Nickel Isotope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC-ICP-MS Bleuenn Gueguen, Olivier Rouxel, Emmanuel Ponzevera, Andrey Bekker, Yves Fouquet

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Bleuenn Gueguen, Olivier Rouxel, Emmanuel Ponzevera, Andrey Bekker, Yves Fouquet. Nickel Iso- tope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC- ICP-MS. Geostandards and Geoanalytical Research, Wiley, 2013, 37, pp.297-317. ￿10.1111/j.1751- 908X.2013.00209.x￿. ￿insu-00846624￿

HAL Id: insu-00846624 https://hal-insu.archives-ouvertes.fr/insu-00846624 Submitted on 18 Feb 2014

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Association of Geoanalysts Association of Geoanalysts AcceptedInternational ©2013 Research andGeoanalytical © 2013TheAuthors.Geostandards 10.1111/j.1751-908X.2013.00209.x version andtheVersi this between differences through the copyediting, typesetting, pagination forpublication accepted This articlehasbeen * Corresponding author.e-mail: (3) University ofManitoba, Department ofGeol (2) IFREMER, Centre deBrest, Unité Géosciences Marines, 29280 Plouzané, France 29280 Plouzané, France (1) Institut Universitaire Européen de la Mer, UMR Fouquet (2) and Yves Article (1, OlivierRouxel (1, 2)*, Gueguen Bleuenn MC-ICP-MS by Measured in Nickel IsotopeVariations Article Type: Original Article Date:17-Dec-2012 Accepted Revised Date:12-Dec-2012 03-Aug-2012 Received Date: TerrestrialSilicateRocksand [email protected] [email protected] ogicalCanada Sciences,2N2, Winnipeg, MB, R3T 2), Emmanuel Ponzevera (2), Andrey Bekker (3) Andrey (2), 2), EmmanuelPonzevera and undergone full peer review buthasnotbeen review undergone fullpeer and on of Record. Please cite of Record.Please on 6538, Université deBretagne Occidentale, BP 80, F- and proofreading process, which may lead to Geological Reference Materials Geological Materials Reference this article this as doi: derived rocks displayed a restricted range of restrictedrange displayed a derived rocks roches magmatiques et les dépôtsdeminerais. et les roches magmatiques gammefractionne des reporter la aust rapport par Globale (BSE) géologiques référence de estimer variés, la (3) déte des compositionsisotopiques ennickel,(2) contribution s’organiseen que ainsi sédimentaires terrestres compositi la biologique, en tantquesignature Bien que les premières démontrent études la pertinence isotopes des dunickel en cosmochimie et Earth, abioticfractionation. Keywords: to -1.03‰. ranging +0.14and+1.06‰, wh between andame (CLB-1) (SDO-1), coal BSE compositionof average suggesting an Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article 986was0.05‰(2 precisionforNIST SRM intermediate measurement standard erro (two Measurement precision in for corrected MS andwere procedure, chromatography through two-stage a Niisotopefracti mass-dependent Ni isotope Earth relativetothe various geological reference materials, (3)to procedure forNi analytical isot poorly known.Our depositsremains rocks, andore ofterrestrialig Niisotopecomposition and asapotentialbiosignature, the Although initialstudieshavedemonstrated Nickel, stable isotopes, MC-ICP-MS, geological reference materials, Bulk Silicate Silicate Bulk materials, reference geological MC-ICP-MS, isotopes, stable Nickel, quatre axes, (1) détailler laprocédur (1)détailler quatreaxes, strumental massbiasusing ope determination,(2) reference material NIST SRM 986, and (4) to report the range of NIST toreporttherange SRM986,and(4) material reference andard isotopique de référence de référence andard isotopique onations inmagmaticrocksand ments isotopiquesdunickel dépe tal-contaminated soil (NIST SRM 2711) showed positivevalues soil (NIST 2711)showed SRM tal-contaminated celle des dépôts de mineraises celledesdépôts ereas komatiite-hosted Ni-rich komatiite-hosted ereas r of the mean) was between 0.02 and 0.04‰ 0.02 mean) wasbetween the r of +0.05‰. Manganese nodules (Nod A1;P1),shale (Nod +0.05‰. Manganesenodules δ assess the isotope composition ofthe Bulk Silicate on isotopique du nickel des roches ignées et ignées on isotopiquedunickeldesroches 60/58 composition isotopique composition de la Terre Silicatée Après purification suivant une procédure de de procédure purificationsuivantune Après applicability of Ni isotopes for cosmochemistry of Niisotopesfor applicability rminer la composition is Ni isotope ratios were measured by MC-ICP- by Ni isotoperatiosweremeasured Ni values between -0.13 and +0.16‰ -0.13 Ni valuesbetween contribution is four-fold: (1)todetailan contribution isfour-fold: to determine the Ni isotopecompositionof to determinethe a double-spike correction method. correction a double-spike e analytique pour e analytique la détermination de nickel NIST SRM986,et(4) nickelNIST de t encore très peu connue. Notre peuconnue.Notre très t encore ore deposits. Afterpurification deposits. ore ndants de lama ndants de neous andsedimentary neous s sulfides varied from -0.10 variedfrom sulfides ). Igneous and mantle- otopique de matériaux otopique dematériaux sse dansles Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards le pour mesure intermédiaire es delamoyenne) standard nos mesures(erreur MS puiscorrigés demasseinstrumental dubiais is étapes,lesrapports endeux chromatographie mantelliques montrent magmatic and only two sulfides, study Tanimizu andHirata by reser systematics ofterrestrial or during mineralcrystallisation. organisms, orabioticpr environments shouldbetheresultof eitherbiotic processes,such It 2007). impliesthat 2004, AnbarandRouxel as isthe casefor other transitionmetals such redox-controlled Earth’s crust, Mots-clés : -1.03‰. allant de-0.10à tandis que les sulfures riches en nickel présen (NIST SRM 271) donnent desvaleurs SRM271)donnent (NIST leshal (Nod A1;P1), manganèse une compositionmoye +0.16‰, cequisuggère of 2.62 Myr (Rugel of 2.62Myr (Rugel 1983, TanimizuandHirata2006,Moynier pro mainly tocosmochemical To and0.9%,respectively. of 68%,26%,1.1%,3.6% Nickel has five naturally occurring isotopes,i.e., occurring Nickel hasfivenaturally Silicatée Globale, fractionnement abiotique. Acceptedany Article 60 Ni anomalymeteorites the iniron rapid resulting decay from of Nickel, isotopes stables, MC-ICP-MS, ma MC-ICP-MS, stables, isotopes Nickel, et al une gamme restreinte une gammerestreinte ocesses such as chemical precipitati as chemical such ocesses . 2009). Since Ni occurs solely in one natural valence state(Ni valence solely inonenatural 2009).SinceNioccurs . NIST SRM986estde0.05‰(2 cesses (e.g., Morand andAlle Morand cesses (e.g., voirs lags othernon-traditi behind (2006) demonstrates significan (2006) demonstrates processes willnotinducemass-de processes e (SDO-1), le charbon (CLB-1) et le sol contaminé en métaux enmétaux etlesolcontaminé (CLB-1) lecharbon e (SDO-1), studies subsequently report Ni studies subsequently report However, despite itspotential, the understanding Niisotope However, despite of δ 60/58 et al Ni positives comprises entre +0.14 et+1.06‰, Ni positives comprisesentre+0.14 de valeurs isotopiques de valeurs as Fe, Mo,CrandCu(e as Fe, ts dansles komatiites ontdes valeurs négatives any observed fractionation in natural in observedfractionation any nne de la BSE à +0.05‰. Les nodulesde BSE à+0.05‰. dela nne otopiques dunickelontét . 2007, Cook . 2007, t comprise entre 0.02 et 0.04‰, etlaprécisionde et 0.04‰, t compriseentre0.02 par laméthodedudouble-sp par 58 Ni, date, Niisotopestudies tériaux géologiques de référence, Terre Terre de référence, géologiques tériaux 60 Ni, gre 1983, Shimamura and Lugmair greLugmair 1983,Shimamuraand on or adsorption in aqueous systems, inaqueoussystems, on oradsorption 61 et al t Ni isotope fractionation in t Niisotopefractionation Ni, s ). Les roches ). Les ignées roches et isotope composition ofcrustal isotopecomposition onal isotope systems. Aninitial onal isotope asassimilationofNiby micro- pendent isotopic fractionations isotopic pendent . 2008), specifically to detect todetect . 2008),specifically 62 Ni, and δ 60/58 .g., Albarede andBeard .g., Albarede 60 Fe, which has a half-life which hasahalf-life Fe, Ni entre -0.13 et Ni entre-0.13 é mesurés parMC-ICP- é 64 Ni, with abundances have been applied havebeen ike. Laike. fidélitéde 2+ ) inthe from Iceland; DNC-1, a dolerite sampledinNort DNC-1,a Iceland; from BHVO namely materials, reference geological Sample description Materials andmethods terrestrial analyses based rocks, ofmantle-derived on rocks and komatiites. composition oftheBulk Silicate Earthnecessary o ofrocktypes range alarge in detectable with thepurpose laboratories and Ni isotopecompositionforRMstoallowacomp method to correct forinstrumental method tocorrect pl coupled collector-inductively isotopic determination ingeological samples, includingsediments igneous and rocks by multi- Ni high-precision protocoltoperform analytical and this studyexperimental at (1)developing an Ni isot growingof studiesapply Since a number with methanogens(Cameron values, and encompassesthe magnitude fractio of ligands, such as Ni ligands, such Theexperimental andhydroxides). carbonates among aqueous abiotic Niisotopefractionations uncertain. More recently, Fujii Identification biosignatures in 2009). ofsuch Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards rocks (Cameron 60 methan producing methanogens –micro-organisms

