Chemical Geology 291 (2012) 38–54

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Chemical Geology

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Research paper A novel extraction chromatography and MC-ICP-MS technique for rapid analysis of REE, 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, USA b Neptune Isotope Laboratory, Division of Marine Geology and Geophysics, The University of Miami, RSMAS, 4600 Rickenbacker Causeway, Miami, FL 33149, USA article info abstract

Article history: A new analytical protocol is introduced for rapid measurement of rare-earth elements (REE), Sc and Y in mete- Received 2 March 2011 oritic and geological materials by multi-collection inductively coupled plasma mass spectrometry (MC-ICP-MS). Received in revised form 14 August 2011 Asimplepurification step was devised to reduce REE, Sc and Y abundances in commercial lithium metaborate Accepted 24 August 2011 (LiBO ) for low-blank flux fusion. Separation of the analytes from the rock matrix was achieved by using a single Available online 30 August 2011 2 TODGA extraction chromatography step. A dynamic multi-collector cup configuration was developed to measure Edited by: K. Mezger REE, Sc and Y using a desolvating nebulizer and standard-sample bracketing technique. To test the accuracy of this analytical protocol, we analyzed aliquots of USGS geological reference materials BHVO-1, BIR-1, BCR-2, Keywords: PCC-1, W-2, G-2 and G-3, specifically selected to encompass a wide range of REE, Sc and Y concentrations and CI-chondrite mineral compositions. Elemental abundances in reference materials are indistinguishable within analytical un- Rare earth elements certainties from compilations of literature values analyzed by various ICP-MS techniques. The average external fl LiBO2 ux fusion reproducibility on REE, Sc and Y concentrations (reported as RSD=100×standard deviation/average) was TODGA extraction chromatography ~2% based on replicates of G-3. With the exception of PCC-1, which has low REE concentrations, adjustments MC-ICP-MS for poly-atomic interferences and procedural blanks in the reference materials were negligible. Post-Archean Australian Shale (PAAS) 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 mean of CI-chondrites from this study, are smoother and show less dispersion compared with literature measure- ments. Eu/Eu*, ΣLREE/ΣHREE, and La/Sc ratios remain constant in these samples. The recommended PAAS composition based on these new measurements is (in μgg−1): 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 Ca–Al-rich inclusions (CAIs) that typically show enrichment in light REE (LREE), depletion in heavy REE (HREE), and negative and positive anomalies for Eu and Tm, respectively. The REE in Tagish Lake and Alais do not show significant fractionations and closely resemble the relatively flat pattern observed in Orgueil. Based on eight high-precision multi-collection ICP-MS measurements of Orgueil (n=5), Ivuna (n=2) and Alais (n=1), we recommend a new CI-composition for REE, Sc and Y normalization and refine the cosmic abundances of these elements (in μgg−1): 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 and Lu=0.0256. © 2011 Elsevier B.V. All rights reserved.

1. Introduction 1997; Potts, 1997; Jarvis, 1988; Robinson et al., 1999; Yu et al., 2001; Bayon et al., 2009). While most ICP techniques have utilized Over the past two decades, inductively coupled plasma mass spec- single collector, sector-field or quadrupole mass spectrometers, trometry (ICP-MS) has increasingly become the preferred method for multi-collector ICP-MS in conjunction with isotope dilution mass determination of REE, Sc and Y abundances in meteoritic and geolog- spectrometry (IDMS) has only been recently explored for REE mea- ical materials (Balaram, 1996; Eggins et al., 1997; Pin and Joannon, surements (Baker et al., 2002; Kent et al., 2004). The ability to simul- taneously measure multiple isotopes with MC-ICP-MS allows techniques such as isotope dilution and standard-sample bracketing ⁎ Corresponding author. Tel.: +1 305 421 4384; fax: +1 305 421 4632. to achieve more precise and accurate elemental concentrations. Con- E-mail address: [email protected] (A. Pourmand). current measurement of multiple isotopes minimizes the influence of

0009-2541/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.chemgeo.2011.08.011 A. Pourmand et al. / Chemical Geology 291 (2012) 38–54 39

fluctuations inherent in the plasma source and sample introduction ICP-MS. Conventional methods that use hotplate or high-pressure systems that otherwise limit precision and accuracy of the analysis Parr Bombs and a mixture of HNO3–HF–HCLO4 (e.g., Eggins et al., with single collector ICP-MS. 1997; Baker et al., 2002; Mahlen et al., 2008) are effective but can In order to improve the accuracy and precision of REE, Sc and Y take days to achieve complete dissolution of samples that contain measurements by MC-ICPMS, the following conditions must be ful- highly refractory phases. High-temperature alkali flux fusion offers a filled: 1) complete digestion of refractory phases and minerals in faster and more efficient alternative to acid digestion, and the result- the samples; 2) low procedural blanks; 3) separation of interfering ing solution can be readily used for matrix separation by extraction or matrix, and 4) elimination of molecular (i.e., oxides and hydrides) ion-exchange chromatography (Bizzarro et al., 2003; Le Fevre and and direct isobaric interferences on the mass of the analytes of inter- Pin, 2005; Connelly, 2006; Pourmand and Dauphas, 2010; Dauphas est. In the following contribution, we introduce a novel analytical pro- and Pourmand 2011). Flux fusion also eliminates the need for multi- tocol to reduce REE, Sc and Y concentrations in commercial LiBO2 flux, ple evaporation and acid conversion steps, which are commonly re- which facilitates processing small aliquots (~15–50 mg) of samples quired in acid dissolution protocols and can potentially result in with concentrations as low as 10 ng g− 1. A novel extraction chroma- sample loss, contamination or elevated blank levels. In practice, how- tography was also developed using a resin from Eichrom Inc. for REE, ever, fewer studies have chosen flux fusion over acid dissolution be- Sc and Y purification. The exceptional affinity of N,N,N′N′ tetraoctyl- cause of relatively higher blank levels associated with commercially 1,5-diglycolamide ligand (hereafter TODGA) for these elements has manufactured flux material and incomplete recovery of the melt. In made this resin a preferred medium for separating the rock matrix a recent study, for example, Bayon et al. (2009) reported very high that interferes with REE, Sc and Y measurements during ICP-MS anal- procedural blanks (e.g., CeN2.7 ng) when using a Na2O2–NaOH flux ysis (Horwitz et al., 2005; Connelly et al., 2006; Sasaki et al., 2007; melting technique. Pourmand and Dauphas (2010) also found high Pourmand and Dauphas, 2010). Our proposed procedure takes advan- levels of actinides and high-field strength elements in three commer- tage of improved sample digestion with low-blank, high-temperature cially available flux materials. While high blank levels are inconse-

LiBO2 fusion, a single TODGA extraction chromatography step for quential for the analysis of most terrestrial materials that have high quantitative matrix separation, and a novel, dynamic multi-collector REE, Sc and Y abundances, significant blank corrections in bulk mete- cup configuration method that allows measurement of REE, Sc and orites and some terrestrial rocks (such as peridotites), with concen- Y by MC-ICP-MS in a single sample solution. The entire analytical proce- trations in a few parts per trillion, can lead to inaccurate results. If dure, from sample fusion to MC-ICP-MS analysis, can be completed in alkali flux fusion is to be successfully utilized with samples that less than a day. In order to examine the accuracy of our protocol, ele- have low levels of REE, Sc and Y, the flux must be further purified to mental concentrations and CI-normalized REE patterns for seven USGS reduce blank contributions. reference materials are measured and compared with high-precision In order to address this need, a simple and highly efficient method data measured by various ICP-MS techniques from the literature. Finally, was developed to remove these elements from commercially avail- we present REE, Sc and Y abundances and REE fractionation patterns in able alkali flux materials using TODGA extraction chromatography. aliquots of Post-Archean Australian Shales (PAAS), Allende (CV3), Tag- Approximately 60 g of Puratronic LiBO2 powder from Alfa Aesar was − 1 ish Lake (CI2-ungrouped), Orgueil (CI1), Alais (CI1) and Ivuna (CV1) dissolved at room temperature in 2 L of 3 mol L HNO3 stocked in meteorites with the aim to re-evaluate the terrestrial and cosmic abun- a PFA Teflon bottle. Adding higher amounts of the flux will result in dances of these elements. incomplete dissolution and precipitation of the flux on the resin. Three 2-mL Eichrom TODGA cartridges were stacked in tandem on 2. Method development the vacuum chamber and 10-mL polypropylene columns were used as loading reservoirs. The cartridge assembly was preconditioned 2.1. Materials with 60 mL of 0.05 mol L− 1 HCl to remove residual REE, Sc and Y on the resin, followed by 20 mL of MQ water and 20 mL of 3 mol L− 1

