior to digestion to min-imize potential contaminations. Fusion was performed at 1070 Cinside a Thermoline furnace for 12 min and the melt was directlypoured into a 30-mL Savillex PFA vial containing 15 mL of3 mol L1 HNO3. In spite of the intense reaction between the meltand the liquid, sample loss does not occur during this stage as evi-denced by processing the multi-element standard solution (see Sec-tion 3.1). The vial containing small fragments of the fusion materialwas then placed on a Thermolyne Vortex at ~6000 rpm and completedissolution was usually achieved within a few minutes. The solutionswere inspected under the microscope and graphite particles wereidentified as the only remaining solid residues.

2.3. TODGA extraction chromatography

High-precision measurements of REE, Sc and Y with ICP-MS re-quire that the analytes of interest be free from matrix elements.

Following dissolution of the fusion melt, REE, Sc and Y were quantita-tively separated from major and trace elements using a single-stageTODGA extraction chromatography. The distribution coefficients(Kd = concentration in TODGA resin/concentration in equilibratedsolution) for REE on the TODGA resin are extremely high and exceed10,000 in 3 mol L1 HNO3 for most lanthanides. In contrast, the Kdsof all REE fall below 1 in 0.05 mol L1 HCl (Pourmand and Dauphas,2010). Such large differentials in the affinity of the TODGA resin forREE make it an ideal medium for separation of these elements fromthe rock matrix. Although Pourmand and Dauphas (2010) did not re-port distribution coefficients for Pr and Sc on the TODGA resin, theseelements were found to behave similarly to other REE, as shown byrecovery of the multi-element standard solution (see Section 3.1below).

The schematic protocol for high-purity LiBO2 fusion and TODGAextraction chromatography of REE, Sc and Y is shown in Fig. 2. Briefly,a 10-mL Bio-Rad polypropylene reservoir, a 2-mL TODGA cartridgeand two disposable connectors were assembled on the vacuum cham-ber in tandem. Vacuumwas regulated at 0.790.98 atm with a single-stage Venturi pump (Mcmaster Carr, Cat# 41605 K13). Flow rates forload/rinse solutions and elution of REE, Sc and Y were maintainedbelow 2 and 3 mL min1, respectively, by adjusting the vacuum.The 2-mL TODGA cartridge was preconditioned with 20 mL of0.05 mol L1 HCl to remove REE, Sc and Y from the resin, followedby 10 mL of MQ water and 10 mL of 3 mol L1 HNO3 to convert tothe loading acid solution. The sample was loaded to the reservoir in15 mL 3 mol L1 HNO3 and was followed by 12 mL of 3 mol L1

HNO3 to remove matrix elements. Residual major and transition ele-ments, including Ca, were stripped in 15 mL of 11 mol L1 HNO3. AllREE, Sc and Y were subsequently eluted in 30 mL of 0.05 mol L1 HClinto 50 mL centrifuge tubes for the reference materials and PAAS, and30-mL PFA Savillex vials for meteorites. The solutions containing thereference materials and PAAS were either gravimetrically diluted to0.45 mol L1 HNO3 or evaporated and diluted by a factor of 20200for analysis. Solutions containing REE, Sc and Y for meteorites wereevaporated to 12 L and diluted in 2 mL of 0.45 mol L1 HNO3prior to MC-ICP-MS analysis. In the case of direct dilution, care mustbe taken to ensure that the concentration of nitric acid in the samplesolution remains identical to the bracketing standard. Otherwise,measured concentrations may be inaccurate by as much as 10%.

Table 1USGS reference materials, Post-Archean Australian Shales and chondritic meteorites analyzed in this study. Aliquots of Ivuna were from homogenizing three separate chips thatweighed between 0.2 and 0.8 g. Orgueil AE came from homogenizing a chip of ~0.2 g, and Orgueil F and G from homogenizing one chip of 219 and two chips of 234, respectively.Digested powders weighed ~0.2 g. Total mass of Tagish Lake was 0.015 g, which came from homogenizing 34 g of this meteorite. The dissolved mass for all other samples was ap-proximately 0.05 g.

Sample type Group Source Collection ID

USGS reference materialBCR-2 (AB, n=2) Basalt, Columbia River, Oregon, USA BHVO-1 Basalt, Kilauea, Hawaii, USA BIR-1 (AB, n=2) Basalt, Reykavik Dolerite, Iceland PCC-1 Peridotite, Austin Creek, California, USA W-2 Diabase, Bull Run Quarry, Virginia, USA G-2 (AC, n=3) Granite. Sullivan Quarry, Rhode Island, USA G-3 (AE, n=5) Granite. Sullivan Quarry, Rhode Island, USA

Post-Archean Australian Shales (PAAS) AO-6 Amadeus Basin, Australia AO-7 Amadeus Basin, Australia AO-9 Amadeus Basin, Australia AO-10 Amadeus Basin, Australia AO-12 Amadeus Basin, Australia SC-7 Camp Hill, Canberra, Australia SC-8 Camp Hill, Canberra, Australia PL-1 Canning Basin, Australia PW-5 Perth Basin, Australia

MeteoritesAlais CI1 Field Museum C3_0067Allende A CV3 USNM, split 8, position 5 3529Allende B CV3 USNM, split 8, position 5 3529Ivuna A CI1 USNM 6630Ivuna B CI1 USNM 6630Ivuna C CI1 USNM 6630Orgueil A CI1 MNHN 219Orgueil B CI1 MNHN 219Orgueil C CI1 MNHN 219Orgueil D CI1 Universty of Chicago collection C3_1146Orgueil E CI1 Universty of Chicago collection C3_1146Orgueil F CI1 MNHN 219Orgueil G CI1 MNHN 234Tagish Lake C2-ung. Private collection


2.4. Multi-collection ICP-MS analysis of REE, Sc and Y

Elemental concentration measurements were performed on Ther-moScientificNeptuneMC-ICP-MS instruments at theOrigins Laboratoryof the University of Chicago and the Neptune Isotope Laboratory of TheUniversity of Miami. A comprehensive description of the Neptune in-strument can be found in Wieser and Schwieters (2005). The instru-ment's 9 Faraday collectors were utilized for measuring REE, Sc and Yconcentrations by standard-sample bracketing technique. The standardsolutions used to determine elemental concentrations were gravimetri-cally prepared from twobatches of certifiedmulti-element solution thatcontained all 14 REE, Sc and Y at ~10 g g1. The concentrations of allREE in the multi-element solutions were certified by SPEX CertiPrepand the results obtained using the two standard batches agree. Sampleand standard solutions were introduced to the plasma in 0.45 mol L1

HNO3 through an Apex-Q+Spiro TMD desolvating nebulizer (Elemen-tal Scientific Inc.) using a 100 L min1 self-aspirating PFA nebulizer.Argon and nitrogen were used as carrier and sweep gasses for the des-olvation inlet system.

One of the main difficulties in measuring elemental concentra-tions and isotopic ratios of REE by ICP-MS has been the presenceof polyatomic interferences with similar mass/charge ratios as REEanalytes, e.g., Ln+, LnO+ and LnOH+ (Evans and Giglio, 1993; Dulski,1994; Eggins et al., 1997; Baker et al., 2002; Raut et al., 2003). Wetook specific measures to minimize contributions from these interfer-ences; the REE isotopes listed in Table 2 were carefully selected toeliminate the influence of isobars. Following matrix removal, REE ox-ides remain as the only interfering species on the selected isotopes ofHREE during MC-ICP-MS analysis. Prior to measuring the samples,oxide contributions were determined by analyzing mono-elemental

standard solutions of REE. In order to detect and reliably measurethe oxides, the standard solutions were analyzed at a high concentra-tion of ~250 ng g1 with the Apex-Q+Spiro TMD desolvating sys-tem. As shown in Table 2, intensity ratios of REE oxide/REE rangedfrom 0.0034% for EuO+/Eu to 0.0976% for NdO+/Nd, with an averageof 0.03% across all REEs. At these levels, the oxide corrections on themeasured isotopes in natural samples were negligible and no correc-tions were required.

In order to measure 14 REE, Sc and Y in a single sample solution, anovel dynamicmethodwas developed usingfivemulti-collector config-urations. The arrangement of representative REE, Sc and Y isotopes andcorresponding collector configurations are shown in Table 3. A uniqueaspect of this technique is that 149Sm and 167Er isotopes are measuredin three collector configurations to allow normalization of LREE andHREE to middle REE (Sm-Er). This set-up is greatly advantageous oversingle-collector ICP-MS, as it minimizes the effect of plasma instabilityand fluctuations in the desolvation inlet system on REE ratiosmeasuredby standard-sample bracketing. Scandium-45 and 89Y were also mea-sured in two additional sub-configurations (3 and 4). Accommodatinga wide mass range that encompass 14 REE in 3 cup configurations wasmade possible by adjusting the zoom optics (Focus and Dispersion)and source lens parameters (Focus, Deflection and Shape) of theNeptune.

A gain calibration was performed for Faraday collectors at the be-ginning of each session. The analysis sequence began with measuringion intensities of each analyte in 0.45 mol L1 HNO3 solution. Thesame solution was also used for sample preparation and standard di-lutions. The data collection method consisted of 1 block of 5 cycleswith 4.2 s integration time and 3 s of idle time (5 s for Sc) in dynamicmode. A take-up time and signal stabilization of 90 s was

Table 2The REE, Sc and Y isotopes used for measuring concentrations by MC-ICP-MS. Isotopeswere selected specifically to avoid isobaric interferences. The contribution of oxide in-terferences to the intensity signal of REE was assessed by measuring REEO+/REE ratiosin ~250 ng g1 monoelemental standard solutions via ESI Apex Q+Spiro TMD deso-lvating nebulizer system. Average REEO+/REE contribution in standard solutions was0.03% and demonstrates the effectiveness of desolvation in removing REE oxides.Oxide interferences were negligible in the samples, which were analyzed at 10100times lower concentrations compared with the standards used to determine oxidelevels.