Accepted ArticleNi/ 58 Ni ratiosby inco 1.5‰ by preferential upto Geological reference materials: materials: reference Geological et al 2+ , NiSO . 2009,Gall 4 , NiCO et al et al asma-mass spectrometry (MC-ICP-MS) and using adouble-spike (MC-ICP-MS) and asma-mass spectrometry et al . 2009). . 2009). of demonstrating thatsignifiof demonstrating massbias,(2)providing asubsta . (2011) report theoreticala . (2011)report 3 , NiHCO . 2012). Interestingly, a recent study demonstrated that studyInterestingly,recent . 2012). a Samples analysed inthisstudy several include USGS ccurring on Earth, and (3) assessing Niisotopic assessing onEarth,and(3) ccurring 3 complex naturalsystem complex + -2, a basalt-2, fromHawaii results indicate that fractionation among indicatethatfractionation Ni results , NiCl ope systematicssamples, tonatural we aimed for interpreting Niisotopefractionation in h Carolina (USA);DTS-1,a dunite sample from species (i.e., chlorides, sulfides, sulfates, sulfates, sulfides, chlorides, (i.e., species arison of Ni isotope data among different ofNiisotopedataamong different arison nation during biological processes associated during associated nation processes biological rporation of the light isotope(Cameron rporation ofthelight e in anaerobic environments –fractionate environments e inanaerobic + andNiOH cant Ni isotope variations are variationsare cant Niisotope nd experimental constraintson experimental nd + isupto 2.5‰in ntial and releva ntial and s, however, remains s, however, (USA); BIR-1,a basalt (USA); nt dataset of nt dataset δ 60/58 Ni et al . study of trace and major element and major study oftrace Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards al during Japan) Eastern (hole C,PacificOcean, thefirstfewmetres in stratigraphic sequence, addition, samplesofa betweenglass, olivine whilstserpentinite and by hand-picking separated were Deep basalts FeMO glass ofthe andfresh Olivine analysed. also were (Ifremer-Genavir) Atalante R/V by the site the from were selected pillow lavaflows recentolivine-phyric from fromseafloorglass basalts andolivine volcanic analysed. Formation geological material reference pr Mn-nodule RMs,Axelsson For Govindaraju (1994). oftheseRMsand description USA). Further NISTalso analysed SRM2711,amodernsoilRM collected and thegraniteG-2 (USA); Kentucky in theCastlemanCoalfield,Maryland, USA) depth) oceans,Lowercoal respectively;Bakerstown bed (Bettinger a CLB-1, fromthe coal Mine theAtlan from manganese nodules No (USA); State Washington the areain Sisters the TwinSisters area Washington inthe PCC-1,a state peridotite (USA); sample fromthe Twin crystallisation. and poten Niisotopecomposition Earth (BSE) this selected set and ofigneous mantle-derived allowed rocks the ofthe estimation Bulk Silicate hydrothermal field (Rouxel hydrothermal field(Rouxel Washington). Samples ofserpentinised ultramafic FeMO the during recovered were These samples

Accepted . 2000,Rouxel Article Selected samples ofbasalts, mantle-derived andmarine rocks sediments: et al . 2003) were also studied. Together w . 2003) alsostudied.Together were ltered and fresh basalts, and deep-sea clays (from the top ofthe (from the clays deep-sea basalts, and andfresh ltered FeMO Deep et al . 2004,Fouquet concentrations. In addition,the concentrations. tic (Blake Plateau at 788 m depth) and Pacific (at 4300m (at at788mdepth)andPacific Plateau tic (Blake at the base of Loihi Seamount(Edwards of at thebase ovided by the CRPG (Nancy, France) was also was also France) (Nancy, by CRPG the ovided ; SDO-1, a Devonian shale from Morehead, from shale aDevonian ; SDO-1, their chemical composition can befoundin chemical compositioncan their to evaluate potential Ni powders were prepared from bulk rocks. Inbulk rocks. from prepared powders were below the seafloor) recovered at IODP at site1149 recovered theseafloor) below cruise 185 by the R/V Joides Resolution (Plank 185 by R/VJoides cruise the tial Ni isotope fractionationduring olivine d-A-1 and Nod-P-1 repr andNod-P-1 d-A-1 in the Sullivan quarry (Rhode Island, USA).We in theSullivanquarry (Rhode et al et cruise by the R/V Thompson (University of R/VThompson(University bycruise the rocks that were recovered from the Logatchev fromthe recovered rocks thatwere affected by metal contamination (Montana, metalcontamination by affected et al . 2010) during the MICROSMOKE cruise . 2010)during theMICROSMOKE . (2002)providean ith volcanic rocks available as RMs, asRMs, available rocks volcanic ith ca . 3.8 IF-GGa BandedIron isotope fractionation isotopefractionation esenting composites of intercomparison et al Fresh Fresh . 2011). et et Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards in Western Australiathe Abitibi greenstone and beltinCanada (Bekker belt greenstone Agnew-Wiluna the areas: two from analysed oreswere sulfide Ni-rich associated Teflon beakers were washed withhot8 moll washed were Teflon beakers previously determined Ni isotopecompositions(Moynier previously Ni determined and content Ni high very their because of procedure and analytical experimental the testing acids. All plastic ware was cleaned with cold 1.2 mol l withcold1.2 cleaned was acids. Allplasticware France apparatus (Analab, fromreag double-distilled and columnworkwere (Milli-Q grade) Bothwas used. concentrated nitricand hydrochloricacids fordissolution used analysed. was also in sulfides; massive andblebby Muir andComba1979,Houlé a kom mineralisation occursin the Abitibigreenstone beltinCanada mine,Alexo where arefrom the sulfide Fe-Ni-Cu-PGE greenstone areamong belt the largest komatiite-hosted Ni-Cu-PGEore deposits. Samples from grains.TheMountKeith pentlandite andpyrrhotite mostly comprising aggregates orsulfide ores sulfide massive sulfides, occurs asdisseminated komatiites withcumulates, thinspinifex-textured unitsand komatiitic basalts. Mineralisation volcanogenic massive sulfidic sulfides, cherts sequencewith felsicmafic and toultramafic comp beltiscomposed greenstone Ga Agnew-Wiluna Accepted Experimental procedure Article Komatiite-hosted Ni-rich sulfides: Iron meteorites: meteorites: Iron Reagents and materials: Reagents andmaterials: Two iron meteorites,na Two iron ). Acids of lower molarity were prepared from these double-distilled fromthese were prepared molarity ). Acidsoflower et al atiitic unitwitholivine cumu addition, brownolivineassociated Ultra-pure 18.2M Ultra-pure . 2012). Nickel-rich sulfideoresse . 2012).Nickel-rich Bulk rock samples comprising bothkomatiites and -1 , carbonaceous shales, and laterally variable variable andlaterally shales, carbonaceous , HNO of a deep-marine volcanic and volcaniclastic volcanic adeep-marine of mely Gibeon and Nantan, were selected for for selected were andNantan, Gibeon mely ent-grade acids using a Cleanacids® distillation aCleanacids® acidsusing ent-grade ositions, whichlocally cont and Perseverance sites of the Agnew-Wiluna of theAgnew-Wiluna sites andPerseverance Ω 3 (reagent grade). grade). (reagent cm water cm with a made Millipore system -1 HCl(reagentgrade), whereas Savillex® et al lates (Naldrett and Mason1968, lates (Naldrett . 2007,Cook withdisseminatedNi-sulfides lected forthisstudylected include et al et et al . 2009).The ains largelensesof . 2008). ca . 2.7 500 µg g 500 µg together proportion toobtainafi mixed inknown HCl, while silicatewere with a rocks mixture digested of2mlconcentrated(28 moll HF through a gravimetric approach. amount ofspikeused,wedidnotattemptto by MC-ICP-MS using nickelNIST SRM the sulfides and ironmeteorit in weighed sample powderwas separatelyconcentrated in distilled HNO Or Laboratory. National theOakRidge provided by Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards withspikes prepared was The double-spikeused Trace Metal Grade or Suprapure grad orSuprapure Grade Metal Trace to digestion orga at 600°Ctooxidise solution madeby thatthesh SCPScience).Note evaporation to dryness. Thesolid evaporation todryness. at 70–80°Covernight put onahotTeflonplate and 6moll one procedural blank and onepure mono-elementa and blank one procedural ofBHVO-2, DTS-1,P with duplicates processed below,allsample As explained optima-grade H Acceptedby dissolv solutions wereprepared fi inthecourseof potential fluoridesformed was repeated toachievecomplete digestion Article Sample digestion: -1 andwitha -1 HCl and further evaporated to dryness at at dryness to evaporated andfurther HCl 2 O 2 was added to each sample to ensure complete oxidation of Fe. of Fe. oxidation complete ensure to eachsample to wasadded 61 Ni/ es were digested with 5 ml of concentrated HNO with5mlofconcentrated es weredigested 62 Depending on their Ni concentrations, between 50 and 250 mg of and between50 Depending ontheirNiconcentrations, Ni ratioof~1.Thedouble-spikec batches, generally including Teflon beakers. Non-siliceous Non-siliceous Teflon beakers. residue was then dissolved in a mixture of concentrated HNO dissolvedinamixtureofconcentrated residuewasthen ingin 10mlof6moll residue the nic matter before chemical dissolution. chemical nic matterbefore e) and 6 ml of concentrated HNO of concentrated and6ml e) 3 and evaporated at 70 °C. Aliquots of the spikes were andevaporatedat70°C.Aliquotsofthespikeswere determinethedoublespikeisotopecomposition of non-siliceous rocks and ensure removal of removal ensure rocksand of non-siliceous 986 standardsolution.Considering limited the and then caps were removed toallow removed thencapswere and rst dissolution step ofsiliceousmaterials.Final rst ale SDO-1 and the coal CLB-1 were ashed prior were coal CLB-1 SDO-1andthe ale CC-1, Nod-P-1 or Nod-A-1 CC-1, Nod-P-1orNod-A-1 61 nal double-spike solution at a concentration of nal double-spikesolutionataconcentration Ni (batch127890)and l solutionofNi(Ni iginal spikesform were inmetal dissolved a temperature of 70–80 °C.Thislatterstep of70–80 a temperature twenty-four samples, were samples, twenty-four materials such asMn-nodules, materials such oncentration was then determined wasthendetermined oncentration -1 HCl, andonedropof Plasma Calstandard 3 . Closed beakers were were . Closedbeakers 62 3 and5mlof6moll Ni (batch233026) reference materials, materials, reference -1