Concentrated, certified ACS Plus hydrochloric (HCl) and nitric HNO3 to convert the resin to the loading acid concentration. The lith- (HNO3) acids from Fisher Scientific were distilled twice in sub-boiling ium metaborate flux solution was subsequently loaded to the car- quartz and PTFE Teflon stills. The working acid solutions were titrated tridge array and the eluent was collected in precleaned PFA Teflon with calibrated sodium hydroxide solutions before use. High-purity bottles at elution rates of 3–4 mL min− 1. A total of five TODGA car- water from a Millipore Milli-Q system (resistivityN18 MΩ cm− 1) tridge arrays were used for 400 mL of flux solution per each array to was used for rinsing labware, extraction chromatography and acid di- avoid elution of REE, Sc and Y from the resin due to high load volume. lutions. Savillex PFA Teflon vials and beakers used for purification of The purified LiBO2 was recovered in two steps. The solution was alkali flux and chromatography elutions were first cleaned in 50% first evaporated to a thin slab in increments of 200 mL in precleaned,

HNO3 at 70 °C, followed by boiling in aqua regia (HCl:HNO3 at 3:1). 250 mL PFA Savillex beakers. The beakers were capped using Platinum evaporation dishes were cleaned in a boiling, 4 mol L− 1 threaded closers with portholes to minimize contamination. The

HCl solution. Pre-packed, 2-mL TODGA cartridges (resin mesh size: LiBO2 slabs (~5 cm in diameter) were subsequently heated in a 50–100 μm), connectors and a Plexiglas vacuum chamber are avail- capped, 100-mL platinum evaporation dish inside a Thermoline fur- able from Eichrom Inc. Polypropylene columns from Bio-rad were nace at 720 °C for 1 h. This temperature is safely below the melting used as loading reservoirs for cartridge chromatography. High-purity, point of LiBO2 (845 °C), yet it is sufficiently high to allow complete re- 8-mL graphite crucibles, LiBr non-wetting agent (Pure grade) and cer- moval of residual HNO3 and water from the flux slabs. Subsequent tified multi-element REE, Sc and Y standard solutions were obtained tests have shown that high-purity quartz crucibles may also be used from SPEX CertiPrep. Commercially manufactured Puratronic lithium as a substitute for expensive platinum evaporation dishes for this metaborate powder (99.997% metals basis, cat# 10739) was pur- step. Approximately 57 g of purified flux was recovered from 60 g of chased from Alfa Aesar. original LiBO2 powder. The flux purification and recovery procedures are summarized in Fig. 1. The effectiveness of this procedure in re- 2.2. Sample digestion moving REE, Sc and Y from the flux material is discussed in Section 3.1. 2.2.1. Purification of lithium metaborate flux Complete dissolution of refractory minerals (such as garnet and 2.2.2. Alkali flux fusion zircon) is a prerequisite for accurate and precise isotopic and elemen- Approximately 15–50 mg of USGS reference materials, PAAS and tal analysis of terrestrial and meteoritic materials with solution-based homogenized meteorite powders were fused with ~450 mg of 40 A. Pourmand et al. / Chemical Geology 291 (2012) 38–54

I. Flux dissolution II. Purification III. Recovery

Cleaning and conditioning 1) 60 mL 0.05 M HCl 2) 20 mL MQ-Water

3) 20 mL 3M HNO3

4) Flux loaded in 3M HNO3 Hot-plate dry-down in 250 mL PFA beakers at ~ 60 g 220 °C for LiBO TODGA TODGA TODGA TODGA TODGA 2 2-3 hr dissolved

in 2L TODGA TODGA TODGA TODGA TODGA 3M HNO3

TODGA TODGA TODGA TODGA TODGA Furnace dry- down in 5) Load solution: Purified Flux capped 100 mL Pt dishes Vacuum range: 0.66-0.79 atm. -1 at 720 °C for Flow rate: 3-4 mL min 1 hr

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 LiBO2 − 1 was dissolved in 2 L of 3 mol L HNO3. The flux solution was loaded onto an array of TODGA cartridges. About 57 g of purified flux powder was recovered by evaporating the elute 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.

purified LiBO2 flux. Previous fusion experiments showed that a flux: Following dissolution of the fusion melt, REE, Sc and Y were quantita- sample ratio of 6 or higher is required for complete digestion of ter- tively separated from major and trace elements using a single-stage restrial and meteoritic materials and successful dissolution of the TODGA extraction chromatography. The distribution coefficients − 1 melt in 3 mol L HNO3 (Pourmand and Dauphas, 2010). The geolog- (Kd = concentration in TODGA resin/concentration in equilibrated ical reference materials were specifically selected to cover a wide solution) for REE on the TODGA resin are extremely high and exceed − 1 range of REE, Sc and Y concentrations, spanning three orders of mag- 10,000 in 3 mol L HNO3 for most lanthanides. In contrast, the Kds nitude. Three chips of the Ivuna meteorite (200–800 mg) were sawn of all REE fall below 1 in 0.05 mol L− 1 HCl (Pourmand and Dauphas, from larger pieces and cleaned in an ultrasonic bath for ~10 s with 2010). Such large differentials in the affinity of the TODGA resin for high-purity ethanol. The chips were dried and powdered separately REE make it an ideal medium for separation of these elements from in a sand-cleaned agate mortar under class-100 clean air. Powdered the rock matrix. Although Pourmand and Dauphas (2010) did not re- aliquots of Orgueil, Alais and Tagish Lake were rinsed with ethanol port distribution coefficients for Pr and Sc on the TODGA resin, these and digested without further processing. Detailed information about elements were found to behave similarly to other REE, as shown by the terrestrial and meteoritic samples can be found in Table 1. In ad- recovery of the multi-element standard solution (see Section 3.1 dition to the samples, an aliquot of the multi-element standard solu- below). tion was also fused with the flux and processed through the TODGA The schematic protocol for high-purity LiBO2 fusion and TODGA resin to establish chemical yields for the REE, Sc and Y on this resin. extraction chromatography of REE, Sc and Y is shown in Fig. 2. Briefly,

Approximately 450 mg of LiBO2 was weighted onto an 8-mL high- a 10-mL Bio-Rad polypropylene reservoir, a 2-mL TODGA cartridge purity graphite crucible. The sample powder was then transferred to a and two disposable connectors were assembled on the vacuum cham- depression at the center of the flux using clean weighing paper. The ber in tandem. Vacuum was regulated at 0.79–0.98 atm with a single- next crucial step was the addition of about 60–150 mg of a high-puri- stage Venturi pump (Mcmaster Carr, Cat# 41605 K13). Flow rates for ty LiBr non-wetting solution (Spex Certiprep) to prevent adhesion of load/rinse solutions and elution of REE, Sc and Y were maintained the fusion melt to the graphite crucible and facilitate its quantitative below 2 and 3 mL min− 1, respectively, by adjusting the vacuum. transfer for dissolution. The crucible containing the flux, sample pow- The 2-mL TODGA cartridge was preconditioned with 20 mL of der and the non-wetting agent was capped prior to digestion to min- 0.05 mol L− 1 HCl to remove REE, Sc and Y from the resin, followed − 1 imize potential contaminations. Fusion was performed at 1070 °C by 10 mL of MQ water and 10 mL of 3 mol L HNO3 to convert to inside a Thermoline furnace for 12 min and the melt was directly the loading acid solution. The sample was loaded to the reservoir in − 1 − 1 poured into a 30-mL Savillex PFA vial containing 15 mL of 15 mL 3 mol L HNO3 and was followed by 12 mL of 3 mol L − 1 3 mol L HNO3. In spite of the intense reaction between the melt HNO3 to remove matrix elements. Residual major and transition ele- − 1 and the liquid, sample loss does not occur during this stage as evi- ments, including Ca, were stripped in 15 mL of 11 mol L HNO3. All denced by processing the multi-element standard solution (see Sec- REE, Sc and Y were subsequently eluted in 30 mL of 0.05 mol L− 1 HCl tion 3.1). The vial containing small fragments of the fusion material into 50 mL centrifuge tubes for the reference materials and PAAS, and was then placed on a Thermolyne Vortex at ~6000 rpm and complete 30-mL PFA Savillex vials for meteorites. The solutions containing the dissolution was usually achieved within a few minutes. The solutions reference materials and PAAS were either gravimetrically diluted to − 1 were inspected under the microscope and graphite particles were 0.45 mol L HNO3 or evaporated and diluted by a factor of 20–200 identified as the only remaining solid residues. for analysis. Solutions containing REE, Sc and Y for meteorites were − 1 evaporated to 1–2 μL and diluted in 2 mL of 0.45 mol L HNO3 2.3. TODGA extraction chromatography prior to MC-ICP-MS analysis. In the case of direct dilution, care must be taken to ensure that the concentration of nitric acid in the sample High-precision measurements of REE, Sc and Y with ICP-MS re- solution remains identical to the bracketing standard. Otherwise, quire that the analytes of interest be free from matrix elements. measured concentrations may be inaccurate by as much as 10%. A. Pourmand et al. / Chemical Geology 291 (2012) 38–54 41