Isotope Isotope abundance (%) Interfering oxide Oxides (%)

45Sc 100.00 89Y 100.00 139La 99.91 140Ce 88.45 141Pr 100.00 146Nd 17.20 149Sm 13.82 151Eu 47.81 157Gd 15.65 141Pr16O 0.0762159Tb 100.00 143Nd16O 0.0976163Dy 24.90 147Sm16O 0.0067165Ho 100.00 149Sm16O 0.0067167Er 22.93 151Eu16O 0.0034169Tm 100.00 153Eu16O 0.0034173Yb 16.13 157Dy16O 0.0127175Lu 97.41 159Tb16O 0.0325

1) 20 mL 0.05 M HCl2) 10 mL MQ water3) 10 mL 3 M HNO3

4) Sample load in 3 M HNO3

5) Load solution: Matrix6) 12 mL 3 M HNO3: Matrix7) 15 mL 11 M HNO3: Ca8) 30 mL 0.05 M HCl: REEs

TOD

GA

Vacuum range: 0.79-0.98 atm. Flow rates: load and elution at < 2 mL min-1

Rinse at 3 mL min-1

Dissolve in 15 mL

3 M HNO3

Highpurityflux

fusion

I. Flux Fusion II. Matrix separation

Flux (~ 450 mg) +Sample (~ 50 mg) +60-150 mg LiBr solution in 8 mL graphite crucibles at 1070 C for 12 min

Cleaning and conditioning

Direct transfer of melt

Fig. 2. Schematic protocol for high-temperature LiBO2 flux fusion and separation of REE, Scand Y from interfering matrix with TODGA extraction chromatography. A homogenizedaliquot of the sample powder was fused at 1070 C with purified LiBO2 flux for 12 minin capped, high-purity graphite crucibles. About 60150 mg of LiBr non-wetting solutionwas used to facilitate quantitative transfer of the fusion melt. The melt was directly dis-solved in 15 mL of 3 mol L1 HNO3 and loaded to a pre-conditioned TODGA cartridge. Fol-lowing matrix removal, REE, Sc and Y were eluted in 30 mL of 0.05 mol L1 HCl.


implemented prior to data collection. The inlet system was rinsedwith 0.45 mol L1 HNO3 for 2 min between each run. This washtime was sufficient to eliminate memory effects from previous sam-ple and standard analyses. Signal intensities from the dilution acidwere subtracted online from procedural blanks, standard and sampleruns at the beginning of each sequence. Every sample measurementwas bracketed with two multi-element standard solution analysesand the REE, Sc and Y concentrations were calculated according tothe following relationship:

CA CS IS=IA 1

where CA and CS represent the concentrations in the sample and themulti-element standard, respectively, and IA and IS represent the in-tensities of the ion beams registered at the faraday detectors. Concen-trations are reported as the mean of up to 3 measurements in thesame sample solution over the course of the run session. All uncer-tainties in this study are reported as relative standard deviation inpercent (100*SD/ x, SD=standard deviation, x=average of sepa-rate digestions) unless otherwise noted.

3. Results and discussion

3.1. Procedural blanks and elemental recovery

In order to examine the effectiveness of flux purification in reduc-ing background levels of REE, Sc and Y, concentrations in purified andcommercial flux materials were determined. About 1 g of commercialand purified LiBO2 was dissolved in 25 mL of 3 mol L1 HNO3 and theanalytes were separated following the TODGA extraction chromatog-raphy procedure presented in Fig. 2. The blank results, shown inTable 4, reveal a dramatic decrease in nearly all REE, Sc and Y concen-trations from commercial to purified LiBO2. The signal intensities ofelements such as Gd, Tm and Lu were below the detection limits of

the Faraday cups in the purified flux solution and improvements forother elements ranged from a factor of ~6 for Ho to more than 6300for La.

During the course of this study, procedural blanks were processedand analyzed similarly to the samples using ~0.45 g of purified flux. Ref-erence materials, PAAS and meteorite samples were processed in threeseparate batches with blank levels slightly elevated for the secondand third batches. Total procedural blanks (Table 4) are based on thegeometric mean for 6 replicate measurements. The REE and Y abun-dances in the peridotite reference material PCC-1 are considerablylower compared with most (extra) terrestrial materials, and requiredrelatively higher blank adjustments (7.4% on average). Proceduralblank contributions to all other reference materials were up to twoorders of magnitude smaller for most elements, with highest adjust-ments made for G-3 at 0.05% on average. Average blank contributionfor PAAS samples was 0.07%. Adjustments to Allende (0.14%), TagishLake (0.86%), Ivuna (0.4%), Orgueil (0.31%) and Alais (1.2%) were alsoimplemented prior to calculating final concentrations.

In order to test the recovery of REE, Sc and Y, an aliquot of themulti-element standard solution (~10 g g1, see Table 4 for concen-tration details) was added to ~0.45 g of purified flux and processedthrough fusion and extraction chromatography similarly to the restof the samples. Elemental concentrations, compared against thesame multi-element standard solution, demonstrate quantitative re-covery for all elements (Table 4).

3.2. REE in geological reference materials and PAAS

In order to assess the accuracy of our analytical methodology, REE,Sc and Y concentrations from this study are compared with the meanof literature values for USGS reference materials BHVO-1 (n=11),BIR-1 (n=10), BCR-2 (n=6), PCC-1 (n=10) W-2 (n=7), G-2(n=10) and G-3 (n=1) referencematerials in Table 5. Literaturemea-surements were acquired by quadrupole, sector field high-resolution(HR-ICP) andmulti-collectionmass spectrometers using standard addi-tion/bracketing or isotope dilution techniques.With the exception of G-3, the abundances of elements in geological reference materials fromthis study are similar to the mean of literature values within analyticaluncertainties, and demonstrate the accuracy of our technique (Fig. 3).In the case of G-3, we found only one study that reports REE and Y

Table 3Faraday cup positions and zoom optics of the Neptune MC-ICP-MS. Measurement of 14 REE, Sc and Y was made possible by utilizing 9 faraday cups and a dynamic collector con-figuration. The intensity of REE measured in sub-configurations 1 and 2 were normalized to 149Sm and 167Er intensities from the Main configuration. This technique minimizes theeffect of fluctuations inherent in the plasma and the inlet system and improves precisions. The use of zoom optics is essential to optimize peak overlaps for 14 lanthanide isotopes. Atotal of 0.5 mL solution was consumed during each measurement using a 100 L min1 PFA nebulizer. Note that Focus and Dispersion voltages can vary depending on cup config-urations of the Neptune.

Configuration L4 L3 L2 L1 Axial H1 H2 H3 H4 Focus (V) Dispersion (V)

Main 149Sm 151Eu 157Gd 159Tb 163Dy 165Ho 167Er 2.0 0.0Sub config. 1 139La 140Ce 141Pr 146Nd 149Sm 15.0 67.5Sub config. 2 167Er 169Tm 173Yb 175Lu 10.0 38.6Sub config. 3 45Sc 0.0 0.0Sub config. 4 89Y 0.0 0.0


concentrations for this referencematerial; our concentrations appear tobe higher compared with those reported in Meisel et al. (2002) for thisreference material (Table 5.g). Considering quantitative recovery of allelements based on processing a multi-element standard solutionthrough fusion and TODGA extraction chromatography (Table 4), accu-rate concentrations for a nearly identical reference material, G-2, com-pared with values from 10 literature measurements (Table 5.f), andconsistency between five replicate analyses of G-3 (Table 5.g), we areconfident that the concentrations of G-3 presented in this study are ac-curate. The uncertainties on the mean of five replicate analyses of G-3range between RSD=1.7% for Sm and RSD=3.1% for Sc, with an aver-age of ~2% for all elements, and represent the overall precision of ouranalytical technique.

Baker et al. (2002) reported high-precision concentrations ofsome REE in BHVO-1, BCR-2 and BIR-1 by MC-ICP-MS. Those valueswere later revised by Kent et al. (2004) using a similar method ofacid digestion, ion exchange chromatography and isotope dilutionmass spectrometry. In spite of major differences between the analyt-ical techniques employed by Kent et al. (2004), and the protocol pre-sented here (flux fusion, extraction chromatography and standard-sample bracketing), the arithmetic mean of REE concentrations forBHVO-1 and BIR-1 (Table 5.ab) from this study are comparablewith those of Kent et al. (2004) within 0.4% and 0.2%, respectively.In the case of BCR-2 and W-2 (Table 5.c and e), the average concen-trations of REE, Sc and Y between the two studies are in agreementwithin 1% and 2%, respectively. Although, in principle, better preci-sions can be achieved by isotope dilution compared with standard-

Table 4Blanks and yields after flux fusion and extraction chormatography separation of REE, Scand Y using the TODGA resin. Concentrations in a gram of commercial (Alfa Aesar Pur-atronic LiBO2, 99.997% trace metals) and purified flux materials demonstrate major im-provements for Y, La, Ce, Gd and Yb after purification. Procedural blanks are based onthe fusion of approximately 0.45 g of purified flux in high-purity graphite crucibles.bDet. = Below the detection limit of the Neptune Faraday cups. MES: multi-elementstandard solution of REE, Sc and Y.