-1 3

1 wa elution work.Nickel column chromatography digestionas were archive kept solutions, 0.24 moll in1mlof dryness at100–120°C on ahotplateandthendissolved thentakento fraction was fractionfinal solutionsin6moll ofthe mol l initially Conditi water. withultrapure washed at pH8–9.About0.5ml(wetvolume) ontheresin,a complex formation oftheNi-DMG prevent the co-precipitation ofmetals inthe form 8–9 toformaninso Ni atpH that scavenges ofpol Ni-resin, made The specific metals. earth alkaline and suchasalkali elements rock-forming major including step, purification anion-exchange the after remaining elements below, theNi-spec use ofthe ensure resin required was complete ofall removal to matrix filled witha specific resin nickel commerciallyavailable fromEichrom (Ni-Spec). Asdiscussed mol l ammonia solution and 4mlofultra-pure water. was Nickel quantitatively eluted fromthe resin wasthenelut matrix maintain apHof8–9.The Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards 15mlof3moll then ml ofultra-purewater, begun 15 loading by columns was ofthe mesh).Thewashingform (BioRad procedure 100-200 filled was with3ml(wet inthe volume)(15 ml)reservoir) chlorideresin ofanionic AG1-X8 columns (i.e.,disposablepolyp chromatography and Cook protoc chemical purification with 0.3mlof1moll loading the sample onto the column,1mloftheinitialsolutionin0.24 loadingmol thesampleonto l Accepted ArticleZn andmostoftheCoa HClduring whichFe, -1 -1 ammonium citrateand11.7 mol l HCl. Conditioningml of6moll carried was outwith5 Nickel chemical purification byion- -1 et al HCl.Thison a solution wasthenpurified . (2007) and followed a two-stage procedure. The first set of ion-exchange The firstsetofion-exchange procedure. followedatwo-stage . (2007)and -1 ammonium citrate,and0.1mlof11.7moll ol used was adapted from previous work by Cameron Cameron previousworkby from ol usedwasadapted ymethacrylate, contains a dimethylglyoxime (DMG) molecule of Ni-Spec resin was loaded resin wasloaded Ni-Spec of -1 -1 HCl on the columns. The final solutions obtainedafter HCl onthe columns.Thefinalsolutions and a only splitwas taken forion-exchange optima-grade ammonia adjusted to pH 8–9. Before to pH8–9.Before optima-gradeadjusted ammonia luble Ni-DMG complex retained ontheresin.To retained luble Ni-DMGcomplex -1 oning was made using a mixture of2.1ml 0.2 oning amixture madeusing was exchange chromatography columns: HNO ed with 4.2mlofmixed ammoniumcitrateand ed nd Cu were retained on the resin. The elutedNi onthe nd Cuwereretained ropylene columns equipped withalarge-volume columnsequipped ropylene of insoluble hydroxides, whichmayof insolublehydroxides, inhibitthe s achieved by passings achievedby 15mlof6moll through mmonium citrate was added to buffer solutions tobuffer mmonium citratewasadded 3 , 15 ml of ultra-pure water, and5mlof0.24 , 15mlofultra-purewater, second series of chromatography columns chromatography of second series -1 HClfollowed by the loading ofa -1 into disposablecolumnsand optima-grade ammonia to to ammonia optima-grade -1 HClwasmixed et al The . (2009) - SRM 986 reference material, respectively; respectively; material, SRM 986reference where R δ as perfollowing: mildeviation (‰) stable isotopedeltanota procedural blanks were generally generally blankswere procedural geologi onthe were notdependent proced publishedexperimental recently yieldsresinthan were 85%,whileIn always throughAG1-X8 contrast quantitative. toanother values blank determine procedural scheme reduction data and procedure Mass spectrometry these blanks. betakentoreduce should care areanalysed, sizes anddidnotrequire negligible was considered footnotes (see chemistry through processed generally spike/natural ratio (i.e., be equal inthe sample. tothe Nicontent Chemistryyields using were determined the measured amount waschosento below, thedouble-spike sample.Asexplained solution wasaddedtoeach through the purification chemical Before 0.28 moll ona todryness eluted Nisolutionwasevaporated prev therefore, with nitricacid.Thistechnique, Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards with 8mlof3moll Acceptedx/58 Article Ni =(R Delta notation: Delta notation: spl -1 andR HNO spl /R NIST NIST 3 when it was ready for isotope determination. isotopedetermination. for whenitwasready