Table 1 USGS reference materials, Post-Archean Australian Shales and chondritic meteorites analyzed in this study. Aliquots of Ivuna were from homogenizing three separate chips that weighed between 0.2 and 0.8 g. Orgueil A–E 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 material BCR-2 (A–B, n=2) – Basalt, Columbia River, Oregon, USA – BHVO-1 – Basalt, Kilauea, Hawaii, USA – BIR-1 (A–B, n=2) – Basalt, Reykavik Dolerite, Iceland – PCC-1 – Peridotite, Austin Creek, California, USA – W-2 – Diabase, Bull Run Quarry, Virginia, USA – G-2 (A–C, n=3) – Granite. Sullivan Quarry, Rhode Island, USA – G-3 (A–E, 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 –

Meteorites Alais CI1 Field Museum C3_0067 Allende A CV3 USNM, split 8, position 5 3529 Allende B CV3 USNM, split 8, position 5 3529 Ivuna A CI1 USNM 6630 Ivuna B CI1 USNM 6630 Ivuna C CI1 USNM 6630 Orgueil A CI1 MNHN 219 Orgueil B CI1 MNHN 219 Orgueil C CI1 MNHN 219 Orgueil D CI1 Universty of Chicago collection C3_1146 Orgueil E CI1 Universty of Chicago collection C3_1146 Orgueil F CI1 MNHN 219 Orgueil G CI1 MNHN 234 Tagish Lake C2-ung. Private collection –

2.4. Multi-collection ICP-MS analysis of REE, Sc and Y standard solutions of REE. In order to detect and reliably measure the oxides, the standard solutions were analyzed at a high concentra- Elemental concentration measurements were performed on Ther- tion of ~250 ng g− 1 with the Apex-Q+Spiro TMD desolvating sys- moScientific Neptune MC-ICP-MS instruments at the Origins Laboratory tem. As shown in Table 2, intensity ratios of REE oxide/REE ranged of the University of Chicago and the Neptune Isotope Laboratory of The from 0.0034% for EuO+/Eu to 0.0976% for NdO+/Nd, with an average University of Miami. A comprehensive description of the Neptune in- of 0.03% across all REEs. At these levels, the oxide corrections on the strument can be found in Wieser and Schwieters (2005). The instru- measured isotopes in natural samples were negligible and no correc- ment's 9 Faraday collectors were utilized for measuring REE, Sc and Y tions were required. concentrations by standard-sample bracketing technique. The standard In order to measure 14 REE, Sc and Y in a single sample solution, a solutions used to determine elemental concentrations were gravimetri- novel dynamic method was developed using five multi-collector config- cally prepared from two batches of certified multi-element solution that urations. The arrangement of representative REE, Sc and Y isotopes and contained all 14 REE, Sc and Y at ~10 μgg−1. The concentrations of all corresponding collector configurations are shown in Table 3. A unique REE in the multi-element solutions were certified by SPEX CertiPrep aspect of this technique is that 149Sm and 167Er isotopes are measured and the results obtained using the two standard batches agree. Sample in three collector configurations to allow normalization of LREE and and standard solutions were introduced to the plasma in 0.45 mol L−1 HREE to middle REE (Sm-Er). This set-up is greatly advantageous over

HNO3 through an Apex-Q+Spiro TMD desolvating nebulizer (Elemen- single-collector ICP-MS, as it minimizes the effect of plasma instability tal Scientific Inc.) using a 100 μLmin−1 self-aspirating PFA nebulizer. and fluctuations in the desolvation inlet system on REE ratios measured Argon and nitrogen were used as carrier and sweep gasses for the des- by standard-sample bracketing. Scandium-45 and 89Y were also mea- olvation inlet system. sured in two additional sub-configurations (3 and 4). Accommodating One of the main difficulties in measuring elemental concentra- a wide mass range that encompass 14 REE in 3 cup configurations was tions and isotopic ratios of REE by ICP-MS has been the presence made possible by adjusting the zoom optics (Focus and Dispersion) of polyatomic interferences with similar mass/charge ratios as REE and source lens parameters (Focus, Deflection and Shape) of the analytes, e.g., Ln+, LnO+ and LnOH+ (Evans and Giglio, 1993; Dulski, Neptune. 1994; Eggins et al., 1997; Baker et al., 2002; Raut et al., 2003). We A gain calibration was performed for Faraday collectors at the be- took specific measures to minimize contributions from these interfer- ginning of each session. The analysis sequence began with measuring −1 ences; the REE isotopes listed in Table 2 were carefully selected to ion intensities of each analyte in 0.45 mol L HNO3 solution. The eliminate the influence of isobars. Following matrix removal, REE ox- same solution was also used for sample preparation and standard di- ides remain as the only interfering species on the selected isotopes of lutions. The data collection method consisted of 1 block of 5 cycles HREE during MC-ICP-MS analysis. Prior to measuring the samples, with 4.2 s integration time and 3 s of idle time (5 s for Sc) in dynamic oxide contributions were determined by analyzing mono-elemental mode. A take-up time and signal stabilization of 90 s was 42 A. Pourmand et al. / Chemical Geology 291 (2012) 38–54

I. Flux Fusion II. Matrix separation the Faraday cups in the purified flux solution and improvements for other elements ranged from a factor of ~6 for Ho to more than 6300 for La. Cleaning and conditioning Flux (~ 450 mg) + During the course of this study, procedural blanks were processed Sample (~ 50 mg) + 1) 20 mL 0.05 M HCl fi fl 60-150 mg LiBr solution 2) 10 mL MQ water and analyzed similarly to the samples using ~0.45 g of puri ed ux. Ref- erence materials, PAAS and meteorite samples were processed in three in 8 mL graphite crucibles at 3) 10 mL 3 M HNO3 1070 °C for 12 min separate batches with blank levels slightly elevated for the second 4) Sample load in 3 M HNO 3 and third batches. Total procedural blanks (Table 4)arebasedonthe geometric mean for 6 replicate measurements. The REE and Y abun- High dances in the peridotite reference material PCC-1 are considerably purity lower compared with most (extra) terrestrial materials, and required flux fusion relatively higher blank adjustments (7.4% on average). Procedural blank contributions to all other reference materials were up to two orders of magnitude smaller for most elements, with highest adjust-

Direct transfer of melt TODGA ments made for G-3 at 0.05% on average. Average blank contribution for PAAS samples was 0.07%. Adjustments to Allende (0.14%), Tagish Lake (0.86%), Ivuna (0.4%), Orgueil (0.31%) and Alais (1.2%) were also implemented prior to calculating final concentrations. Dissolve in 5) Load solution: Matrix In order to test the recovery of REE, Sc and Y, an aliquot of the 15 mL 6) 12 mL 3 M HNO : Matrix − 1 3 multi-element standard solution (~10 μgg , see Table 4 for concen- 3 M HNO 7) 15 mL 11 M HNO : Ca 3 3 tration details) was added to ~0.45 g of purified flux and processed 8) 30 mL 0.05 M HCl: REEs through fusion and extraction chromatography similarly to the rest Vacuum range: 0.79-0.98 atm. Flow rates: load and elution at < 2 mL min-1 of the samples. Elemental concentrations, compared against the -1 Rinse at 3 mL min same multi-element standard solution, demonstrate quantitative re- covery for all elements (Table 4).