Element PuratronicLiBO2(pg g1)

PurifedLiBO2(pg g1)

Proceduralblank(n=6)(pg)

MES(g g1)

MES after fluxfusion and TODGAseparation(g g1)

Yield(%)

Sc b Det. b Det. 91 10.00 10.24 102.4Y 3089 13 472 9.95 10.02 100.7La 83,206 13 120 9.88 9.94 100.7Ce 6087 31 247 10.00 10.07 100.7Pr 89 4 53 10.00 10.07 100.7Nd 295 33 225 9.96 10.03 100.7Sm 66 8 75 9.88 9.95 100.7Eu 217 1 28 10.00 10.07 100.7Gd 2499 b Det. 88 9.97 10.04 100.7Tb 97 1 26 10.00 10.07 100.7Dy 98 7 84 10.00 10.06 100.6Ho 7 1 26 9.99 10.05 100.6Er 54 1 57 9.96 10.01 100.5Tm 3 b Det. 16 9.91 9.97 100.6Yb 644 2 58 10.00 10.06 100.6Lu 45 b Det. 18 9.94 9.99 100.5

sample bracketing technique, preparation and calibration of REEspikes can be more demanding than the multi-collection dynamicmethod presented here. Furthermore, mono-isotopic elements (Pr,Tb, Ho, Tm, Sc and Y) cannot be directly measured by IDMS. Additionof enriched spikes can also introduce interferences on some of themeasured isotopes (for example 149Sm and 153Eu spikes can causeoxide interferences on 165Ho and 169Tm, respectively, see Table 2).

REE abundances of Post-Archean Australian Shales are often usedfor normalization of REE patterns (Nance and Taylor, 1976; Taylorand McLennan, 1985). These abundances were obtained by spark-source mass spectrometry, which suffers from relatively poor preci-sion. In addition, some REEs in PAAS (Tm and Yb) were not actuallymeasured but instead, the abundances of these elements were de-rived by interpolation between neighbor REEs (Taylor and McLennan,1985). We have analyzed nine PAAS samples from four basins acrossAustralia (Table 1) using our new MC-ICP-MS technique and the re-sults, which include measured abundances of Tm and Yb, are pre-sented in Table 6. The normalized REE pattern for PAAS from thisstudy are smoother and overall, our data is of higher quality com-pared with those reported by Nance and Taylor (1976) (Fig. 4). Werecommend that these new values of PAAS be used for normalizationof REE concentration measurements.

Recently, Bendel et al. (2011) studied the REE patterns in a num-ber of bulk terrestrial rocks and raised the possibility of Tm, and toa lesser degree, Yb anomalies. On close inspection of the data, itcould be argued that a small Tm depletion may exist (Fig. 4) butgiven the analytical uncertainty of ~2% for Tm based on replicates ofG-3 reference material, and the uncertainties in the mean of CI-chon-drites (see Section 3.4), the potential Tm depletion cannot be con-vincingly resolved in these PAAS samples.

3.3. REE in carbonaceous chondrites

With the exception of volatile elements and Li that is burnt in theSun, the concentrations of most elements in CI carbonaceous chon-drites represent our best estimate of the solar nebula composition(Haskin et al., 1966; Evensen et al., 1978; Palme, 1988; Anders andGrevesse, 1989; Evans and Giglio, 1993; Lodders et al., 2009). Thesample digestion, extraction chromatography and multi-collectionICP-MS technique developed during this study were employed tomeasure REE, Sc and Y abundances in Allende (CV3), Tagish Lake(CI2-ungrouped), Orgueil (CI1), Alais (CI1) and Ivuna (CV1). Elemen-tal concentrations determined for these meteorites are compiled inTables 7 and 8 and their REE fractionations relative to the mean ofCI-chondrites will be discussed in the following sections. Resultsfrom this study will be also compared with previously published,high-precision values where data is available.

3.3.1. Allende (CV3)Two aliquots of bulk Allende powder from the Smithsonian Insti-

tute were analyzed and the results are shown in Table 7. A compari-son between REE abundances (Fig. 5), normalized to the mean ofCI-chondrites from this study, with bulk analysis of this meteorite

Table 5Rare-earth element, Y and Sc concentrations (g g1) in a) BHVO-1, b) BIR-1, c) BCR-2, d) PCC-1, e) W-2, f) G-2 and g) G-3 reference material from this study are compared with literature values measured by Quadrupole (Q), single-collectorhigh-resolution (SC), and multi-collection (MC) ICPMS techniques. RSD% = Relative standard deviation (100SD/average) for multiple analyses of the same sample. The concentrations of REE in PCC-1 were particularly difficult to measuredue to their exceptionally low abundances and relatively higher blank corrections. Concentrations of mono-isotopic elements (Pr, Tb, Ho and Tm) from the literature are not directly measured by isotope dilution mass spectrometry.

a. BHVO-1

Element [1] RSD% [2] RSD% [3] RSD% [4] RSD% [5] RSD% [6] RSD% [7] RSD% [8] RSD% [9] RSD% [10] RSD% [11] RSD% Lit. Mean RSD% This study

Sc 31.00 3.5 31.90 1.8 30.40 0.8 29.70 7.7 32.60 5.2 31.00 4.7 31.10 3.3 31.00Y 24.00 4.2 25.30 1.5 24.90 1.9 26.40 0.4 24.60 4.5 26.30 0.3 22.70 1.7 26.48 1.2 27.40 3.9 25.34 5.8 24.14La 15.50 3.6 15.31 0.5 15.50 1.5 16.00 1.0 15.41 0.3 15.40 0.5 15.60 4.0 15.10 1.1 14.90 0.9 15.13 1.9 16.00 1.4 15.44 2.2 15.08Ce 38.00 3.2 38.40 0.8 38.10 1.5 39.00 3.0 38.38 0.3 37.90 0.4 38.60 4.0 37.70 0.8 37.30 0.5 38.23 1.3 39.40 4.7 38.27 1.5 38.20Pr 5.500 3.7 5.460 0.8 5.590 1.6 5.650 1.7 5.411 0.3 5.300 0.5 5.270 4.0 5.260 0.7 5.200 0.8 5.580 0.7 5.720 1.7 5.449 3.2 5.390Nd 25.00 4.6 24.65 0.7 24.50 2.2 25.10 2.2 24.79 0.2 24.70 0.6 25.10 2.5 24.60 0.9 24.80 0.3 24.76 1.3 26.10 2.8 24.92 1.8 25.07Sm 6.230 4.9 6.070 1.1 6.000 1.9 6.260 3.1 6.097 0.3 6.130 0.8 6.270 3.0 6.130 0.6 6.040 1.3 6.300 1.9 6.360 2.2 6.172 1.9 6.089Eu 2.140 3.4 2.060 0.7 2.100 1.8 2.120 2.0 2.067 0.3 2.100 1.6 2.060 3.0 2.140 0.8 2.060 0.8 2.060 2.4 2.090 4.1 2.091 1.5 2.103Gd 6.350 6.6 6.260 1.8 6.600 2.4 6.260 3.1 6.300 0.3 6.390 2.3 6.300 3.0 6.390 1.3 6.520 0.8 5.710 1.9 6.280 2.2 6.305 3.6 6.317Tb 0.9400 5.2 0.9490 0.9 0.9400 3 0.9700 3.8 0.9590 0.8 0.9500 5.5 0.9260 1.2 0.9450 0.9 0.9300 0.0 1.0000 4.1 0.9509 2.3 0.9360Dy 5.280 5.3 5.260 0.9 5.400 2.3 5.340 2.6 5.363 0.3 5.380 1.8 5.410 3.5 5.340 1.3 5.440 1.2 5.280 1.7 5.510 1.8 5.364 1.4 5.394Ho 1.010 6.4 1.010 0.9 0.980 2.8 1.020 4.0 0.969 1.7 0.970 4.0 0.962 0.7 1.000 1.4 1.040 1.9 1.050 3.2 1.001 3.1 0.984Er 2.570 6.4 2.530 0.5 2.550 1.9 2.590 2.4 2.575 0.3 2.540 0.9 2.560 5.0 2.560 0.4 2.560 1.3 2.510 2.0 2.530 4.4 2.552 0.9 2.562Tm 0.3400 5.4 0.3400 2.9 0.3270 3.2 0.3300 6.5 0.3280 0.9 0.3320 0.9 0.3400 2.9 0.3500 4.8 0.3359 2.4 0.3320Yb 2.000 5.7 1.990 0.7 2.100 4.9 1.990 3.5 1.978 0.3 1.990 1.8 2.040 4.0 1.940 0.7 2.010 1.2 2.060 1.9 2.150 3.5 2.023 3.0 1.998Lu 0.2800 6.8 0.2850 1.2 0.2800 2.4 0.2800 3.7 0.2739 0.3 0.2710 2.1 0.2700 5.0 0.2760 1.4 0.2830 0.9 0.2900 3.4 0.3100 3.4 0.2817 3.9 0.2704[1] Robinson et al. (1999) SC-ICP-MS, [2] Barrat et al. (2000) ICP-QMS, [3] Dulski (2001) ICP-QMS, [4] Yu et al. (2001) SC-ICP-MS, [5] Kent et al. (2004) MC-ICP-MS, [6] Willbold and Jochum (2005) HR-ICP-MS, [7] Debaille et al. (2006) ICP-QMS, [8] Dia et al. (2006) ICP-QMS, [9] Makishima and Nakamura (2006) ICP-QMS, [10] Huang et al. (2007) ICP-QMS, [11] Hu and Gao (2008) ICP-QMS.