-1 – are the isotopicratios the are HNO 1) 62 Nickel isotope compositionisexpr Nickel isotope tion, i.e.,sampleisotopicratiosareexpr x x Ni/ 1000 (1) 3 , which ensured oxidation anddest , whichensuredoxidation 58 Ni). Chemistry blanks were also were Ni). Chemistry blanks ca. cal matrix and amount ofnickel andamount cal matrix yields through. Chemistry Ni-s 3–4 ng, and since between 0.5 and > 1 µg of nickel was ofnickel 1 µg 0.5and> since between and 3–4ng, ure for nickel purification (Gall purification(Gall nickel for ure Ni-spec column, aknownamountofdouble-spike column, Ni-spec x x Ni stands for one of the following isotopes: three foroneofthe Ni stands Ni/ any correction. However, when smaller sample when However, correction. any ented any regeneration and reuse of the resin. The reuse ofthe and regeneration any ented 58 Ni of the unknown sample and thenickelNISTNi oftheunknownsample hot plate at 90 °C and the residuedissolvedin hot plateat90°Candthe in Tables 3, 4, 5, 6 and 7),thisblanklevel inTables3,4,5,6and essed following the conventional theconventional essed following spiked,whichenabledusto ruction of the Ni-DMG complex Ni-DMGcomplex ruction ofthe essed relative to essed relative pec resin were generally better better generally were resin pec loaded on thecolumn.Nickel loaded on et al . 2012), our yields . 2012),our a standard ratio a standard not exceed 0.5 mV and 0.2 mVonthespikedisotope 0.5mVand0.2 not exceed al or Al (e.g., other conetypes samples was negligible, the since measured blank instrumental signal intensity mass on and skimmer cones contribution tothe were (Xcone) ofNi,their Niisotopic made ratios of The main interferences on Ni isotopes included Fe (e.g., (e.g., NiisotopesincludedFe on The maininterferences analysis total timerequiredper often whereas washoutconsisted an integr eachhaving cycles, Fifty measurement desolvation introductionsystem. Ca) oxides generated in the argon generated inthe Ca) oxides interfering Fe monitored at mass coupled with a 50 µl min coupled witha50µl measurement of measurement was equipped withni Thisinstrument France. ICP-MS operatedPôle at the Spectrométrie Océan Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards 60 resolution mode with the ApexQ was typically ~ 50–75 V/µg ml was typically V/µg resolution modewiththeApexQ ~50–75 Ni isotopesas on interferences resolution mode,butthemedium-resolutionmode data inthisstudy is belongs to the ‰ symbol ratherthantothe belongs tothe‰symbol inthedeltanota multiplication factorof1000 thatfollowing Copl note abundant). However, Ni, Acceptedch a spray waseither . (2007).Theinletsystem Article 61 Ni or MC-ICP-MS settings: settings: MC-ICP-MS 62 Ni, andthelight isotope, 58 Ni, 60 Ni/ 60 Ni, Ni, 58 -1 Ni anditwill bereportedas PFA micro-concentricnebulise 61 Pt cones) was unnecessary, as already demonstrated by Moynier Moynier by demonstrated asalready Pt cones)wasunnecessary, Ni and discussed below. Nickel ionbeam intensityin amedium discussed below. All samplesanalysed were ona was, therefore, approximately approximately was, therefore, 57 measurement cycles,measurement eachwithanintegration timeof 4s.The plasma with identicalplasma masses (e.g., Fe. Theinstrumentwasrunin 62 Ni, 58 Ni, is placed in the denominator (it is also the most most the also is (it denominator the placedin is Ni, 63 δ Cu and notation. Theratiothatwill notation. tion couldbepermitted ne Faraday cups that allowed simultaneous allowed Faraday cupsthat ne en's (2011) recommendation, omissionofthe (2011)recommendation, en's ation timeof4s,were ation amber (i.e., Stable Intr amber (i.e.,Stable was sufficient to resolve argide and oxide andoxide argide was sufficienttoresolve (PSO) located at IFREMER, Centre de Brest, deBrest, Centre IFREMER, at located (PSO) 65 Cu isotopes,aswellisobarically- 62 δ Ni. Thisalsoindicated thattheuseof 60/58 58 r) or an ApexQ (ESI, USA) USA) (ESI, an ApexQ r) or Fe on Ni. 4 min (analysis pluswashout). 4 min(analysis Neptune (Thermo-Electron) Neptune (Thermo-Electron) MC- -1 58 either a medium orhigh mass- a either on Ni), Ar or other element (e.g., (e.g., Ni), Arorotherelement because technically it technically because 40 58 performed onsamples, performed Ar Ni. Although bothsample oduction System (SiS) oduction be usedtodescribethe 18 O + on 58 Ni + ), and 58 Ni did et et interferences Thefrom Xe other isotopes. major potential spectral interference on reported by Fehr Fehr reported by argon resu of ultrapure solution; and(3)theuse 64 potentialand(2)no a high first-ionisation Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards ions(e.g., doubly-charged isotope inthisstudy. Argide measurement of the interference-free interference-free ofthe measurement 36 to resolve polyatomic interferences on 40 criticalgiven that itaffects the major isotope ofargon oxide. duetotheproduction USA) system (ESI, the ApexQ separated from Ni during chemical fromNiduring separated where ( measured and the interference of interference and the measured ( corrected natural iron ratio; M ironratio; natural corrected correction was negligible forNi isotopes(<0.1‰) wasnegligible correction 3‰ per massunit(e as may asmuch by vary isonlyimportant tonotethatthis correction an solution at nickelmixed and measurements ofiron nickel (f nickel f 58 Fe Zn. configurationofth cup SincetheFaraday Ar Ar isthe mass discrimination factor considered equivalent tothe mass discrimination factor of AcceptedFe/ Article 25 18 57 Mg O Fe isotope interference correction: correction: interference Fe isotope Fe) 58 + Ni , and Fe/ + ), which is generally around 1.8. The disc generally around1.8.The ), whichis , and measured 57 Fe) 42 38 Ca =( et al measured Ar 16 23 O 58 . (2004) forTeisotopemeasurements . (2004) Na + Fe/ on on is the raw ratio measured by is MC-ICP-MS; measured therawratio ( + 57 on 124 58 Fe) Ni and oxide interferences included interferences and oxide Xe 61 58 natural + Ni . Medium-resolution modes allowedus (andalsohigh-resolution) istheatomicweightof 2+ 58 + on ; Fe on .(M purification prior to analysis, toanalysis, prior purification 36 Ar 66 62 58 Zn isotope, we did not attempt to measure the Zn wedidnotattempttomeasurethe isotope, Ni). The latter was negligible considering has (1)Xe that 58 26 Ni 58 /M Mg 124 Ni was corrected using Equation 2: Equation using Ni wascorrected + , which stillremained significant even when using 57 Consideration ofisobaric interference fromFewas Xe .g., Dauphas and Rouxel 2006). However, this 2006). However, Dauphas andRouxel .g., + 58 , ) approximation since the natural Fe isotope ratio sincethenatural Fe isotope approximation fFe Ni. Therefore, quantitativelyevenFe if was e mass spectrometer didnotallowsimultaneous spectrometer e mass 38 lted innegligible aspreviously Xeintensity, lted 2+ Ar

was measured on mass 62 intheblank onmass62 was measured

the beginning of each analytical session. It session. analytical is each thebeginning of given that iron interference was very small wasvery given thatironinterference rimination factorwa ( 24 Mg 58 + Fe; M Fe; , and withpotentialimportantisobaric 36 46 Ar 57 Ca 57 isthe atomic mass of 24 Fe was systematically Fe wassystematically 16 Mg 58 O Fe/ + + s estimatedbasedon on on and 57 Fe) 62 44 Ni natural Ca + ; 16 2 64 23 ) O is the Ni isfrom