Fig. 2. Schematic protocol for high-temperature LiBO2 flux fusion and separation of REE, Sc and Y from interfering matrix with TODGA extraction chromatography. A homogenized 3.2. REE in geological reference materials and PAAS aliquot of the sample powder was fused at 1070 °C with purified LiBO2 flux for 12 min in capped, high-purity graphite crucibles. About 60–150 mg of LiBr non-wetting solution was used to facilitate quantitative transfer of the fusion melt. The melt was directly dis- In order to assess the accuracy of our analytical methodology, REE, −1 solved in 15 mL of 3 mol L HNO3 and loaded to a pre-conditioned TODGA cartridge. Fol- Sc and Y concentrations from this study are compared with the mean −1 lowing matrix removal, REE, Sc and Y were eluted in 30 mL of 0.05 mol L HCl. of 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 implemented prior to data collection. The inlet system was rinsed (n=10) and G-3 (n=1) reference materials in Table 5. Literature mea- − 1 with 0.45 mol L HNO3 for 2 min between each run. This wash surements were acquired by quadrupole, sector field high-resolution time was sufficient to eliminate memory effects from previous sam- (HR-ICP) and multi-collection mass spectrometers using standard addi- ple and standard analyses. Signal intensities from the dilution acid tion/bracketing or isotope dilution techniques. With the exception of G- were subtracted online from procedural blanks, standard and sample 3, the abundances of elements in geological reference materials from runs at the beginning of each sequence. Every sample measurement this study are similar to the mean of literature values within analytical was bracketed with two multi-element standard solution analyses uncertainties, and demonstrate the accuracy of our technique (Fig. 3). and the REE, Sc and Y concentrations were calculated according to In the case of G-3, we found only one study that reports REE and Y the following relationship:

¼ ðÞ= ðÞ CA CS IS IA 1 Table 2 The REE, Sc and Y isotopes used for measuring concentrations by MC-ICP-MS. Isotopes fi where CA and CS represent the concentrations in the sample and the were selected speci cally to avoid isobaric interferences. The contribution of oxide in- terferences to the intensity signal of REE was assessed by measuring REEO+/REE ratios multi-element standard, respectively, and IA and IS represent the in- in ~250 ng g− 1 monoelemental standard solutions via ESI Apex Q+Spiro TMD deso- tensities of the ion beams registered at the faraday detectors. Concen- lvating nebulizer system. Average REEO+/REE contribution in standard solutions was trations are reported as the mean of up to 3 measurements in the 0.03% and demonstrates the effectiveness of desolvation in removing REE oxides. same sample solution over the course of the run session. All uncer- Oxide interferences were negligible in the samples, which were analyzed at 10–100 tainties in this study are reported as relative standard deviation in times lower concentrations compared with the standards used to determine oxide ― ― percent (100*SD/ x , SD=standard deviation, x =average of sepa- levels. rate digestions) unless otherwise noted. Isotope Isotope abundance (%) Interfering oxide Oxides (%)

45Sc 100.00 –– 3. Results and discussion 89Y 100.00 –– 139La 99.91 –– 140 3.1. Procedural blanks and elemental recovery Ce 88.45 –– 141Pr 100.00 –– 146Nd 17.20 –– fl fi In order to examine the effectiveness of ux puri cation in reduc- 149Sm 13.82 –– ing background levels of REE, Sc and Y, concentrations in purified and 151Eu 47.81 –– commercial flux materials were determined. About 1 g of commercial 157Gd 15.65 141Pr16O 0.0762 − 1 159Tb 100.00 143Nd16O 0.0976 and purified LiBO2 was dissolved in 25 mL of 3 mol L HNO3 and the 163Dy 24.90 147Sm16O 0.0067 analytes were separated following the TODGA extraction chromatog- 165Ho 100.00 149Sm16O 0.0067 raphy procedure presented in Fig. 2. The blank results, shown in 167Er 22.93 151Eu16O 0.0034 Table 4, reveal a dramatic decrease in nearly all REE, Sc and Y concen- 169Tm 100.00 153Eu16O 0.0034 173 157 16 trations from commercial to purified LiBO . The signal intensities of Yb 16.13 Dy O 0.0127 2 175 159 16 elements such as Gd, Tm and Lu were below the detection limits of Lu 97.41 Tb O 0.0325 A. Pourmand et al. / Chemical Geology 291 (2012) 38–54 43

Table 3 Faraday 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 the effect 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. A total of 0.5 mL solution was consumed during each measurement using a 100 μL min− 1 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 0.0 Sub config. 1 139La 140Ce 141Pr 146Nd 149Sm −15.0 67.5 Sub config. 2 167Er 169Tm 173Yb 175Lu 10.0 −38.6 Sub config. 3 45Sc 0.0 0.0 Sub config. 4 89Y 0.0 0.0 concentrations for this reference material; our concentrations appear to sample bracketing technique, preparation and calibration of REE be higher compared with those reported in Meisel et al. (2002) for this spikes can be more demanding than the multi-collection dynamic reference material (Table 5.g). Considering quantitative recovery of all method presented here. Furthermore, mono-isotopic elements (Pr, elements based on processing a multi-element standard solution Tb, Ho, Tm, Sc and Y) cannot be directly measured by IDMS. Addition through fusion and TODGA extraction chromatography (Table 4), accu- of enriched spikes can also introduce interferences on some of the rate concentrations for a nearly identical reference material, G-2, com- measured isotopes (for example 149Sm and 153Eu spikes can cause pared with values from 10 literature measurements (Table 5.f), and oxide interferences on 165Ho and 169Tm, respectively, see Table 2). consistency between five replicate analyses of G-3 (Table 5.g), we are REE abundances of Post-Archean Australian Shales are often used confident that the concentrations of G-3 presented in this study are ac- for normalization of REE patterns (Nance and Taylor, 1976; Taylor curate. The uncertainties on the mean of five replicate analyses of G-3 and McLennan, 1985). These abundances were obtained by spark- range between RSD=1.7% for Sm and RSD=3.1% for Sc, with an aver- source mass spectrometry, which suffers from relatively poor preci- age of ~2% for all elements, and represent the overall precision of our sion. In addition, some REEs in PAAS (Tm and Yb) were not actually analytical technique. measured but instead, the abundances of these elements were de- Baker et al. (2002) reported high-precision concentrations of rived by interpolation between neighbor REEs (Taylor and McLennan, some REE in BHVO-1, BCR-2 and BIR-1 by MC-ICP-MS. Those values 1985). We have analyzed nine PAAS samples from four basins across were later revised by Kent et al. (2004) using a similar method of Australia (Table 1) using our new MC-ICP-MS technique and the re- acid digestion, ion exchange chromatography and isotope dilution sults, which include measured abundances of Tm and Yb, are pre- mass spectrometry. In spite of major differences between the analyt- sented in Table 6. The normalized REE pattern for PAAS from this ical techniques employed by Kent et al. (2004), and the protocol pre- study are smoother and overall, our data is of higher quality com- sented here (flux fusion, extraction chromatography and standard- pared with those reported by Nance and Taylor (1976) (Fig. 4). We sample bracketing), the arithmetic mean of REE concentrations for recommend that these new values of PAAS be used for normalization BHVO-1 and BIR-1 (Table 5.a–b) from this study are comparable of REE concentration measurements. with those of Kent et al. (2004) within 0.4% and 0.2%, respectively. Recently, Bendel et al. (2011) studied the REE patterns in a num- In the case of BCR-2 and W-2 (Table 5.c and e), the average concen- ber of bulk terrestrial rocks and raised the possibility of Tm, and to trations of REE, Sc and Y between the two studies are in agreement a lesser degree, Yb anomalies. On close inspection of the data, it within 1% and 2%, respectively. Although, in principle, better preci- could be argued that a small Tm depletion may exist (Fig. 4) but sions can be achieved by isotope dilution compared with standard- given the analytical uncertainty of ~2% for Tm based on replicates of G-3 reference material, and the uncertainties in the mean of CI-chon- drites (see Section 3.4), the potential Tm depletion cannot be con- Table 4 vincingly resolved in these PAAS samples. Blanks and yields after flux fusion and extraction chormatography separation of REE, Sc and 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- 3.3. REE in carbonaceous chondrites provements for Y, La, Ce, Gd and Yb after purification. Procedural blanks are based on the fusion of approximately 0.45 g of purified flux in high-purity graphite crucibles. With the exception of volatile elements and Li that is burnt in the b Det. = Below the detection limit of the Neptune Faraday cups. MES: multi-element Sun, the concentrations of most elements in CI carbonaceous chon- standard solution of REE, Sc and Y. drites represent our best estimate of the solar nebula composition Element Puratronic Purifed Procedural MES MES after flux Yield (Haskin et al., 1966; Evensen et al., 1978; Palme, 1988; Anders and μ − 1 LiBO2 LiBO2 blank ( gg ) fusion and TODGA (%) Grevesse, 1989; Evans and Giglio, 1993; Lodders et al., 2009). The (pg g−1) (pg g− 1) (n=6) separation (pg) (μgg−1) sample digestion, extraction chromatography and multi-collection ICP-MS technique developed during this study were employed to Sc b Det. b Det. 91 10.00 10.24 102.4 Y 3089 13 472 9.95 10.02 100.7 measure REE, Sc and Y abundances in Allende (CV3), Tagish Lake La 83,206 13 120 9.88 9.94 100.7 (CI2-ungrouped), Orgueil (CI1), Alais (CI1) and Ivuna (CV1). Elemen- Ce 6087 31 247 10.00 10.07 100.7 tal concentrations determined for these meteorites are compiled in Pr 89 4 53 10.00 10.07 100.7 Tables 7 and 8 and their REE fractionations relative to the mean of Nd 295 33 225 9.96 10.03 100.7 CI-chondrites will be discussed in the following sections. Results Sm 66 8 75 9.88 9.95 100.7 Eu 217 1 28 10.00 10.07 100.7 from this study will be also compared with previously published, Gd 2499 b Det. 88 9.97 10.04 100.7 high-precision values where data is available. Tb 97 1 26 10.00 10.07 100.7 Dy 98 7 84 10.00 10.06 100.6 Ho 7 1 26 9.99 10.05 100.6 3.3.1. Allende (CV3) Er 54 1 57 9.96 10.01 100.5 Two aliquots of bulk Allende powder from the Smithsonian Insti- Tm 3 b Det. 16 9.91 9.97 100.6 tute were analyzed and the results are shown in Table 7. A compari- Yb 644 2 58 10.00 10.06 100.6 son between REE abundances (Fig. 5), normalized to the mean of b Lu 45 Det. 18 9.94 9.99 100.5 CI-chondrites from this study, with bulk analysis of this meteorite 44