b. BIR-1

Element [1] RSD% [2] RSD% [3] RSD% [4] RSD% [5] RSD% [6] RSD% [7] RSD% [8] RSD% [9] RSD% [10] RSD% Lit.Mean

RSD% BIR-1 A BIR-1 B This study(n=2)

Sc 44.10 1.6 43.80 1.9 42.00 3.1 46.00 5.0 43.98 3.7 42.49 42.98 42.74Y 16.28 0.9 16.20 0.6 14.10 1.8 14.90 3.5 16.11 4.0 15.10 5.3 15.20 2.0 17.00 3.6 15.61 6.0 14.15 14.60 14.38La 0.6030 0.7 0.6040 1.2 0.6240 2.6 0.6300 5.5 0.6200 3.7 0.6330 4.0 0.6050 0.2 0.6100 4.9 0.6040 2.0 0.6000 5.0 0.6133 2.0 0.5968 0.5839 0.5904Ce 1.888 0.2 1.897 0.9 1.890 0.6 1.890 5.3 1.890 2.5 1.892 3.0 1.905 1.920 4.2 1.890 1.9 1.910 3.2 1.897 0.6 1.894 1.926 1.910Pr 0.3750 0.8 0.3780 1.1 0.3680 0.6 0.3800 4.6 0.3900 3.0 0.3704 5.0 0.3680 0.0 0.3800 2.6 0.3740 1.8 0.3720 1.5 0.3755 1.8 0.3685 0.3761 0.3723Nd 2.360 0.9 2.380 1.0 2.390 0.5 2.310 3.8 2.350 3.1 2.371 4.0 2.380 0.1 2.410 2.5 2.370 1.1 2.400 1.2 2.372 1.2 2.380 2.432 2.406Sm 1.115 1.7 1.117 1.5 1.090 0.3 1.070 2.6 1.080 4.9 1.069 1.0 1.092 0.1 1.100 1.8 1.090 1.4 1.102 0.7 1.092 1.5 1.073 1.101 1.087Eu 0.5210 0.9 0.5240 1.0 0.5150 0.3 0.520 3.4 0.5300 2.6 0.5035 3.0 0.5217 0.2 0.5200 5.8 0.5080 1.9 0.5300 1.1 0.5193 1.6 0.5198 0.5341 0.5270Gd 1.864 0.7 1.850 1.0 1.870 0.6 1.770 2.5 1.910 3.0 1.650 5.0 1.887 0.1 1.800 11.1 1.790 0.9 1.810 1.3 1.820 4.1 1.821 1.907 1.864Tb 0.3790 1.4 0.3790 1.3 0.3600 0.4 0.350 3.5 0.3600 3.0 0.3574 4.0 0.3500 5.7 0.3990 0.9 0.3660 1.2 0.3667 4.4 0.3553 0.3661 0.3607Dy 2.520 0.7 2.530 0.9 2.550 0.3 2.430 2.8 2.550 3.5 2.489 0.5 2.592 0.1 2.500 4.0 2.520 0.7 2.590 1.0 2.527 1.9 2.563 2.640 2.602Ho 0.5800 0.9 0.5850 1.1 0.5680 0.3 0.5500 3.5 0.5600 3.9 0.5521 2.0 0.5600 3.6 0.5590 0.6 0.5910 1.3 0.5672 2.6 0.5642 0.5801 0.5721Er 1.731 0.9 1.734 0.8 1.650 0.2 1.640 3.1 1.710 4.8 1.620 5.0 1.738 0.1 1.570 5.1 1.680 0.6 1.740 1.5 1.681 3.5 1.710 1.756 1.733Tm 0.2620 0.2 0.2400 4.7 0.250 4.4 0.2587 11.0 0.250 8.0 0.2400 1.8 0.2501 3.7 0.2486 0.2561 0.2523Yb 1.643 1.2 1.649 1.1 1.670 0.4 1.610 2.7 1.640 3.5 1.670 9.0 1.653 0.2 1.540 3.2 1.620 1.1 1.630 1.8 1.633 2.3 1.642 1.686 1.664Lu 0.2480 1.3 0.2470 1.0 0.2690 0.2 0.2400 3.9 0.2500 3.9 0.2635 3.0 0.2461 0.2 0.220 4.5 0.2410 1.0 0.2430 2.2 0.2468 5.4 0.2421 0.2497 0.2459[1] Garbe-Schonberg (1993) ICP-QMS, [2] Eggins et al. (1997) ICP-QMS, [3] Pin and Joannon (1997) ICP-QMS, [4] Robinson et al. (1999) SC-ICP-MS, [5] Dulski (2001) ICP-QMS, [6] Coogan et al. (2004) ICP-MS, [7] Kent et al. (2004) MC-ICP-MS, [8] Melluso et al. (2005) ICP-MS, [9] Willbold and Jochum (2005) SC-ICP-MS, [10] Bayon et al. (2009) HR-ICP-MS.

c. BCR-2

Element [1] RSD% [2] RSD% [3] RSD% [4] RSD% [5] RSD% [6] RSD% Lit. Mean RSD% BCR-2 A BCR-2 B This study (n=2)

Sc 32.00 6.3 32.50 4.9 33.41 1.0 36.00 4.9 33.48 5.3 31.81 32.61 32.21Y 35.30 3.8 37.33 3.4 36.15 0.6 37.05 1.4 40.10 2.4 37.19 4.9 33.54 32.66 33.10

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c. BCR-2

Element [1] RSD% [2] RSD% [3] RSD% [4] RSD% [5] RSD% [6] RSD% Lit. Mean RSD% BCR-2 A BCR-2 B This study (n=2)

La 24.94 0.5 25.60 1.2 25.19 2.4 24.59 1.3 24.36 2.7 26.00 2.7 25.11 2.5 25.14 24.50 24.82Ce 53.52 0.5 55.30 0.5 53.23 4.2 53.30 1.7 52.21 1.3 55.40 2.2 53.83 2.3 54.34 52.61 53.48Pr 6.756 0.7 6.760 0.5 6.900 2.9 7.040 1.0 6.797 1.6 7.070 0.6 6.887 2.0 6.922 6.675 6.798Nd 28.71 0.5 28.60 0.5 29.19 2.0 28.50 1.1 28.25 1.5 29.67 0.4 28.82 1.8 29.43 28.37 28.90Sm 6.534 0.5 6.410 0.2 6.590 1.7 6.680 1.5 6.698 1.3 6.760 2.7 6.612 1.9 6.604 6.441 6.522Eu 1.949 0.6 2.060 2.3 1.920 2.1 1.990 1.5 1.921 0.9 2.010 2.9 1.975 2.8 2.011 1.917 1.964Gd 6.727 0.6 6.680 0.8 6.690 2.2 6.240 1.4 6.838 1.2 7.070 0.5 6.708 4.0 6.863 6.716 6.790Tb 1.060 0.4 1.050 1.0 1.040 1.0 1.059 1.2 1.090 1.0 1.060 1.8 1.062 1.029 1.046Dy 6.441 0.4 6.330 0.7 6.440 2.0 6.200 1.8 6.607 1.2 6.580 0.8 6.433 2.4 6.553 6.335 6.444Ho 1.260 2.4 1.350 1.5 1.330 0.8 1.328 1.8 1.350 1.5 1.324 2.8 1.296 1.272 1.284Er 3.707 0.5 3.620 1.6 3.670 1.1 3.480 0.9 3.650 1.3 3.770 1.0 3.650 2.7 3.642 3.641 3.642Tm 0.5120 1.1 0.5200 1.9 0.516 1.1 0.5149 0.5159 0.5154Yb 3.348 0.5 3.360 2.4 3.350 2.7 3.350 1.5 3.436 0.9 3.400 2.0 3.374 1.1 3.318 3.375 3.347Lu 0.4961 0.4 0.5040 1.0 0.4800 4.2 0.5000 0.5080 0.9 0.5000 3.2 0.498 1.9 0.4817 0.4967 0.4892[1] Kent et al. (2004) MC-ICP-MS, [2] Willbold and Jochum (2005) SC-ICP-MS, [3] Barrat et al. (2007) SC-ICP-MS, [4] Huang et al. (2007) ICP-QMS, [5] Mori et al. (2007) ICP-QMS, [6] Bayon et al. (2009) SC-ICP-MS.