Na + 64 on 35 Ni 57 Cl Fe; and 60 + Ni , + ; sessions, which allowed us tousef sessions, whichallowed mass fractionation law as Niisotopes;(2)f as mass fractionationlaw isotope ratiosofNIST SRM976 relationship (plotnotshown)be fractionationwith thebeing fractionation law “f” factor each specific element. The for linear (R (Equation 4). Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Marechal instrumentalmassbi for which isusedtocorrect amountof aknown method isbasedonadding fo waslowerthan precision analytical why the each and after solution wasmeasuredbefore instrumental massbiasusing thecalibrato ofNISTratios. TheNiisotopecomposition minor amountsofiron(Fe/Niratiosfrom0.001to SRM 986solutions dopedwithvariousamountsof we estimated the ofnickel irononthe effect isotopic of by composition several measuring NIST afterchemical when separation, ironwas quantitatively removedanalyte. fromtheAdditionally, (R Considering that nickel recovery nickel that Considering by significant analytical artefacts. Hence, this Hence, artefacts. analytical by significant ofpurified compositions Niisotope 99%, itispossiblethatCu-corrected meas Acceptedmeas Article /R /R Inter-elemental correction of Ni instrumental mass bias using Cu isotopes: isotopes: Cu using mass bias instrumental Ni of correction Inter-elemental true true et al ) ) Cu Ni =(M =(M . 1999), instrumental massbiasonMC . 1999),instrumental 60 65 Ni/M Cu/M 58 63 Ni) Cu) fNi tween logarithmstween ofNiisotope SRM986andCu ratiosofNIST fCu yield on the Ni-spec resinpurifi yield ontheNi-spec confirmed that (1) Cuisotope confirmed that(1)

Cu ( ( determinedonNIST SRM976 r-bracketing method (a non-doped NIST SRM986 method(anon-doped r-bracketing Cu SRM 986 Fe-doped solutions was corrected for solutions wascorrected SRM 986Fe-doped /f Fe-doped NIST SRM 986 solution), which explains NISTFe-doped SRM986solution),whichexplains correction method is only suitable for Ni-rich ores forNi-rich methodisonly correction suitable Ni r the samples corrected with the double-spike. withthedouble-spike. samplescorrected r the Cu standard solution (i.e., NIST SRM976), standard solution(i.e.,NIST Cu was individualanalytical constantduring as. As demonstrated in previous studies(e.g.,as. Asdemonstratedinprevious 0.010) didnotproduceany biasinNiisotope iron. The results (see Table 1)showthat (seeTable iron. Theresults -ICP-MS follows an exponential mass- -ICP-MSexponential followsan s follow the same exponential s followthesameexponential cation step ranged from 85%to from ranged cation step (Equation 3)tocalculatef (Equation samples were affected affected were samples 3 4 ) )

This Ni

spike method can be visualised asathree-dime spike methodcanbevisualised byupon themethoddescribed Siebert 2. presented inTable rinse timeand double-spike solution,anextended solution andthe In betweenthestandard spike solution. toavoidcross-contamination order solution was used tocalculate the f 61 isotopic ratios,i.e., was then determined usingwas thendetermined theCu-doping calculate mass-discrimination the instrumental factor f Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards al and ironmeteoritespur RM are calibratedsame onthe instrument spike andRMisotopecompositiondonotintrodu Indeed, Siebert by previously instrument. asdiscussed bothisot tocross-calibrate critical therefore isotope ratios might be and influenced instrumental by ofinstrument the type settings, and itis yield precise compositi does not asufficiently such asNIST SRM986(Gramlich nor orafter gravimetrically determined either thedo Determination of usingNi isotopedataobtained Cu a The isotopiccompositionofNIST SRM986wasfirs Ni/ 60 Accepted Article. 2006,Moynier Ni/ 58 Ni and 58 Double spike correction scheme: scheme: correction spike Double Ni ratioof0.385199 ± 0.000728(2 62 Ni/ et al 58 62 Ni ratios ofthespikevs.NIST SRM986.ACu-dopedpurestandard Ni/ . 2007,Cook ified through anion-exchange resin as throughanion-exchange ified 58 uble-spike composition: composition: uble-spike Ni and 61 -doping and double-spike methods. and double-spike -doping Cu Ni/ et al et al /f 58 et al Ni . 1989). In practice, however, Ni. Theisotopic composition ratio, which was then applied toCu-dopedpuredouble- ratio,whichwasthenapplied . 2008). Inwas usedtocompare . 2008). addition,thisapproach correction methodtodeterminethetrue correction and that isotope data are expressed as expressed isotopedataare and that The double-spike calculation procedure was based procedure calculation double-spike The . (2001) for Mo isotope determination. Thedouble- forMoisotopedetermination. . (2001) s ope reference materials and spike onthesame andspike materials ope reference ) (Gramlich malisation to a known isotopic reference material, material, toaknownisotopicreference malisation on for small quantities of spike. In smallquantitiesofspike. addition, on for nsional diagram where axes represent the three thethree represent axes diagramwhere nsional ce bias providing that both doublespikeand thatboth ce biasproviding “on-peak zero”method Incomposition canbe double-spike theory, t determined by intern t determinedby Ni et al , which allowed the calculation of other calculationofother , whichallowedthe et al . (2001), uncertainties onthenatural . (2001),uncertainties . 1989).Thisratiowasthenusedto used in previous studies(Quitté used inprevious the gravimetric technique the of thenickeldoublespike was used.Resultsare al normalisationusing δ 60/58 60 Ni/ Ni values. 58 Ni, et et Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards instrumental mass bias and the assumption that f rati corrected (because precision overall analytical concentra and accuratenickel separa chemical fractionation during bracketing or sample-calibrator double spikemethodoffers that ofthesamples.The of NIST SRM986nickelsolutionsatthesameni by measurements the wasbracketed analysis sample Each analysis. sample during acquired were In analy fifty to obtainsatisfactory precision, order Matlab™. orusing spreadsheet either onanExcel™ run toproperly iterations were tothemeasur appliedsubsequently which were toaccountforbothna making calculations iterative (AlbaredeBeard Atemplate andestablished 2004). tocalculate was those intercepts plane by used todetermine fractionati MC-ICP-MS, by are andsamplemeasured compositions ofthedouble-spike,standardsolution asspeci measured isotopicratios spike correction, the precision of theprecision spike correction, ofmeasurement cycles fifty calculated on mean the error of standard asatwo reported is precision measurement the analysis, For each Measurement precision and limit ofdetection Results of analytical method development ng, by MC-ICP-MS. measuremen accurate session);and(iv) analytical Acceptedsamples withnickel concentr Article on factors between the measured and corrected isotopic ratios ratios isotopic andcorrected measured the between on factors ations ranging from 100 ng g ng from100 ations ranging tions of samples using theisot tions ofsamplesusing obtain the fractionation factors.Th thefractionation obtain methods by allowing: (i) the correction of potential isotopic ofpotential correction (i)the allowing: methods by fied above.Line and plane in δ 60/58 tion through Ni-spec resin; (ii) Ni-spec resin; tion through Ni values was usually around ± (2SE) for Ni valueswasusually 0.02–0.04‰ during MC-ICP-MSduring thedouble- acquisition.With ed raw isotope ratios. Atleasttwonested rawisotoperatios. ed Cu ckel concentration and spike/standard ratio as ratio andspike/standard ckel concentration t of very small amounts of nickel,downto50 t ofvery smallamounts of os were less affected by the stability the by of os werelessaffected /f tical cycles (~ 4 min of total integration time) tical cycles (~4minoftotal tural andinstrumental several advantages relative totheCu-doping relative advantages several Ni remainedconstantthroughout the -1 to 1 µg g to1µg opic dilutionmethod;(iii)better tercepts, defined by isotopic defined tercepts, e template could be performed couldbeperformed e template the determination of precise ofprecise thedetermination -1 . Precision atlower . Precision fractionation factors, fractionation ± 0.07‰, but became worse at 10 ng g ± at10ng 0.07‰,butbecameworse Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards showsthatbelow30ngg and nickel concentrations, the against reported is analysis foreach calculated mean the errorof standard two 1,the Figure NIST analysing by wasassessed concentrations unit between analytical sessions but remained constant within0.02–0.05‰(2 remainedconstant sessionsbut unit betweenanalytical to0.2‰permass method may usingNIST up by thedouble-spike deviate SRM986calculated an (CSB) bracketing similar tothecalibrator-sample A spikedNIST SRM986solution wasmeasured RMs 986and NIST SRM of precision measurement Intermediate systems ontheMC-ICP-MS instrument. method. For 2 instance, compositiondeterminedby oftheNiisotope thedouble-spike conditions intermediate precision 986allowedusto for NIST SRM set acquired NIST SRM986Niisotoperatiosdeterminedduring wenormaliseddelt session.Asaresult, analytical g 100–200 ng of nickel concentrations For optimummeasurement precision during measurements, isotope we usually ran samples with of nickel. analyses of these samples (see footnotes of Table 3 for details). A value of 0.041‰ (2 of 3 fordetails).Avalue Table of (seefootnotes samples ofthese analyses PCC-1,DTS-1,DNC-1,BIR- materials (BHVO-2, The precisionunderintermediate measurements. for 320 a valueof0.045‰ Accepted tothe repeatability precisionwas similar under (n= duplicates BHVO-2 11) calculatedfor Article s determined using all NIST SRM986de determinedusing all NIST precision conditionswasalso -1 -1 , when using either the ApexQ or SiS introduction orSiS theApexQ either , whenusing and lower concentrations, e.g., 2SE = 0.59‰ at 2 ng g 2SE=0.59‰at2ng e.g., concentrations, andlower evaluate the measurement precision under precision themeasurement evaluate SRM 986 solution at different concentrations. In SRM 986solutionatdifferentconcentrations. before and after each sample inamanner sample each and after before a values of the samples relative to the average totheaverage relative a valuesofthesamples 1, Nod-A-1 and Nod-P-1) using duplicate Nod-P-1) 1, Nod-A-1and the same analytical session. The large data Thelarge data session. analytical thesame -1 alysis. We found that the Niisotoperatiosof alysis. Wefound thatthe the precision slightly deteriorated toabout slightly theprecision deteriorated estimated for certified reference reference certified estimated for lta values calculated so far gave far lta valuescalculatedso s ) during each each ) during s ) -1