Table 5 − Rare-earth element, Y and Sc concentrations (μgg 1 ) 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-collector high-resolution (SC), and multi-collection (MC) ICPMS techniques. RSD% = Relative standard deviation (100 ×SD/average) for multiple analyses of the same sample. The concentrations of REE in PCC-1 were particularly difficult to measure due 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 31.00 Y 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 24.14 La 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 15.08 Ce 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 38.20 Pr 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 5.390 Nd 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 25.07 Sm 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 6.089 Eu 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 2.103 38 (2012) 291 Geology Chemical / al. et Pourmand A. Gd 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 6.317 Tb 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 0.9360 Dy 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 5.394 Ho 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 0.984 Er 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 2.562 Tm 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 0.3320 Yb 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 1.998 Lu 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. RSD% BIR-1 A BIR-1 B This study Mean (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 42.74 –– ––

Y 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 14.38 – La 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 0.5904 54 Ce 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 1.910 Pr 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 0.3723 Nd 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 2.406 Sm 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 1.087 Eu 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 0.5270 Gd 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 1.864 Tb 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 0.3607 Dy 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 2.602 Ho 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 0.5721 Er 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 1.733 Tm –– –– 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 0.2523 Yb 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 1.664 Lu 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 32.21 Y –– 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 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 24.82 Ce 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 53.48 Pr 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 6.798 Nd 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 28.90 Sm 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 6.522 Eu 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 1.964 Gd 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 6.790 Tb –– 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 1.046 Dy 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 6.444 Ho –– 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 1.284 Er 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 3.642 Tm –– 0.5120 1.1 –– 0.5200 1.9 –– –– 0.516 1.1 0.5149 0.5159 0.5154 Yb 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 3.347 Lu 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 7.413 38 (2012) 291 Geology Chemical / al. et Pourmand A. Y –– 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 0.0783 La 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 0.0348 Ce 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 0.0578 Pr 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 0.0075 Nd 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 0.0290 Sm 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 0.0061 Eu 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 0.0012 Gd 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 0.0070 Tb 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 0.0012 Dy 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 0.0100 Ho 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 0.0028 Er 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 0.0115 Tm 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 0.0024 Yb 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 0.0224 Lu 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] Qi et al. (2005) ICP-QMS, [9] Willbold and Jochum (2005) SC-ICP-MS, [10] Makishima and Nakamura (2006) ICP-QMS. – 54 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 32.94 Y 23.00 22.80 0.8 21.90 20.10 –– 20.11 20.19 21.35 6.5 19.58 La 10.00 10.59 0.9 10.07 10.52 10.23 0.8 10.52 10.54 10.35 2.4 10.31 Ce 23.00 23.08 0.7 22.79 23.20 22.80 0.5 23.22 23.26 23.05 0.8 23.23 Pr 3.027 3.027 0.7 3.040 3.030 2.919 2.9 3.030 3.032 3.015 1.4 2.981 Nd 13.00 12.95 0.5 12.90 12.91 12.71 0.6 12.91 12.94 12.90 0.7 13.07 Sm 3.300 3.310 0.5 3.240 3.270 3.234 0.6 3.270 3.274 3.271 0.9 3.240 Eu 1.000 1.0930 0.6 1.100 1.094 1.072 0. 60 1.090 1.096 1.078 3.3 1.109 Gd 3.690 3.960 0.7 3.730 3.710 3.692 0.8 3.710 3.714 3.744 2.6 3.741 Tb 0.6300 0.6220 0.7 0.6320 0.6500 –– 0.6200 0.6160 0.6283 1.9 0.6077

(continued on next page) 45 46

Table 5 (continued) 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 3.887 Ho 0.7600 0.7980 0.9 0.8000 0.8030 –– 0.8000 0.8050 0.7943 2.1 0.7825 Er 2.500 2.260 0.8 2.170 2.220 2.248 0.5 2.220 2.231 2.264 4.8 2.239 Tm 0.3800 –– – 0.3270 –– 0.3300 0.3280 0.3413 7.6 0.3170 Yb 2.050 2.030 1.4 1.980 2.060 2.020 0.6 2.060 2.058 2.037 1.5 2.041 Lu 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 RSD% (n=3)

Sc –– – –– 3.900 8.7 ––––––3.590 3.640 3.710 4.5 3.448 3.571 3.499 3.506 1.8

Y 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 2.3 38 (2012) 291 Geology Chemical / al. et Pourmand A. La 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 0.6 Ce 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 0.5 Pr 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 0.4 Nd 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 0.4 Sm 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 1.3 Eu 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 0.9 Gd 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 1.6 Tb 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 2.3 Dy 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 2.6 Ho 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 2.5 Er 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 2.3 Tm 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 3.2 Yb 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 2.3 Lu 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 54