d. PCC-1

Element [1] RSD%

[2] RSD%

[3] RSD%

[4] RSD%

[5] RSD%

[6] RSD%

[7] RSD%

[8] RSD%

[9] RSD%

[10] RSD%

Lit. Mean RSD%

This study

Sc 9.000 7.6 8.0000 4.7 9.650 6.2 8.883 9.4 7.413Y 0.0870 5.3 0.0790 3.4 0.0770 0.7 0.0784 2.4 0.0770 2.3 0.0692 14.0 0.0781 7.3 0.0783La 0.0390 3.8 0.0290 7.4 0.0460 10.7 0.0330 3.0 0.0290 6.9 0.0290 3.4 0.0480 9.0 0.0501 2.2 0.0309 1.5 0.0315 9.0 0.0366 23.3 0.0348Ce 0.0570 1.8 0.0530 9.7 0.0528 1.8 0.0600 1.7 0.0540 3.7 0.0530 4.4 0.0710 6.0 0.0822 4.5 0.0598 0.6 0.0570 9.0 0.0600 15.9 0.0578Pr 0.0085 5.9 0.0068 8.3 0.0076 9.0 0.0076 1.3 0.0070 7.1 0.0076 3.6 0.0098 7.5 0.0088 2.4 0.0081 4.4 0.0065 13.0 0.0078 12.8 0.0075Nd 0.0300 3.3 0.0250 6.4 0.0260 2.5 0.0260 2.7 0.0300 6.7 0.0270 5.1 0.0320 4.0 0.0321 9.0 0.0256 1.5 0.0282 9.0 0.0282 9.5 0.0290Sm 0.0080 18.8 0.0050 50.2 0.0070 19.5 0.0049 8.2 0.0070 21.4 0.0060 13.6 0.0070 8.0 0.0060 4.9 0.0079 8.8 0.0053 19.0 0.0064 17.8 0.0061Eu 0.0018 5.6 0.0011 40.8 0.0009 22.7 0.0009 11.1 0.0017 17.6 0.0010 16.8 0.0020 8.0 0.0010 5.8 0.0006 4.3 0.0011 10.0 0.0012 37.6 0.0012Gd 0.0080 6.3 0.0061 19.7 0.0059 16.9 0.0053 9.4 0.0080 25.0 0.0055 4.1 0.0076 7.7 0.0053 5.9 0.0089 1.1 0.0062 29.0 0.0067 19.8 0.0070Tb 0.0015 6.7 0.0012 25.0 0.0011 16.7 0.0010 10.0 0.0014 14.3 0.0011 8.0 0.0016 6.2 0.0011 8.1 0.0015 5.6 0.0011 21.0 0.0013 17.4 0.0012Dy 0.0130 3.8 0.0087 14.1 0.0110 13.9 0.0085 5.9 0.0110 4.5 0.0095 7.1 0.0120 5.0 0.0096 4.4 0.0109 5.8 0.0099 9.0 0.0104 13.8 0.0100Ho 0.0038 1.3 0.0027 13.8 0.0030 7.6 0.0023 4.3 0.0030 13.3 0.0026 8.1 0.0031 7.6 0.0028 8.0 0.0031 1.3 0.0029 10.0 0.0029 13.5 0.0028Er 0.0123 4.1 0.0113 10.8 0.0117 8.3 0.0100 6.0 0.0130 15.4 0.0115 3.0 0.0120 4.0 0.0111 7.2 0.0110 0.1 0.0115 16.0 0.0115 7.0 0.0115Tm 0.0025 6.0 0.0028 7.4 0.0020 5.0 0.0027 5.6 0.0024 2.4 0.0027 7.7 0.0024 5.3 0.0024 2.2 0.0025 7.0 0.0025 9.5 0.0024Yb 0.0215 3.5 0.0213 6.7 0.0227 4.6 0.0200 3.5 0.0235 3.0 0.0205 2.9 0.0230 4.0 0.0217 5.1 0.0255 0.8 0.0233 10.0 0.0223 7.3 0.0224Lu 0.0049 3.1 0.0046 13.3 0.0047 4.9 0.0045 11.1 0.0054 3.7 0.0045 2.9 0.0050 6.2 0.0044 4.3 0.0049 1.2 0.0049 9.0 0.0048 6.2 0.0045[1] Ionov et al. (1992) ICP-QMS, [2] Eggins et al. (1997) ICP-QMS, [3] Robinson et al. (1999) SC-ICP-MS, [4] Jain et al. (2000) ICP-QMS. [5] Takazawa et al. (2000) ICP-QMS, [6] Dulski (2001) ICP-QMS, [7] Olive et al. (2001) ICP-QMS, [8] Qiet al. (2005) ICP-QMS, [9] Willbold and Jochum (2005) SC-ICP-MS, [10] Makishima and Nakamura (2006) ICP-QMS.

e. W-2

Element [1] [2] RSD% [3] [4] [5] RSD% [6] [7] Lit. Mean RSD% This study

Sc 36.00 36.20 2.6 35.00 36.10 36.10 35.88 1.4 32.94Y 23.00 22.80 0.8 21.90 20.10 20.11 20.19 21.35 6.5 19.58La 10.00 10.59 0.9 10.07 10.52 10.23 0.8 10.52 10.54 10.35 2.4 10.31Ce 23.00 23.08 0.7 22.79 23.20 22.80 0.5 23.22 23.26 23.05 0.8 23.23Pr 3.027 3.027 0.7 3.040 3.030 2.919 2.9 3.030 3.032 3.015 1.4 2.981Nd 13.00 12.95 0.5 12.90 12.91 12.71 0.6 12.91 12.94 12.90 0.7 13.07Sm 3.300 3.310 0.5 3.240 3.270 3.234 0.6 3.270 3.274 3.271 0.9 3.240Eu 1.000 1.0930 0.6 1.100 1.094 1.072 0. 60 1.090 1.096 1.078 3.3 1.109Gd 3.690 3.960 0.7 3.730 3.710 3.692 0.8 3.710 3.714 3.744 2.6 3.741Tb 0.6300 0.6220 0.7 0.6320 0.6500 0.6200 0.6160 0.6283 1.9 0.6077

(continued on next page)

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Table 5 (continued)

e. W-2

Element [1] [2] RSD% [3] [4] [5] RSD% [6] [7] Lit. Mean RSD% This study

Dy 3.600 3.790 1.1 3.830 3.810 3.825 0.7 3.810 3.822 3.784 2.2 3.887Ho 0.7600 0.7980 0.9 0.8000 0.8030 0.8000 0.8050 0.7943 2.1 0.7825Er 2.500 2.260 0.8 2.170 2.220 2.248 0.5 2.220 2.231 2.264 4.8 2.239Tm 0.3800 0.3270 0.3300 0.3280 0.3413 7.6 0.3170Yb 2.050 2.030 1.4 1.980 2.060 2.020 0.6 2.060 2.058 2.037 1.5 2.041Lu 0.3300 0.2990 1.4 0.3000 0.3010 0.2937 0.5 0.3000 0.3020 0.3037 3.9 0.2951[1] Govindaraju (1994) compilation, [2] Eggins et al. (1997) ICP-QMS, [3] Kelley et al. (2003) ICP-QMS, [4] Li et al. (2003) ICP-QMS, [5] Kent et al. (2004) MC-ICP-MS, [6] Bolhar et al. (2005) ICP-QMS, [7] Jupiter (2008) SC-ICP-MS.

f.G-2

Element [1] RSD% [2] [3] RSD% [4] RSD% [5] [6] RSD% [7] RSD% [8] [9] [10] Lit. Mean RSD% G-2 A G-2 B G-2 C This study(n=3)

RSD%

Sc 3.900 8.7 3.590 3.640 3.710 4.5 3.448 3.571 3.499 3.506 1.8Y 9.400 3.5 10.00 9.940 3.0 9.400 1.9 10.30 10.00 4.0 9.240 0.8 9.760 9.280 9.980 9.730 3.8 9.268 9.466 9.045 9.260 2.3La 87.00 2.8 89.20 84.36 11.0 88.90 1.0 88.60 89.60 3.5 88.00 89.60 79.70 85.80 87.08 3.6 88.28 88.99 89.31 88.86 0.6Ce 158.0 1.6 160.0 154.0 11.0 164.2 0.8 159.0 164.0 3.8 177.0 161.0 151.0 151.0 159.92 4.8 164.907 166.26 166.41 165.9 0.5Pr 16.30 3.0 17.00 17.35 8.0 16.81 0.7 16.50 16.70 3.8 17.00 2.3 16.90 15.90 17.70 16.82 3.0 16.60 16.73 16.69 16.67 0.4Nd 51.50 2.2 54.70 52.90 7.0 53.24 0.8 54.50 54.80 4.0 54.00 1.7 58.50 49.80 53.70 53.76 4.2 54.04 54.48 54.11 54.21 0.4Sm 6.800 2.1 7.330 7.010 7.0 7.170 1.5 7.260 7.480 4.0 7.130 0.8 7.250 6.950 7.360 7.174 2.9 7.206 7.283 7.096 7.195 1.3Eu 1.410 5.0 1.440 1.400 6.0 1.330 1.8 1.500 1.480 3.8 1.340 2.2 1.300 1.380 1.520 1.410 5.3 1.353 1.366 1.341 1.353 0.9Gd 4.100 4.0 4.490 4.390 6.0 4.030 1.7 5.300 4.080 4.2 4.080 1.1 4.460 4.370 5.360 4.466 10.9 4.514 4.598 4.456 4.523 1.6Tb 0.4900 8.6 0.4800 0.4500 6.0 0.4800 2.4 0.4900 0.4900 4.2 0.5120 0.4 0.520 0.4700 0.5300 0.4912 4.9 0.4754 0.4838 0.4622 0.4738 2.3Dy 2.080 3.3 2.300 2.170 5.0 2.210 1.6 2.410 2.320 4.4 2.240 1.7 2.260 2.040 2.340 2.237 5.2 2.207 2.244 2.131 2.194 2.6Ho 0.3500 3.8 0.3800 0.3500 5.0 0.3800 1.8 0.3900 0.3800 4.5 0.3560 0.9 0.3640 0.3500 0.3700 0.3670 4.1 0.3641 0.3707 0.3530 0.3626 2.5Er 0.8800 5.1 0.9600 0.8400 4.0 0.9100 1.8 1.020 0.9700 4.5 0.9040 0.6 1.020 0.8500 0.9700 0.9324 7.0 0.9220 0.9401 0.8978 0.9200 2.3Tm 0.1170 4.4 0.1200 0.1200 7.0 0.1200 2.4 0.1200 0.1250 5.1 0.1250 2.2 0.1220 0.1200 0.1200 0.1209 2.0 0.1197 0.1253 0.1179 0.1210 3.2Yb 0.7200 5.8 0.7300 0.7200 5.0 0.7400 1.8 0.7800 0.7400 4.4 0.7120 0.3 0.7140 0.6800 0.7300 0.7266 3.5 0.7467 0.7673 0.7335 0.7492 2.3Lu 0.1200 13.0 0.1000 0.1100 6.0 0.1000 1.9 0.1100 0.1070 5.0 0.0990 3.1 0.1100 0.1000 0.1000 0.1056 6.6 0.1021 0.1066 0.1015 0.1034 2.7[1] Dulski (2001) SC-ICP-MS, [2] Jiang et al. (2007) ICP-MS, [3] Madinabeitia et al. (2008) ICP-QMS, [4] Bolhar et al. (2005) ICP-QMS, [5] Zhu et al. (2009) ICP-QMS. [6] Meisel et al. (2002) ICP-QMS, [7] Willbold and Jochum (2005) SC-ICP-MS, [8] Wang et al. (2007) ICP-QMS, [9] Yu et al. (2001) SC-ICP-MS, [10] Huang et al. (2007) ICP-QM.