samples and 23 degrees of freedom (notincluding freedom of samples and23degrees BHVO-2 spiked after the purification procedure), 2 purificationprocedure), the spikedafter BHVO-2 similar. From data 3withfive inTable samples 21degrees and (not including freedom of the mean. Thismethodisa where duplicate and their andtheir duplicate RMs, i.e.,PCC-1,Nod-A-1,N Ni-resindidnotin the ofNithrough recovery sample and after spiked before s² = k s² (5) (Steele conditions wouldbetopoolallth anothermethodforestimatin Alternatively, standard solution. Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards results gave similarvalues,i.e.,0.006± 0.041‰(2 purification. Although onesamp only complete purificationprocedure Oneofth variability inisotopemeasurements. conditions. Thissuggests thatthechemical Acceptedvalue of0.020± (2 0.065‰ anaverage yielded 2) (Figure procedure chromatography entire the through processed science) ArticleIn themono-elem addition, ofnickel. and 5µg 0.2 i.e.,between chemistry, the through ofsamplematerial processed amounts even fordifferent theisotopi important tonotethatforBHVO-2 and 7),whichissimilartothein -1 s

is the standard deviation, deviation, isthestandard ∑ i

d et al i 2

( . 2011): δ 60/58 ppropriate when conditions ppropriate when Ni values generally did not deviate by more than 0.069‰ (2 generally morethan0.069‰ didnotdeviateby Ni values s , n= tothat fordirect 24),which issimilar analysis ofNi-PCal od-P-1, BIR-1, DNC-1 and DTS-1, were also analysed in analysed also andDTS-1,were DNC-1 od-P-1, BIR-1, purification, respectively. This indicates that theincomplete purification, respectively. Thisindicatesthat termediate measuremen to evaluate potential Niisotope evaluate potential to e data and to calculate thest e dataandtocalculate k is the degree of freedom and freedom of isthedegree le was spiked subsequentto was spiked le g the precision underin g the purification methoddid not introduce additional purification troduce Ni isotope fractionation (Table 3). Other (Table3).Other Niisotopefractionation troduce c composition and recovery remained invariant remained andrecovery c composition e BHVO-2 basalt duplicates was spiked after a was spikedafter duplicates e BHVO-2basalt ental solution of Ni-PCal (Ni Plasmacal®, SCP SCP (NiPlasmacal®, ental solutionofNi-PCal single measurements on USGS G-2, IF-GUSGS G-2, and single on measurements ofsampleprocessing s s ) and-0.067± (2SE)forthesamples 0.017‰ was 0.045‰; from data in Table 7 with six inTable7withsix was0.045‰;fromdata t precision of NIST SRM 986. It SRM986. t precisionofNIST isalso andard deviation using Equation deviation andard fractionation during chemical during fractionation d the purification procedure, the procedure, the purification isthe deviation fromthe termediate precision termediate and measurement are 5 )

s ; Tables3 weused aspike/ and 8, ratios between0.7 δ 0.01 ± around 0.02‰.Evenspike/sa values clustering intensities (correctedinstrumental mass for bias), isotopic masses, and true SRM986),thespike/ ofNIST spike/concentration Instead reportin ofsimply of theratio). from nickel whereas ratio), (denominator ofthe from theNIST SRM986solutionisequivalentto ratio,oneshoul ratios. Tosimply ofthespike/sample visualisethe meaning (2SE) and -0.24 ± 0.06‰ for NIST SRM 986, whereas ratios higher than 0.6 yielded (2SE) and-0.24± higher forNIST ratios than0.6 SRM 986,whereas 0.06‰ spike/sample ratios lower spike/sample ratioslower samp under-spiked As showninFigure 3,only NISTdouble-spike mixture. SRM986andthe solutions added tomakefinal ofNIST SRM986waskeptfixe concentration correction. the robustnessofdouble-spike ratios(b spike/sample with different undertaken Several testswere Optimum spike/sampleratio for Niisotope determination precision'). for assessi adequate study bothmethodswere following Steele of deviation calculated themethodology NIST SRM986 reproducibility of as themeasurement samples and 44 degrees of freedom), 2 freedom), of samples and44degrees Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards NIST SRM2711),2 Accepted60/58 Article Ni valuesof0.04± 0.02‰.Although anoptimum s was 0.053‰. Taking samples from both Tables 3 and 7(i.e.,eleven 0.053‰.Taking frombothTables3and was samples or equal to 0.6 yielded or equalto0.6 with different spike/sample ra with differentspike/sample s g a concentration ratio (concentration of ratio(concentration a concentration g was 0.050‰. Hence, the 2 Hence,the was0.050‰. sample ratio~ 1throughoutstudy. sample this ng the measurement reproducibility ('external ('external reproducibility measurement ng the For each sample used for the tests, the forthe each sampleused For d and different amounts of double-spike were amounts ofdouble-spike were d anddifferent les may not be properly corrected. Indeed, Indeed, corrected. mayles notbeproperly the double-spikesolutionisspike(numerator δ the nickel present in a natural sample inanatural the nickelpresent 60/58 sample ratio was calculated using measured sample ratiowascalculated mple ratios of up to 7 gave consistent mple ratiosofupto7 Ni values ranging between -0.05±Ni valuesranging between 0.02‰ (see above) is comparable to the standard tothestandard iscomparable (see above) precision was obtained forspike/sample precisionwasobtained et al tios, which is tantamount to tios, whichistantamount . (2011), indicating that inour that . (2011),indicating etween 0.03 and 8) to evaluate 0.03 and8)toevaluate etween s value of 0.045‰ calculated 0.045‰calculated valueof d considerthatnickel 61 Ni/ 58 Ni ratiosof δ 60/58 61 Ni/ Ni 58 Ni 10 as low as10 as low 64 for Cuand>10 solutions (separation efficiency >>10 efficiency (separation solutions interference from interference to monitorall natural Niisotope ratios. Ass me bracketing acalibrator-sample using analysed interferencesfrom calcium (e.g., oxides elementsproxyfor matrix-forming insilicate rocks. solutions.Th in analysed and 0.5 ratios between2 of theinfluence column purification,wetested with Caand separately effect Potential matrix if even chemical procedure during the divided by the mass of the element divided by themassof estimated separation efficiency factor,the mass defined as (g) an element of loaded onresin concentrations inpurifiedsamples were all Brest. II)at PSO, X-series (ICP-Q-MS, ICP-Quadrupole elementswithan ofmatrix concentrations measuring basalts andshale)by checked was Chemical purificationefficiency Evaluation of potential matrix effect spike/sample ratios between ~0.6and ~ 4, spike/sample ratiosbetween optimum spike/sample ratio. Calculations indicated that the best results were obtained with Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards The Matlab®templatec Ni wasnotconsideredinourdouble-spikecalc