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 3.1 Y 10.30 3.4 8.899 8.719 8.988 8.802 8.562 8.794 1.9 La 92.40 1.5 88.74 86.10 89.72 89.36 85.87 87.96 2.1 Ce 171.0 2.2 165.2 160.4 167.1 166.0 160.2 163.8 2.0 Pr 17.40 2.5 16.55 16.10 16.72 16.70 16.09 16.43 1.9 Nd 56.80 2.3 53.65 52.33 54.25 54.05 52.21 53.30 1.8 Sm 7.690 2.4 7.049 6.912 7.161 7.029 6.868 7.004 1.7 Eu 1.500 3.1 1.316 1.284 1.337 1.311 1.275 1.305 1.9 Gd 4.070 3.1 4.403 4.336 4.503 4.403 4.299 4.389 1.8 Tb 0.4700 3.1 0.4538 0.447 0.4631 0.4502 0.4393 0.4506 2.0 Dy 2.230 2.9 2.072 2.044 2.107 2.052 1.999 2.055 1.9 Ho 0.3700 2.8 0.342 0.3354 0.3457 0.3379 0.3286 0.3379 1.9 Er 0.9400 3.0 0.871 0.8523 0.8753 0.8607 0.8346 0.8588 1.9 Tm 0.1230 3.3 0.116 0.1137 0.1154 0.1137 0.1100 0.1137 2.0 Yb 0.7400 3.5 0.729 0.7102 0.7274 0.7206 0.6947 0.7164 2.0 Lu 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. A. Pourmand et al. / Chemical Geology 291 (2012) 38–54 47

1.2 BHVO-1 BIR-1

1.1

1.0

0.9

0.8 1.2 PCC-1 G-2

1.1

1.0

0.9

0.8 1.2 BCR-2 W-2

1.1 normalize to REE Concentrations, this study normalize to REE Concentrations,

Mean REE concentrations, USGS reference materials USGS reference Mean REE concentrations, 1.0

0.9

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

Fig. 3. Abundances of REE in six reference materials from literature compilations are indistinguishable from those measured in this study within analytical uncertainties, and attest to the accuracy of the measurements. The error bars represent 1 SD on the mean of literature values. from literature measurements (Jarosewich et al., 1987; Shinotsuka powder is homogenized from a large piece of Allende, the origin of this and Ebihara, 1997) demonstrates very similar fractionation patterns, discrepancy remains unknown to us. with relative enrichment in LREE and depletion in HREE. These pat- Fractionation patterns similar to those presented in Fig. 5 have terns along with a negative anomaly for Eu and a prominent positive also been reported in group II-type Ca–Al-rich inclusions in carbona- anomaly for Tm distinguish the Allende carbonaceous chondrite from ceous chondrites (Tanaka and Masuda, 1973; Martin and Mason, other meteorites. It must be noted that while the REE pattern in 1974; Grossman, 1980; Mason and Taylor, 1982; MacPherson et al., Allende A and B (Table 7) analyzed in this study are closely replicated, 1988). Partial removal of refractory condensates and incomplete con- Eu depletion in the former is not as pronounced. Given that the USNM densation of most volatile elements have been proposed as possible

Table 6 The composition of Post-Archean Australian Shales (PAAS) based on nine samples. Uncertainty on the ratiospffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi is 2SD. While absolute concentrations are variable between individual samples, indices reflective of secular composition changes, such as Eu/Eu* (Eu enrichment factor = EuN= ½ðSmNÞðGdNÞ, N: normalized to CI-chondrites), LREE/ HREE and La/Sc ratios, remain relatively constant for all PAAS samples.

PAAS

Element AO-6 AO-7 AO-9 AO-10 AO-12 SC-7 SC-8 PL-1 PW-5 Mean (n=9)

Sc 13.55 14.97 14.88 17.15 20.18 14.18 15.31 14.21 18.61 15.89 Y 21.80 23.64 22.01 25.79 27.80 26.70 27.45 31.61 39.01 27.31 La 37.87 40.30 38.65 45.69 44.59 43.08 44.52 42.77 63.53 44.56 Ce 75.23 78.27 74.56 87.48 82.50 87.61 91.38 90.40 126.8 88.25 Pr 8.60 8.96 8.66 10.14 10.02 9.90 10.29 10.02 14.72 10.15 Nd 31.46 32.29 31.50 37.01 37.01 36.75 38.28 36.82 54.78 37.32 Sm 5.728 5.878 5.759 6.935 6.149 6.835 7.141 7.240 10.29 6.884 Eu 0.990 1.031 1.002 1.264 1.115 1.211 1.192 1.210 1.917 1.215 Gd 4.911 5.127 4.944 6.102 5.388 5.983 6.218 6.588 9.127 6.043 Tb 0.720 0.761 0.720 0.861 0.857 0.867 0.895 1.013 1.328 0.8914 Dy 4.273 4.557 4.283 5.027 5.291 5.135 5.299 6.243 7.816 5.325 Ho 0.839 0.910 0.844 0.982 1.064 1.009 1.047 1.264 1.515 1.053 Er 2.446 2.687 2.477 2.865 3.121 2.911 3.044 3.814 4.314 3.075 Tm 0.360 0.400 0.365 0.421 0.456 0.421 0.442 0.578 0.617 0.4510 Yb 2.419 2.703 2.459 2.819 3.064 2.774 2.926 3.916 4.030 3.012 Lu 0.354 0.399 0.360 0.412 0.451 0.400 0.425 0.569 0.578 0.4386 Eu/Eu* 0.56 0.57 0.57 0.59 0.58 0.57 0.54 0.53 0.60 0.57±0.02 LREE/ HREE 9.73 9.44 9.67 9.61 9.16 9.45 9.44 7.81 9.21 9.28±1.17 La/Sc 2.79 2.69 2.60 2.66 2.21 3.04 2.91 3.01 3.41 2.81±0.67 48 A. Pourmand et al. / Chemical Geology 291 (2012) 38–54

a

100 mean of CI-chonsdrites, this study PAAS REE concentrations, this study normalized to 10 b

100

?? normalized to mean of CI-chonsdrites, this study

PAAS REE concentrations, Nance and Taylor (1976) 10 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

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 to the 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 Nance and 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 7 Concentrations of REE, Sc and Y (μgg− 1) in Tagish Lake (CI2-ung), Allende (CV3), Ivuna (CI1) and Alais (CI1). Allende A and B are replicate measurements of Allende bulk powder from USNM. Ivuna A, B and C are separate analyses on different chips from this meteorite.

Element Tagish Lake Allende Allende Ivuna Ivuna Ivuna Alais (C2. ung) (CV3) A (CV3) B (CI1) A (CI1) B (CI1) C (CI1)

Sc 8.39 10.94 11.72 5.56 5.93 5.96 5.93 Y 1.768 2.742 2.664 1.434 1.492 1.470 1.560 La 0.3182 0.5628 0.5325 0.2720 0.2710 0.2623 0.2670 Ce 0.7952 1.407 1.341 0.6998 0.6894 0.6724 0.6858 Pr 0.1209 0.2184 0.20603 0.1054 0.1043 0.1017 0.1035 Nd 0.6172 1.121 1.052 0.5379 0.5256 0.5164 0.5299 Sm 0.1989 0.3562 0.33491 0.1681 0.1682 0.1653 0.1702 Eu 0.0781 0.1232 0.11333 0.0638 0.0645 0.0634 0.0656 Gd 0.2618 0.4433 0.45021 0.2094 0.2257 0.2225 0.2318 Tb 0.0481 0.0801 0.08123 0.0383 0.0407 0.0396 0.0414 Dy 0.3300 0.5389 0.54977 0.2480 0.2753 0.2730 0.2858 Ho 0.0699 0.1078 0.10975 0.0504 0.0594 0.0581 0.0612 Er 0.2113 0.3135 0.31955 0.1453 0.1787 0.1762 0.1847 Tm 0.0333 0.0557 0.05457 0.0224 0.0287 0.0272 0.0288 Yb 0.2206 0.3258 0.33086 0.1455 0.1833 0.1800 0.1882 Lu 0.0319 0.0450 0.04698 0.0205 0.0300 0.0263 0.0292 A. Pourmand et al. / Chemical Geology 291 (2012) 38–54 49

Table 8 Concentrations of REE, Sc and Y (μgg− 1) in seven replicates of Orgueil (A–G) 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 (100×SD/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. RSD% A B C D E F G This study RSD% Mean Mean (n=5)