g. G-3

Element [1] RSD% A B C D E This study (n=5) RSD%

Sc 3.253 3.127 3.262 3.178 3.023 3.169 3.1Y 10.30 3.4 8.899 8.719 8.988 8.802 8.562 8.794 1.9La 92.40 1.5 88.74 86.10 89.72 89.36 85.87 87.96 2.1Ce 171.0 2.2 165.2 160.4 167.1 166.0 160.2 163.8 2.0Pr 17.40 2.5 16.55 16.10 16.72 16.70 16.09 16.43 1.9Nd 56.80 2.3 53.65 52.33 54.25 54.05 52.21 53.30 1.8Sm 7.690 2.4 7.049 6.912 7.161 7.029 6.868 7.004 1.7Eu 1.500 3.1 1.316 1.284 1.337 1.311 1.275 1.305 1.9Gd 4.070 3.1 4.403 4.336 4.503 4.403 4.299 4.389 1.8Tb 0.4700 3.1 0.4538 0.447 0.4631 0.4502 0.4393 0.4506 2.0Dy 2.230 2.9 2.072 2.044 2.107 2.052 1.999 2.055 1.9Ho 0.3700 2.8 0.342 0.3354 0.3457 0.3379 0.3286 0.3379 1.9Er 0.9400 3.0 0.871 0.8523 0.8753 0.8607 0.8346 0.8588 1.9Tm 0.1230 3.3 0.116 0.1137 0.1154 0.1137 0.1100 0.1137 2.0Yb 0.7400 3.5 0.729 0.7102 0.7274 0.7206 0.6947 0.7164 2.0Lu 0.1100 3.7 0.103 0.1002 0.1013 0.1013 0.0975 0.1006 1.9

[1] Meisel et al. (2002) ICP-QMS.

Table 5 (continued)

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Mea

n R

EE

co

nce

ntr

atio

ns,

US

GS

ref

eren

ce m

ater

ials

n

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aliz

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RE

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0.9

1.0

1.1

PCC-1

0.9

1.0

1.1

1.2BHVO-1

0.8

0.9

1.0

1.1

BCR-2

BIR-1

G-2

La

W-2

0.81.2

0.81.2

LuYbTmErHoDyTbGdEuSmNdPrCeLa LuYbTmErHoDyTbGdEuSmNdPrCe

Fig. 3. Abundances of REE in six reference materials from literature compilations are indistinguishable from those measured in this study within analytical uncertainties, and attestto the accuracy of the measurements. The error bars represent 1 SD on the mean of literature values.


from literature measurements (Jarosewich et al., 1987; Shinotsukaand Ebihara, 1997) demonstrates very similar fractionation patterns,with relative enrichment in LREE and depletion in HREE. These pat-terns along with a negative anomaly for Eu and a prominent positiveanomaly for Tm distinguish the Allende carbonaceous chondrite fromother meteorites. It must be noted that while the REE pattern inAllende A and B (Table 7) analyzed in this study are closely replicated,Eu depletion in the former is not as pronounced. Given that the USNM

Table 6The composition of Post-Archean Australian Shales (PAAS) based on nine samples. Uncertaisamples, indices reflective of secular composition changes, such as Eu/Eu* (Eu enrichmentratios, remain relatively constant for all PAAS samples.

PAAS

Element AO-6 AO-7 AO-9 AO-10 AO-12

Sc 13.55 14.97 14.88 17.15 20.18Y 21.80 23.64 22.01 25.79 27.80La 37.87 40.30 38.65 45.69 44.59Ce 75.23 78.27 74.56 87.48 82.50Pr 8.60 8.96 8.66 10.14 10.02Nd 31.46 32.29 31.50 37.01 37.01Sm 5.728 5.878 5.759 6.935 6.149Eu 0.990 1.031 1.002 1.264 1.115Gd 4.911 5.127 4.944 6.102 5.388Tb 0.720 0.761 0.720 0.861 0.857Dy 4.273 4.557 4.283 5.027 5.291Ho 0.839 0.910 0.844 0.982 1.064Er 2.446 2.687 2.477 2.865 3.121Tm 0.360 0.400 0.365 0.421 0.456Yb 2.419 2.703 2.459 2.819 3.064Lu 0.354 0.399 0.360 0.412 0.451Eu/Eu* 0.56 0.57 0.57 0.59 0.58LREE/ HREE 9.73 9.44 9.67 9.61 9.16La/Sc 2.79 2.69 2.60 2.66 2.21

powder is homogenized from a large piece of Allende, the origin of thisdiscrepancy remains unknown to us.

Fractionation patterns similar to those presented in Fig. 5 havealso been reported in group II-type CaAl-rich inclusions in carbona-ceous chondrites (Tanaka and Masuda, 1973; Martin and Mason,1974; Grossman, 1980; Mason and Taylor, 1982; MacPherson et al.,1988). Partial removal of refractory condensates and incomplete con-densation of most volatile elements have been proposed as possible

nty on the ratios is 2SD. While absolute concentrations are variable between individualfactor = EuN=

ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiSmNGdNp , N: normalized to CI-chondrites), LREE/ HREE and La/Sc

SC-7 SC-8 PL-1 PW-5 Mean (n=9)

14.18 15.31 14.21 18.61 15.8926.70 27.45 31.61 39.01 27.3143.08 44.52 42.77 63.53 44.5687.61 91.38 90.40 126.8 88.259.90 10.29 10.02 14.72 10.1536.75 38.28 36.82 54.78 37.326.835 7.141 7.240 10.29 6.8841.211 1.192 1.210 1.917 1.2155.983 6.218 6.588 9.127 6.0430.867 0.895 1.013 1.328 0.89145.135 5.299 6.243 7.816 5.3251.009 1.047 1.264 1.515 1.0532.911 3.044 3.814 4.314 3.0750.421 0.442 0.578 0.617 0.45102.774 2.926 3.916 4.030 3.0120.400 0.425 0.569 0.578 0.43860.57 0.54 0.53 0.60 0.570.029.45 9.44 7.81 9.21 9.281.173.04 2.91 3.01 3.41 2.810.67

10

100P

AA

S R

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th

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orm

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of

CI-

cho

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rite

s, t

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10

100

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

AO-6 AO-7 AO-10 AO-9 AO-12 SC-7 SC-8 PL-1 PW-5

PA

AS

RE

E c

on

cen

trat

ion

s, N

ance

an

d T

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r (1

976)

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f C

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on

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tes,

th

is s

tud

y

? ?

a

b

Fig. 4. Rare earth element patterns in Post-Archean Australian Shales from this study (a) are compared with results from Nance and Taylor (1976) (b). All values are normalized tothe mean of CI-chondrites from this study (Table 9). Normalized REE patterns from our study are smoother, particularly for HREE. Thulium and Yb, which are not reported in Nanceand Taylor (1976), are also presented. Although a small Tm depletion may be present, it cannot be resolved given the analytical uncertainty for the mean of CI-chondrites.

Table 7Concentrations of REE, Sc and Y (g g1) in Tagish Lake (CI2-ung), Allende (CV3), Ivuna (CI1) and Alais (CI1). Allende A and B are replicate measurements of Allende bulk powderfrom USNM. Ivuna A, B and C are separate analyses on different chips from this meteorite.