Accepted6 Article ), although care should betake ), although should care 3 . On the other hand, Zn was well separated (s Zn wellseparated was . Ontheotherhand, 7 for Mn. Titanium was found more difficult Titanium wasfoundmore forMn. 64 Zn was not critical for our study. Iron was not detected in all analysed inallanalysed Iron study. wasnotdetected Zn notcriticalforour was s were further assessed using seve assessed using further s were S. Since several Ni-rich sulfides we Ni-richsulfides S. Sinceseveral onstructed by Rudge onstructed by n to avoid Zn dur n toavoid contamination remaining after purification, was > 10 purification,was after remaining 6 samples had high amounts of iron. high amountsofiron. sampleshad ), which suggests quantitatively that ironwas separated andchemical purification efficiency Potassium, Na,Ca,Cr, 40 Ca which is consistent below thebelow detection limitofthe instrument. The hown in Table 1, the results suggest that isobaric thatisobaric hown inTable1,theresults suggest 18 et al et for a number of RMs (e.g., manganese nodules, a numberofRMs(e.g., for O on sulfur on the instrumental mass biaswithS/Ni ontheinstrumental mass sulfur ulations andfinalresu ulations thod and without a nickel double-spike inorder andwithoutanickel thod e same was also done with Ca, which is a good Ca,whichisa also donewith e samewas . (2009) allowed us to further evaluate the evaluate . (2009)allowedustofurther Calcium isalso a sour 58 Ni). Matrix-doped nickelsolutionswere Ni). Matrix-doped ral NIST SRM 986 solutionsdoped ral NIST SRM986 eparation efficiency factor betterthan factor efficiency eparation re analysed withoutNi-specresin analysed re to separate with a separation factor factor aseparation with to separate withourresults. Mn, Fe, Mo andCo Mn, Fe,Mo ing sample preparation. Since preparation. ing sample lts, potential isobaric lts, potential 6 for Na and Mg, ~10 and Mg, forNa ce ofpotential isobaric ce 6

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards yieldingand 0.5, between 1 interferencesand ininstrumental changes mass bias were insignificantelement/Ni for ratios uncertainties the total range for of cal AsshowninFigure 4,values correction. involvedpurification method doping. Thesecond anion-excha purification through involvedsample method massbiasusing methods.One instrumental two different for corrected Several sulfides aswell as Ni-rich andanalysed ironmeteoriteswere(i.e., Ni-rich meteorites) mass bias Comparison between Cu-doping and double-spike correctionmethods for instrumental non-doped NIST SRM986. isthetwostandarddevi precision The reported instrumental massbias for corrected and Swere section onMC-ICP-MS settings), measuredNiis fromCaO. interferences resolved majorisobaric Ca/Ni = 1and S/Ni= 1,respectively. also imply results These the mode medium-resolution that validate the reliability of the doubl of validate thereliability Accepted incl igneous rocks, isotope valuesinvarious compare Niisotopefractionation It estimate isimportantan to have ofthe Bulk Silicateto interpret Earthvalue and inorder Assessment of the Bulk Silicate Ea Sample analysis results and discussion Article δ 60/58 nge resin andinstrumentalma nge resin Ni valuesof-0.18± 0.14‰(2 in natural samples. Hence, our approach was to measure Ni tomeasure was approach Hence,our in naturalsamples. δ e-spike data re e-spike data 60/58 rth (BSE)Niisotope composition Ni values from -0.60‰ to 0.40‰. These results further Ni valuesfrom-0.60‰to0.40‰.Theseresultsfurther culated withthetwomethodsfallwithin culated uding oceanic basalts and Archaean komatiites. The andArchaean oceanic basalts uding ation value based on replicate measurements of measurements replicate ation valuebasedon using the sample-calibrator bracketing method. method. bracketing using thesample-calibrator Note thatsimilartotheFe-doping (see tests duction scheme. scheme. duction otope values for NIST SRM986dopedwithCa valuesfor otope through the entire procedure and double-spike anddouble-spike entireprocedure through the ss bias correction basedonCu- ss biascorrection s ) and 0.02 ±) and0.02 0.14‰(2 s ) for Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards mantleisotopecomposition. Earth’s theearly represent of themodernman yieldestimate an former values between -0.10‰ and +0.15‰; BHVO-2 gave a near zero zero gave anear +0.15‰;BHVO-2 -0.10‰and values between δ (Plank Incomposition of-0.07‰. addition, perido value of-0.13‰,whereas For comparison, previously published previously For comparison, significant. beconsidered to uncertainty analytical the to close ultramafic RMs(i.e., dunite basalt, and peridotite) closelyclustereda range within of and IODP core 1149, displayed a small range of IODP asmallrange 1149,displayed and core fre BIR-1, DTS-1andPCC-1) (BHVO-2, DNC-1, reported inthisstudy.Insummary, all mantle-derived rocks analysed inthisstudy, i.e., RMs Ni with agreement in andare basalts, altered positive value of +0.10‰. Serpentinitefromth positive valueof+0.10‰. +0.07‰, whilehand-picked yielded of Loihi avalue BSE Ni which isimportantfordetermining the (Kurz (Kurz systematically heavier with valuesupto+0.34± systematically 0.08‰ (2 heavier 2 probably derivedfrom deep enrichedEart the (Logatchev field).Fresh pillow basalts from Lo Seamount)andse (Loihi samples fromHawaii reference material heterogeneity or toanas or heterogeneity material reference inth smalldiscrepancy The (~+0.1‰). BHVO-2 In Gall contrast, for BHVO-2. 60/58 s