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 7.3 Y ––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 2.2 La 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 1.7 Ce 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 1.5 Pr ––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 1.3 Nd 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 1.9 Sm 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 2.0 Eu 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 1.7 Gd 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 2.2 Tb ––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 1.5 Dy 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 2.4 Ho ––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 2.0 Er 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 2.4 Tm ––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 2.2 Yb 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 3.2 Lu 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 fractionation 3.3.3. Orgueil, Alais and Ivuna (CI1) patterns observed in these objects (Wänke et al., 1974; Boynton, There have been more high-precision analyses of REE by ICP-MS and 1975; Davis and Grossman, 1979; Palme and Boynton, 1993; Palme, thermal ionization mass spectrometry in bulk aliquots of Orgueil than 2000). other primitive meteorites. This is mostly due to sample availability of CI chondrites; the recovered mass of Orgueil was 14 kg compared with 3.3.2. Tagish Lake (C2-ung) Alais (6 kg), Ivuna (705 g), Revelstoke (1 g) and Tonk (7.7 g). As a result, TheaverageREEconcentrationsinTagishLakeareabout24%higher meteoritic estimates of REE, Sc and Y abundances in the solar system are than the mean of CI-chondrites (Tables 7 and 9). Nevertheless, the REE largely based on the analyses of Orgueil (Anders and Grevesse, 1989; pattern in this meteorite, shown in Fig. 6, is relatively flat. Tagish Lake Palme and Jones, 2003; Lodders et al., 2009). is a unique meteorite with trace-element patterns that differ from CM The results for REE, Sc and Y concentrations in seven samples of and CI chondrites (Brown et al., 2000; Friedrich et al., 2002; Mittlefehldt, Orgueil homogenized from different chips of MNHN 219, 234 and 2002). Rare earth elements in the sample from this study show slightly the University of Chicago collection C3_1146, are presented in higher enrichment for all REE but less deviation from the mean com- Table 8. While five Orgueil measurements (A–E) are indistinguishable pared with previous bulk measurements of this meteorite (Fig. 6). Al- from literature compilations within analytical uncertainties, two though the sample quantity analyzed in this study was relatively small measurements on separate chips of Orgueil (F and G) show clear en- (15mg),itcamefrom34gofhomogenizedpowder(Jadhav, 2009), richment in LREE and Eu relative to the mean of CI-chondrites, as whichmayexplainthesmootherREEpatterncomparedwithprevious shown in Fig. 7a. A comparison with CI-normalized REE pattern measurements of this meteorite. with literature compilations (Fig. 7b) shows less scatter in REE

2.35 2.30 2.25 2.20 2.15 2.10 2.05 2.00 1.95 1.90 1.85 1.80

mean of CI-Chondrites, this study 1.75

Allende REE concentrations normalized to 1.70 1.65 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Allende A (this study) Allende B (this study) Shinotsuka and Ebihara (1997) Jarosewich et al. (1987)

Fig. 5. Rare earth element patterns for two separate analyses of bulk Allende are compared with measurements of this meteorite from previous studies. Abundances are normalized to the mean of CI-chondrites (Table 9). The REE pattern in Allende samples is similar to group-II Ca–Al inclusions in carbonaceous chondrites, with enrichment in LREE, depletion in HREE, a negative anomaly in Eu and positive anomaly in Tm. 50 A. Pourmand et al. / Chemical Geology 291 (2012) 38–54

Table 9 Recommended mean of CI-chondrite concentrations (μgg− 1) for REE, Sc and Y based on MC-ICP-MS measurements of 8 CI-chondrites (five Orgueil (A–E), two Ivuna (B and C) and one 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 and Ivuna samples are adjusted to the mean of Orgueil. RSD% = Relative standard deviation (100×SD/average) based on Orgueil A–E measurements.

Element [1] [2] [3] [4] Estimated [5] Estimated This study RSD% accuracy% accuracy% (n=8)

Sc 5.800 5.820 5.920 5.900 3 5.900 5 5.493 5.6 Y 1.440 1.560 1.570 1.560 3 1.530 10 1.395 1.9 La 0.2340 0.2347 0.2370 0.2450 5 0.2420 5 0.2469 1.5 Ce 0.6160 0.6032 0.6130 0.6380 5 0.6220 5 0.6321 1.3 Pr 0.0929 0.0891 0.0928 0.0964 10 0.0946 7 0.0959 1.2 Nd 0.4570 0.4524 0.4570 0.4740 5 0.4710 5 0.4854 1.5 Sm 0.1490 0.1471 0.1480 0.1540 5 0.1520 5 0.1556 1.6 Eu 0.0560 0.0560 0.0563 0.0580 5 0.0578 5 0.0599 1.4 Gd 0.1970 0.1966 0.1990 0.2040 5 0.2050 5 0.2093 1.8 Tb 0.0355 0.0363 0.0361 0.0375 10 0.0384 7 0.0378 1.3 Dy 0.2450 0.2427 0.2460 0.2540 5 0.2550 5 0.2577 2.0 Ho 0.0547 0.0556 0.0546 0.0567 10 0.0572 7 0.0554 1.6 Er 0.1600 0.1589 0.1600 0.1660 5 0.1630 5 0.1667 1.9 Tm 0.0247 0.0242 0.0247 0.0256 10 0.0261 7 0.0261 1.8 Yb 0.1590 0.1625 0.1610 0.1650 5 0.1690 5 0.1694 2.5 Lu 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, not distributed homogenously and are concentrated in trace phases Y and Sc concentration based on five replicate analyses of Orgueil A–E such as apatite (phosphates) and merrillite in CI and other groups of are also generally smaller than those calculated based on the mean of chondrites (Rocholl and Jochum, 1993; Goreva and Burnett, 2001; Morlok 6 literature measurements. et al., 2006; Bouvier et al., 2008). With the exception of an apparent small enrichment in Lu, the REE pattern of Alais is quite similar to Orgueil with an overall enrichment 3.4. Revised REE, Sc and Y in CI-chondrites of 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- Although Alais and two Ivuna chips (B and C) are generally enriched in iable. As shown in Fig. 8, two of the analyzed chips have almost flat REE all REE relative to the mean of CI chondrites, REE ratios in these samples patterns (B and C) while Ivuna A is characterized by a significant deple- do not show fractionations that significantly deviate from the flat pattern tion in HREE. Interestingly, the REE abundances for Ivuna from Lodders seen in Orgueil A–E and the mean of CI-chondrites from literature compi- (2003) form an entirely different pattern, with overall depletion in lations (Tables 8 and 9). The patterns for these CI-chondrites are very sim- REE, negative anomalies for Tb and Tm and a positive anomaly for Ho. ilar to Tagish Lake (Fig. 6), which came from 34 g of homogenized powder The deviations from a flat pattern observed in some Ivuna specimens and is not affected by inhomogeneity inherent to small sample sizes. After could result from REE redistribution by aqueous fluids on the parent- adjusting the abundances of Alais and Ivuna B and C to the mean of body of CI-chondrites. The petrographic texture of CI-chondrites shows Orgueil A–E, we propose new, fiducial values for the concentrations of great abundance of microbreccias with a wide range of mineralogical REE, Sc and Y in CI-chondrites based on the average of MC-ICP-MS mea- compositions. It is indeed well documented that REE and actinides are surements in Orgueil (5), Alais (1), and Ivuna (2), while excluding the

1.35

1.30

1.25

1.20

1.15

1.10

1.05

to Mean of CI-Chondrites, This Study 1.00 Tagish Lake REE Concentrations Normalized 0.95 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

This study Brown et al. (2000) Friedrich et al. (2002)

Fig. 6. The abundances of REE in Tagish Lake from this study, normalized to mean of CI-chondrites (Table 9), are compared with previous analyses of this meteorite. Although Tagish Lake is geochemically different from CI-chondrites, it shows a similarly flat pattern. The sample analyzed in this study came from homogenizing 34 g of Tagish Lake meteorite, which may explain the relatively smooth pattern compared with others. A. Pourmand et al. / Chemical Geology 291 (2012) 38–54 51

1.40 a 1.35

1.30

1.25

1.20

1.15

1.10

1.05

1.00 mean of CI-Chondrites, this study

Orgueil REE concentrations normalized to 0.95

0.90 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Orgueil A (MNHN 219) Orgueil B (MNHN 219) Orgueil C (MNHN 219) Orgueil D (C3_1146) Orgueil E (C3_1146) Alais FM C3_0067 Orgueil F (MNHN 219,) different chip Orgueil G (MNHN 234)