Element Tagish Lake(C2. ung)

Allende(CV3) A

Allende(CV3) B

Ivuna(CI1) A

Ivuna(CI1) B

Ivuna(CI1) C

Alais(CI1)

Sc 8.39 10.94 11.72 5.56 5.93 5.96 5.93Y 1.768 2.742 2.664 1.434 1.492 1.470 1.560La 0.3182 0.5628 0.5325 0.2720 0.2710 0.2623 0.2670Ce 0.7952 1.407 1.341 0.6998 0.6894 0.6724 0.6858Pr 0.1209 0.2184 0.20603 0.1054 0.1043 0.1017 0.1035Nd 0.6172 1.121 1.052 0.5379 0.5256 0.5164 0.5299Sm 0.1989 0.3562 0.33491 0.1681 0.1682 0.1653 0.1702Eu 0.0781 0.1232 0.11333 0.0638 0.0645 0.0634 0.0656Gd 0.2618 0.4433 0.45021 0.2094 0.2257 0.2225 0.2318Tb 0.0481 0.0801 0.08123 0.0383 0.0407 0.0396 0.0414Dy 0.3300 0.5389 0.54977 0.2480 0.2753 0.2730 0.2858Ho 0.0699 0.1078 0.10975 0.0504 0.0594 0.0581 0.0612Er 0.2113 0.3135 0.31955 0.1453 0.1787 0.1762 0.1847Tm 0.0333 0.0557 0.05457 0.0224 0.0287 0.0272 0.0288Yb 0.2206 0.3258 0.33086 0.1455 0.1833 0.1800 0.1882Lu 0.0319 0.0450 0.04698 0.0205 0.0300 0.0263 0.0292


Table 8Concentrations of REE, Sc and Y (g g1) in seven replicates of Orgueil (AG) from this study are compared with 6 literature values measured by thermal ionization mass spectrom-etry (TIMS) and ICP-MS techniques. Orgueil F and G are enriched in LREE and were not included in calculations of the mean of Orgueil and CI-chondrites (see Table 9). RSD% =Relative standard deviation (100SD/average). Isotope dilution analyses of REE from Nakamura (1974) do not include mono-isotopic elements (Pr, Tb, Ho and Tm).

Element [1] [2] [3] [4] [5] [6] Lit.Mean

RSD% A B C D E F G This studyMean (n=5)

RSD%

Sc 6.450 5.420 5.200 5.690 11.7 5.852 5.883 5.057 5.097 5.575 6.135 6.516 5.493 7.3Y 1.530 1.780 1.490 1.430 1.558 9.9 1.425 1.344 1.395 1.403 1.413 1.503 1.489 1.396 2.2La 0.2610 0.2440 0.2360 0.2360 0.2450 0.2370 0.2432 4.0 0.2417 0.2454 0.2521 0.2506 0.2454 0.3401 0.3170 0.2471 1.7Ce 0.6680 0.6210 0.6190 0.6230 0.6180 0.6020 0.6252 3.6 0.6240 0.6242 0.6472 0.6371 0.6306 0.8328 0.7797 0.6326 1.5Pr 0.0900 0.0958 0.0980 0.0940 0.0945 3.6 0.0947 0.0957 0.0980 0.0962 0.0964 0.1186 0.1176 0.0962 1.3Nd 0.4900 0.4610 0.4630 0.4490 0.4900 0.4670 0.4700 3.5 0.4864 0.4712 0.4966 0.4843 0.4909 0.5732 0.6004 0.4859 1.9Sm 0.1590 0.1480 0.1440 0.1510 0.1550 0.1510 0.1513 3.5 0.1570 0.1513 0.1589 0.1541 0.1579 0.1726 0.1847 0.1558 2.0Eu 0.0592 0.0581 0.0547 0.0554 0.0590 0.0608 0.0579 4.1 0.0601 0.0590 0.0610 0.0591 0.0613 0.0619 0.0685 0.0601 1.7Gd 0.2100 0.1980 0.1990 0.2010 0.2040 0.2060 0.2030 2.2 0.2062 0.2036 0.2142 0.2078 0.2138 0.2222 0.2359 0.2091 2.2Tb 0.0353 0.0390 0.0395 0.0376 0.0379 5.0 0.0382 0.0375 0.0382 0.0373 0.0387 0.0400 0.0413 0.0380 1.5Dy 0.2590 0.2440 0.2460 0.2100 0.2640 0.2580 0.2468 8.0 0.2636 0.2492 0.2608 0.2545 0.2628 0.2746 0.2782 0.2582 2.4Ho 0.0552 0.0530 0.0574 0.0577 0.0558 3.9 0.0565 0.0543 0.0554 0.0547 0.0568 0.0586 0.0586 0.0555 2.0Er 0.1710 0.1600 0.1620 0.1540 0.1550 0.1600 0.1603 3.8 0.1705 0.1611 0.1662 0.1660 0.1709 0.1787 0.1747 0.1669 2.4Tm 0.0220 0.0270 0.0268 0.0256 0.0254 9.1 0.0263 0.0254 0.0257 0.0258 0.0269 0.0271 0.0261 0.0260 2.2Yb 0.1770 0.1600 0.1660 0.1580 0.1790 0.1710 0.1685 5.2 0.1712 0.1601 0.1681 0.1719 0.1737 0.1838 0.1762 0.1690 3.2Lu 0.0262 0.0244 0.0245 0.0280 0.0262 0.0254 0.0258 5.2 0.0253 0.0241 0.0247 0.0257 0.0260 0.0276 0.0258 0.0252 3.0

[1] Nakamura (1974) TIMS, [2] Nakamura (1974) TIMS, [3] Shinotsuka and Ebihara (1997) ICP-MS, [4] Friedrich et al. (2002) ICP-MS, [5] Makishima and Nakamura (2006) ICP-QMS,[6] Makishima and Nakamura (2006) ICP-QMS.


mechanisms that may be responsible for the REE fractionationpatterns observed in these objects (Wnke et al., 1974; Boynton,1975; Davis and Grossman, 1979; Palme and Boynton, 1993; Palme,2000).

3.3.2. Tagish Lake (C2-ung)The average REE concentrations in Tagish Lake are about 24% higher

than the mean of CI-chondrites (Tables 7 and 9). Nevertheless, the REEpattern in this meteorite, shown in Fig. 6, is relatively flat. Tagish Lakeis a unique meteorite with trace-element patterns that differ from CMand CI chondrites (Brown et al., 2000; Friedrich et al., 2002; Mittlefehldt,2002). Rare earth elements in the sample from this study show slightlyhigher enrichment for all REE but less deviation from the mean com-pared with previous bulk measurements of this meteorite (Fig. 6). Al-though the sample quantity analyzed in this study was relatively small(15 mg), it came from 34 g of homogenized powder (Jadhav, 2009),which may explain the smoother REE pattern compared with previousmeasurements of this meteorite.

1.65

1.70

1.75

1.80

1.85

1.90

1.95

2.00

2.05

2.10

2.15

2.20

2.25

2.30

2.35

Allende A (this study)Shinotsuka and Ebihara

Alle

nd

e R

EE

co

nce

ntr

atio

ns

no

rmal

ized

to

mea

n o

f C

I-C

ho

nd

rite

s, t

his

stu

dy

La Ce Pr Nd Sm Eu

Fig. 5. Rare earth element patterns for two separate analyses of bulk Allende are compared wto the mean of CI-chondrites (Table 9). The REE pattern in Allende samples is similar to grouHREE, a negative anomaly in Eu and positive anomaly in Tm.

3.3.3. Orgueil, Alais and Ivuna (CI1)There have been more high-precision analyses of REE by ICP-MS and

thermal ionization mass spectrometry in bulk aliquots of Orgueil thanother primitive meteorites. This is mostly due to sample availability ofCI chondrites; the recovered mass of Orgueil was 14 kg compared withAlais (6 kg), Ivuna (705 g), Revelstoke (1 g) and Tonk (7.7 g). As a result,meteoritic estimates of REE, Sc and Y abundances in the solar system arelargely based on the analyses of Orgueil (Anders and Grevesse, 1989;Palme and Jones, 2003; Lodders et al., 2009).

The results for REE, Sc and Y concentrations in seven samples ofOrgueil homogenized from different chips of MNHN 219, 234 andthe University of Chicago collection C3_1146, are presented inTable 8. While five Orgueil measurements (AE) are indistinguishablefrom literature compilations within analytical uncertainties, twomeasurements on separate chips of Orgueil (F and G) show clear en-richment in LREE and Eu relative to the mean of CI-chondrites, asshown in Fig. 7a. A comparison with CI-normalized REE patternwith literature compilations (Fig. 7b) shows less scatter in REE

Allende B (this study)(1997) Jarosewich et al. (1987)

Gd Tb Dy Ho Er Tm Yb Lu

ith measurements of this meteorite from previous studies. Abundances are normalizedp-II CaAl inclusions in carbonaceous chondrites, with enrichment in LREE, depletion in

Table 9Recommended mean of CI-chondrite concentrations (g g1) for REE, Sc and Y based on MC-ICP-MS measurements of 8 CI-chondrites (five Orgueil (AE), two Ivuna (B and C) andone Alais) are compared with most commonly cited literature compilations. The anomalous values for Ivuna A and Orgueil F and G are not included. The abundances for Alais andIvuna samples are adjusted to the mean of Orgueil. RSD% = Relative standard deviation (100SD/average) based on Orgueil AE measurements.

Element [1] [2] [3] [4] Estimatedaccuracy%

[5] Estimatedaccuracy%

This study(n=8)

RSD%

Sc 5.800 5.820 5.920 5.900 3 5.900 5 5.493 5.6Y 1.440 1.560 1.570 1.560 3 1.530 10 1.395 1.9La 0.2340 0.2347 0.2370 0.2450 5 0.2420 5 0.2469 1.5Ce 0.6160 0.6032 0.6130 0.6380 5 0.6220 5 0.6321 1.3Pr 0.0929 0.0891 0.0928 0.0964 10 0.0946 7 0.0959 1.2Nd 0.4570 0.4524 0.4570 0.4740 5 0.4710 5 0.4854 1.5Sm 0.1490 0.1471 0.1480 0.1540 5 0.1520 5 0.1556 1.6Eu 0.0560 0.0560 0.0563 0.0580 5 0.0578 5 0.0599 1.4Gd 0.1970 0.1966 0.1990 0.2040 5 0.2050 5 0.2093 1.8Tb 0.0355 0.0363 0.0361 0.0375 10 0.0384 7 0.0378 1.3Dy 0.2450 0.2427 0.2460 0.2540 5 0.2550 5 0.2577 2.0Ho 0.0547 0.0556 0.0546 0.0567 10 0.0572 7 0.0554 1.6Er 0.1600 0.1589 0.1600 0.1660 5 0.1630 5 0.1667 1.9Tm 0.0247 0.0242 0.0247 0.0256 10 0.0261 7 0.0261 1.8Yb 0.1590 0.1625 0.1610 0.1650 5 0.1690 5 0.1694 2.5Lu 0.0245 0.0243 0.0246 0.0254 10 0.0253 5 0.0256 4.4

[1] Wasson and Kallemeyn (1988), [2] Anders and Grevesse (1989), [3] McDonough and Sun (1995), [4] Palme and Jones (2003), [5] Lodders et al. (2009).


patterns in the data from our study. The uncertainties (RSD%) on REE,Y and Sc concentration based on five replicate analyses of Orgueil AEare also generally smaller than those calculated based on the mean of6 literature measurements.

With the exception of an apparent small enrichment in Lu, the REEpattern of Alais is quite similar to Orgueil with an overall enrichmentof about 7% relative to the mean of CI-chondrites (Fig. 7a).

The REE abundances in three chips of Ivuna (A, B and C) are quite var-iable. As shown in Fig. 8, two of the analyzed chips have almost flat REEpatterns (B and C) while Ivuna A is characterized by a significant deple-tion in HREE. Interestingly, the REE abundances for Ivuna from Lodders(2003) form an entirely different pattern, with overall depletion inREE, negative anomalies for Tb and Tm and a positive anomaly for Ho.The deviations from a flat pattern observed in some Ivuna specimenscould result from REE redistribution by aqueous fluids on the parent-body of CI-chondrites. The petrographic texture of CI-chondrites showsgreat abundance of microbreccias with a wide range of mineralogicalcompositions. It is indeed well documented that REE and actinides are

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Fig. 6. The abundances of REE in Tagish Lake from this study, normalized to mean of CI-chondLake is geochemically different from CI-chondrites, it shows a similarly flat pattern. The sawhich may explain the relatively smooth pattern compared with others.

not distributed homogenously and are concentrated in trace phasessuch as apatite (phosphates) and merrillite in CI and other groups ofchondrites (Rocholl and Jochum, 1993; Goreva andBurnett, 2001;Morloket al., 2006; Bouvier et al., 2008).

3.4. Revised REE, Sc and Y in CI-chondrites

AlthoughAlais and two Ivuna chips (B andC) are generally enriched inall REE relative to the mean of CI chondrites, REE ratios in these samplesdo not show fractionations that significantly deviate from the flat patternseen in Orgueil AE and themean of CI-chondrites from literature compi-lations (Tables 8 and9). The patterns for these CI-chondrites are very sim-ilar to Tagish Lake (Fig. 6),which came from34 gof homogenizedpowderand is not affected by inhomogeneity inherent to small sample sizes. Afteradjusting the abundances of Alais and Ivuna B and C to the mean ofOrgueil AE, we propose new, fiducial values for the concentrations ofREE, Sc and Y in CI-chondrites based on the average of MC-ICP-MS mea-surements in Orgueil (5), Alais (1), and Ivuna (2), while excluding the

et al. (2000) Friedrich et al. (2002)

Gd Tb Dy Ho Er Tm Yb Lu

rites (Table 9), are compared with previous analyses of this meteorite. Although Tagishmple analyzed in this study came from homogenizing 34 g of Tagish Lake meteorite,

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Orgueil A (MNHN 219) Orgueil B (MNHN 219) Orgueil C (MNHN 219)Orgueil D (C3_1146) Orgueil E (C3_1146) Alais FM C3_0067Orgueil F (MNHN 219,) different chip Orgueil G (MNHN 234)

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Nakamura (1974) Shinotsuka et al. (1997) Friedrich et al. (2002)

Makishima and Nakamura (2006) Makishima and Nakamura (2006) Nakamura (1974)

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Fig. 7. a) The REE patterns in Alais and seven samples of Orgueil are compared. Abundances are normalized to the mean of CI-chondrites (Table 9). While Orgueil AE show asmooth pattern and their abundances are closely replicated, Orgueil F and G show varying degrees of enrichment, particularly in LREE. These samples were not included in calcu-lation of the mean of CI-chondrites in this study. Rare earth element abundances in Alais are enriched by an average of 7% compared with the mean of Orgueil AE with slightlyhigher enrichment of HREE compared with LREE. b) Six literature measurements by ICP-MS and TIMS. Isotope dilution results from Nakamura (1974) do not include mono-isotopicelements Pr, Tb, Ho and Tm. Literature data for Orgueil shows more scatter than those measured in this study.


outliers Ivuna A, Orgueil F and G. The values listed in Table 9, define thecosmic abundances of these elements and are recommended as referenceconcentrations to normalize REE, Sc and Y abundance patterns of terres-trial and extraterrestrialmaterials. Our recommendedREE concentrationsand literature compilations for CI-chondrites that are commonly used forREE normalization are in good agreement within estimated accuraciesreported by Palme and Jones (2003) and Lodders et al. (2009), with im-proved uncertainties from our study (Table 9). The average ratio (byweight) for the twin elements Y and Ho for CI-chondrites derived hereis 25.20.2 (2 of the mean), which is slightly lower but comparableto previous estimates of Y/Ho for carbonaceous chondrites (e.g., 25.940.08; Pack et al., 2007).

4. Summary

1. A simple purification procedure is developed to reduce REE, Sc and Yblank levels in commercial LiBO2 flux by up to 3 orders ofmagnitude.Homogenized aliquots of terrestrial reference materials, PAAS and

meteorite samples were digested using low-blank LiBO2 fusion andREE, Sc and Y were separated from the matrix with a single TODGAextraction chromatography step. A newmethod was also developedto take advantage of 9 Faraday collectors, source lens voltage adjust-ments and zoom optics on the Neptune MC-ICP-MS for measure-ment of REE, Sc and Y in a single sample solution, whileminimizing the effect of fluctuations in the Ar plasma and inlet sys-tems. An Apex-Q+Spiro TMD desolvation system interfaced withthe Neptune rendered the corrections for polyatomic interferenceson heavy rare earth elements negligible. The entire procedure fromsample digestion to data collection can be completed in a day.

2. The accuracy of the proposed procedurewas tested by comparing REE,Sc and Y concentrations in USGS reference materials BHVO-1, BCR-2,BIR-1, PCC-1, W-2 and G-2 with ICP-MS and TIMS data from the liter-ature. Procedural blank corrections were negligible for BHVO-1, BCR-2, BIR-1, W-2, G-2 and G-3. Higher blank corrections for PCC-1 weredue to exceptionally low REE concentrations in this peridotite refer-ence material. The elemental concentrations and CI-normalized REE

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Ivuna (CI1) A Ivuna (CI1) B Ivuna (CI1) C Ivuna (CI1) Lodders (2003)

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Fig. 8. The CI-chondrite normalized patterns (Table 9) of REE in three chips of Ivuna are compared. With the exception of an apparent positive anomaly for Lu in Ivuna B, the REEpatterns in Ivuna B and C are relatively flat. In contrast, Ivuna A shows distinct fractionations in HREE. The normalized REE pattern in a sample of Ivuna from Lodders (2003) showsan entirely different fractionation pattern, with negative anomalies for Tb and Tm and a positive Ho anomaly. The observed deviations in some of Ivuna specimens may be due toheterogeneous distribution of REE in different mineralogical phases (such as phosphates) in some CI-chondrites.


patterns in reference materials from our study were indistinguishablefrom literature values within uncertainties and attest to the accuracyof our analytical technique. The REE concentrations of PAAS were an-alyzed, yielding REE patterns that are smoother and more completethan previous studies, which did not report measured values for Tmand Yb. We recommend that these new values be used to definePAAS for normalization purposes.

3. Rare-earth element concentrations were determined in primitivechondrites Orgueil (CI1), Alais (CI1) and Ivuna (CI1), as well asAllende (CV3) powder and Tagish Lake (C2-ung). The fractionationpattern of REE in Allende was similar to group II-type CAI, with en-richment in LREE, depletion in HREE, negative Eu and positive Tmanomalies. Out of the 11 CI-chondrite measurements, 8 show verysimilar REE patterns, while one chip of Ivuna and two chips ofOrgueil demonstrate significant shifts in LREE and HREE. Theseanomalous patterns may be the result of REE fractionation duringparent-body alteration and redistribution of REE in trace carrierphases such as apatite and merrilite. Excluding these outliers, werecommend revised values for REE, Sc and Y concentration of CI-chondrites and refine the solar abundances of these elements.

Acknowledgements

The authorswould like to thank Junjun Zhang for assistancewith pu-rification of commercial LiBO2 flux. This work was supported by a Pack-ard fellowship and NASA through grants NNG06GG75G andNNX09AG59G to N.D. Discussions with Jean-Alix Barrat, who sharedwith us a preprint of his work on REE in CI-chondrites, and AndreasPack regarding Y/Ho ratios, were greatly appreciated. We are gratefulto Roberta Rudnick and Frdric Moynier for making powder aliquotsof PAAS and Tagish Lake available for this study, respectively. Additionalmeteorite samples were generously provided by the FieldMuseum,Mu-seum National d'Histoire Naturelle and the Smithsonian Museum.

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