1.10 b

1.05

1.00

0.95

0.90

0.85 mean of CI-Chondrites, this study

Orgueil REE concentrations normalized to 0.80 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Nakamura (1974) Shinotsuka et al. (1997) Friedrich et al. (2002) Makishima and Nakamura (2006) Makishima and Nakamura (2006) Nakamura (1974)

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 A–E show a smooth 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 A–E with slightly higher 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-isotopic elements 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 the meteorite samples were digested using low-blank LiBO2 fusion and cosmic abundances of these elements and are recommended as reference REE, Sc and Y were separated from the matrix with a single TODGA concentrations to normalize REE, Sc and Y abundance patterns of terres- extraction chromatography step. A new method was also developed trial and extraterrestrial materials. Our recommended REE concentrations to take advantage of 9 Faraday collectors, source lens voltage adjust- and literature compilations for CI-chondrites that are commonly used for ments and zoom optics on the Neptune MC-ICP-MS for measure- REE normalization are in good agreement within estimated accuracies ment of REE, Sc and Y in a single sample solution, while reported by Palme and Jones (2003) and Lodders et al. (2009),withim- minimizing the effect of fluctuations in the Ar plasma and inlet sys- proved uncertainties from our study (Table 9). The average ratio (by tems. An Apex-Q+Spiro TMD desolvation system interfaced with weight) for the twin elements Y and Ho for CI-chondrites derived here the Neptune rendered the corrections for polyatomic interferences is 25.2±0.2 (2σ of the mean), which is slightly lower but comparable on heavy rare earth elements negligible. The entire procedure from to previous estimates of Y/Ho for carbonaceous chondrites (e.g., 25.94± sample digestion to data collection can be completed in a day. 0.08; Pack et al., 2007). 2. The accuracy of the proposed procedure was tested by comparing REE, Sc and Y concentrations in USGS reference materials BHVO-1, BCR-2, 4. Summary 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- 1. A simple purification procedure is developed to reduce REE, Sc and Y 2, BIR-1, W-2, G-2 and G-3. Higher blank corrections for PCC-1 were

blank levels in commercial LiBO2 flux by up to 3 orders of magnitude. due to exceptionally low REE concentrations in this peridotite refer- Homogenized aliquots of terrestrial reference materials, PAAS and ence material. The elemental concentrations and CI-normalized REE 52 A. Pourmand et al. / Chemical Geology 291 (2012) 38–54

1.20 Ivuna B 1.15

1.10

1.05 Ivuna C 1.00

0.95 Ivuna Lodders (2003) 0.90

0.85 mean of CI-Chondrites, this study 0.80 Orgueil REE concentrations normalized to Ivuna A 0.75 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

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

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 REE patterns 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) shows an 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 to heterogeneous distribution of REE in different mineralogical phases (such as phosphates) in some CI-chondrites.

patterns in reference materials from our study were indistinguishable Balaram, V., 1996. Recent trends in the instrumental analysis of rare earth elements in geological and industrial materials. TRAC Trends in Analytical Chemistry 15 (9), from literature values within uncertainties and attest to the accuracy 475–486. of our analytical technique. The REE concentrations of PAAS were an- Barrat, J.A., Blichert-Toft, J., Gillet, P., Keller, F., 2000. The differentiation of eucrites: the alyzed, yielding REE patterns that are smoother and more complete role of in situ crystallization. Meteoritics & Planetary Science 35 (5), 1087–1100. Barrat, J.A., Yamaguchi, A., Greenwood, R.C., Bohn, M., Cotten, J., Benoit, M., Franchi, I.A., than previous studies, which did not report measured values for Tm 2007. The Stannern trend eucrites: contamination of main group eucritic magmas andYb.Werecommendthatthesenewvaluesbeusedtodefine by crustal partial melts. Geochimica et Cosmochimica Acta 71 (16), 4108–4124. PAAS for normalization purposes. Bayon, G., Barrat, J.A., Etoubleau, J., Benoit, M., Bollinger, C., Révillon, S., 2009. Determi- 3. Rare-earth element concentrations were determined in primitive nation of rare-earth elements, Sc, Y, Zr, Ba, Hf and Th in geological samples by ICP- MS after Tm addition and alkaline fusion. Geostandards and Geoanalytical Re- chondrites Orgueil (CI1), Alais (CI1) and Ivuna (CI1), as well as search 33 (1), 51–62. Allende (CV3) powder and Tagish Lake (C2-ung). The fractionation Bendel, V., Patzer, A., Pack, A., Hezel, D.C., Münker, C., 2011. Rare earth elements in bulk pattern of REE in Allende was similar to group II-type CAI, with en- chondrites and chondrite components. 42nd Lunar and Planetary Science Confer- ence, 1608, p. 1711. richment in LREE, depletion in HREE, negative Eu and positive Tm Bizzarro, M., Baker, J.A., Ulfbeck, D., 2003. A new digestion and chemical separation technique anomalies. Out of the 11 CI-chondrite measurements, 8 show very for rapid and highly reproducible determination of Lu/Hf and Hf isotope ratios in geolog- similar REE patterns, while one chip of Ivuna and two chips of ical materials by MC-ICP-MS. Geostandard Newsletter 27 (2), 133–145. fi Bolhar, R., Kamber, B.S., Moorbath, S., Whitehouse, M.J., Collerson, K.D., 2005. Chemical char- Orgueil demonstrate signi cant shifts in LREE and HREE. These acterization of earth's most ancient clastic metasediments from the Isua Greenstone Belt, anomalous patterns may be the result of REE fractionation during southern West Greenland. Geochimica et Cosmochimica Acta 69 (6), 1555–1573. parent-body alteration and redistribution of REE in trace carrier Bouvier, A., Vervoort, J.D., Patchett, P.J., 2008. The Lu-Hf and Sm-Nd isotopic composi- tion of CHUR: Constraints from unequilibrated chondrites and implications for phases such as apatite and merrilite. Excluding these outliers, we the bulk composition of terrestrial planets. Earth and Planetary Science Letters recommend revised values for REE, Sc and Y concentration of CI- 273 (1–2), 48–57. chondrites and refine the solar abundances of these elements. Boynton, W.V., 1975. Fractionation in the solar nebula: condensation of yttrium and the rare earth elements. Geochimica et Cosmochimica Acta 39 (5), 569–584. Brown, P.G., Hildebrand, A.R., Zolensky, M.E., Grady, M., Clayton, R.N., Mayeda, T.K., Tagliaferri, E., Spalding, R., MacRae, N.D., Hoffman, E.L., Mittlefehldt, D.W., Wacker, Acknowledgements J.F., Bird, J.A., Campbell, M.D., Carpenter, R., Gingerich, H., Glatiotis, M., Greiner, E., Mazur, M.J., McCausland, P.J.A., Plotkin, H., Mazur, T.R., 2000. The fall, recovery, The authors would like to thank Junjun Zhang for assistance with pu- orbit, and composition of the Tagish Lake meteorite: a new type of carbonaceous – fi fl chondrite. Science 290 (5490), 320 325. ri cation of commercial LiBO2 ux. This work was supported by a Pack- Connelly, J.N., 2006. Improved dissolution and chemical separation methods for Lu-Hf ard fellowship and NASA through grants NNG06GG75G and garnet chronometry. Geochemistry, Geophysics, Geosystems 7. doi:10.1029/ NNX09AG59G to N.D. Discussions with Jean-Alix Barrat, who shared 2005GC001082. Connelly, J.N., Ulfbeck, D.G., Thrane, K., Bizzarro, M., Housh, T., 2006. A method for pu- with us a preprint of his work on REE in CI-chondrites, and Andreas rifying Lu and Hf for analyses by MC-ICP-MS using TODGA resin. Chemical Geology Pack regarding Y/Ho ratios, were greatly appreciated. We are grateful 233 (1–2), 126–136. to Roberta Rudnick and Frédéric Moynier for making powder aliquots Coogan, L.A., Thompson, G.M., MacLeod, C.J., Dick, H.J.B., Edwards, S.J., Hosford Scheirer, A., Barry, T.L., 2004. 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