Accepted ArticleFigure 5display isot and , n=11).Table4 Ni values between -0.03 and +0.10‰, without an and+0.10‰,without Ni valuesbetween-0.03 et al et al Igneous and ultramaf . 1983). Therefore, they might represen they might . 1983).Therefore, . 2000,Rouxel et al ic rock rock ic samples: et al . 2003) were also analysed (Tab also analysed . 2003)were tite PCC-1hadthevalueof . (2012) obtained resultssimila . (2012)obtained fresh andalteredbasaltsrec δ 60/58 Ni values (figure 5 in Cameron Ni values 5inCameron (figure tle isotope composition, tle isotope yet unclear difference in analytical methods. inanalytical yet difference unclear opic and chemical compositionofthebasalt and chemical opic isotope values for other mafic igneous rocks igneous rocks other mafic isotope valuesfor h’s mantle as indicated by their high their mantle asindicatedby h’s rpentinite fromtheMid-AtlanticRidgerpentinite e Logatchev hydrothermal field hada field Logatchev hydrothermal e isotope composition. Fresh glass isotopecomposition.Fresh from material ihi Seamountwereselect ihi As presented in Table 3 and Figure 5,maficand Figure inTable3and As presented δ e data, although minor, e data,although 60/58 t themostprimitivemantle composition, olivine crystals displayed a slightly more Ni values,lessthan0.1‰,whichistoo sh and altered basalts from Loihi from seamount altered basalts sh and y significant difference between fresh and fresh between y difference significant s ) for PCC-1 and +0.13 ±) forPCC-1and 0.03‰(2 +0.12‰ and dunite DTS-1hada +0.12‰ anddunite le 5 and Figure 5). They gave 5).They and Figure le 5 overed at IODP coresite1149 overed at δ 60/58 r tooursforbothPCC-1and whereas thelattermay Ni value (0.01± 0.04‰, ed since they were ed might to berelated et al . 2009)are 3 He/ δ δ 60/58 60/58 4 He ratios Ni Ni s ) Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards As expected, ofth asrepresentative composition canbetaken both detritalandchemical repos sedimentsarethe Deep-sea onEarth. important sedimentary reservoir the mostcommoncomponentofsedimentson fresh 1149 along and withaltered these samples, ranging from -0.10to-1.03‰(T from these samples,ranging large Anunexpected BE-2). (BE-1and separates composed ofalmost purekomatiitic materials (B andA) twosamples were olivine mineral dominated by mineralisation( pentlandite were representative of Ni-sulfide-mineralised obtainedforig values of fall intherange Acceptedvalues aslow-0.82±0.02‰, withmost Zimbabwesulfides from that showa systematic enrichment inlowatomic number isotopes to magmatic Ni-rich Archaean for data isotope Ni recent by confirmed further is interpretation pr themagmatic Ni isotopestookplaceduring fractionation inkomatiites, ourresults clearly dem isotope composition ofkomatiites.yet Regardless as ofthe, unclear, mechanism ofNiisotope toobtain didnotexpect BSE composition,andwe The choice these of was samples essentially motivated by ourattempt a toassess the value for 0.26 to-0.10‰. whereas olivine minerals and pure komatiiteclose were samples basalt tomodern values, from- were values, from-0.62to-1.03‰, Article Ni isotopecompositio Ni isotope composition of koma of Ni isotopecomposition δ 60/58 Ni values of +0.04 and +0.02‰ for deep-sea clays (Table 5, Figure 5) clearly clearly 5) 5,Figure clays (Table fordeep-sea +0.02‰ Ni valuesof+0.04and origin derived from the continents. Therefore, their Niisotope their continents. Therefore, origin fromthe derived n of deep-sea clays: clays: deep-sea of n basalts describe basalts determined on samples withelev on determined neous and ultramafic rocks in our study. inourstudy. ultramaficrocks neous and tiite-hosted Ni-sulfide ores: Ni-sulfide tiite-hosted AX-1, AX-2, MC-1, TD21, MKTD76), others were otherswere MC-1,TD21,MKTD76), AX-1, AX-2, values clustering around -0.40‰ (Hofmann around -0.40‰ values clustering ultramafic magmas. While some samples were ocesses that formed these rocks. This rocks. thatformedthese ocesses able 6, Figure 5), butthemostnegative 6,Figure 5), able e average composition of the continental crust. crust. continental ofthe composition e average range of Ni isotope values was measured on wasmeasured ofNiisotopevalues range d above(Plank oceanic seafloor; hence they represent an represent they hence oceanic seafloor; onstrate that significant abiotic fractionation of such a large range of variation intheNi ofvariation range such alarge Deep-sea clays were collected at IODP at site collected clays were Deep-sea et al ated content ofpentlandite, content ated . 2000). Clay minerals are Clay are . 2000). minerals Our komatiite samples itory of ofmaterials et al δ 60/58 . Ni Rouxel 2006,Teng Rouxel to non-traditionalisotopes,including a Mg isotope systems traditionallowat from ranging temperature mass-dependent fracti inferences other fromstudies stable of precluding isotope a systems, straightforwardestimate of could be potentially toinvestigate used crystallisation processes at system the magmatic scale. promising totheirubiquitousoccu resultscoupled athighthat govern Niisotopefractionation temp inma and crystallisation effects indicates that Niisotopes are at least as sensitive asFe isotopes tohigh-temperature processes Niisotopeva of of ~0.2‰.Sincetherange magmatic differentiation inthe KilaueaIki lava Feisotopefractionati temperature either crustalcontamin to-0.30‰in from+0.36 witharange samples waslessvariable, high temperatures at occurring Ni isotopefractionations theobserved Therefore, andcrustal reservoirbe ismostprobablyfrom a sourced linked withpartial mantle melting. sulfidesaturation to promoted emplacement, which reactions. Although Sisotopes indicate forsulfurduring crustalcontribution komatiite itunde where poor atmosphere, suggest that these values negative reflectass Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Articlepreviously yielded negative All Archaean komatiite and samples associated mineralisation Ni-sulfide fromthisstudy komatiites ofNi-rich reflect sulfides.contribution the submitted). Therefore,seems very it likely that negativeNi isotopemeasured values these for Ni isotope composition of theBulk Silicate of Ni isotopecomposition Earth: et al ation orhigh-temperatu . 2008). Our results for Ni isotopes are, forNi . 2008).Ourresults Δ 33 (i.e., abiotic Ironfractionation). S values(Table6;Bekker rwent mass-independent frac rwent mass-independent gmatic adeta Although systems. on has been documented by Teng on hasbeendocumented onation processes have been infe havebeen onation processes nd Fe (e.g., Young and Galy 2004, Dauphasand Fe andGalyYoung 2004, (e.g.,nd riations reported in our study was ~0.90‰,it was reportedinourstudy riations imilation ofsulfurprocessed throughan oxygen- re fractionation (Bekker re fractionation omic number isotopes, O and S(e.g., 2001), Eiler omic numberisotopes,Oand lake (Hawaii) produced Fe produced (Hawaii) lake erature is beyond the scope of this paper, these ofthispaper,these isbeyond thescope erature are solely the result ofmagmatic processes rrence in mantle rocks mean thatNiisotopes inmantlerocksmean rrence form sulfide mineralisation, Niisunlikelyform sulfidemineralisation, to et al tionation during photochemical Mantle heteroge . 2009). Bekker Bekker . 2009). to some extent, consistentwith tosomeextent, isotope composition ofthesame isotope composition iled discussion of parameters ofparameters iled discussion terpreted as being the result of beingas the terpreted rred from studiesofstable from rred et al et al . (2008), whoshowthat . (2008), isotope fractionations . 2009).High- neity andhigh- neity et al . (2009) Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards in range observed anarrow we since However, value. Earth Silicate Bulk the (e.g., Algeo 2004,BrumsackTribovillard andMaynard 2006, metals such Cu,Vand as Zn, metal/Al Mo,Ni,U, ratios to leading well crustal above values by arecharacterised shales 1961), organic-rich for bulkcr proxyas a considered generally with environments temperature positive values relative BSE provide Niisotope strong fractionation evidence inlow- to for metals suchasNi,Cu,Zn andCoformin Mn-nodul respectively. and +0.36‰, values of+1.03‰ Nod-P-1) that represent composite samples from the Atlantic and Pacific oceans gave oceans andPacific Atlantic the from samples composite represent that Nod-P-1) USA) gave (Maryland, and CLB-1 coal USA) Kentucky, Ohioshale(Morehead, Devonian namely SDO-1 Ni isotopesin BSE. compositionof clays of theNiisotope improvesourunderstanding minerals suchasdeep-sea our in analysed rocks ofmantle-derived range Steele 0.036‰ determinedby BSE estimate reproducibility). Our 0.05‰ (measurement common basalts of composition totheaverage value -0.1 and between~ rocks, from mantle-derived

Accepted fromseawater eitherdirectly sources, derived pr sediments organic matter-rich water column orduring diagenesis insediments. Hence,values positive Niisotope inmarine organometallic and withironsulfides complexes, (e.g., formeither which may pyrite), inthe et al Article . 2011). In marine sediments nickelhasast In. 2011). marinesediments Organic matter-rich samples: matter-rich Organic Mn-nodule RMs: Mn-nodule δ 60/58 selected RMs RMs selected Ni valuesof+0.58‰and+ Geological reference materials materials reference Geological et al interesting prospects for future studies. Although shales are are Althoughinteresting shales forfuture studies. prospects obably reflect the contribution the reflect obably . (2011) on Japanese basalt JP-1 basalt . (2011)onJapanese Samples containing c high Samples ustal composition (e.g., Turekian and Wedepohl andWedepohl (e.g., Turekian composition ustal 0.47‰, respectively (Table 7 and Figure 5). These 5).These and Figure 7 (Table respectively 0.47‰, or in association orin deep-sea sediments generally at water depths depths generallyat water sediments deep-sea study and the inclusion of common sedimentary inclusionofcommon and the study authigenic enrichments of redox-sensitive enrichments trace authigenic of redox-sensitive +0.1‰, we feel confident to ascribe the BSE ascribethe confidentto wefeel +0.1‰, rong affinity to organic matter, forming forming matter, toorganic affinity rong and mantle-derived rocks, whichis+0.05±rocks, andmantle-derived es are typically enriched intransition enriched es aretypically of manganese nodules (Nod-A-1 and nodules(Nod-A-1 of manganese is slightly thatof+0.179± lowerthan et al with organic matter. matter. with organic of isotopically heavy nickel of isotopically heavy ontents of organic matter, ontents oforganic . 2006,Scott and dunite DTS-2. The large andduniteDTS-2.Thelarge δ 60/58 et al Ni values . 2008,Scott δ 60/58 Ni 2010, Schmitt Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards 2004; Rehkämper (Dideriksen for previously analysed These noduleshadbeen individual Mn-nodulescollectedfromtheAtlantic of alarge number from RMswereprepared twoMn-nodule The interface. at thesediment-water concentri and 6km.Theyconsist of between 4 matter re-mineralisation, (4) matter re-mineralisation, matter tothesediments a high oforganic supply (3)biological produ ontooxyhydroxides, seawater from directly growth, (2)adsorptionofmetals duringscavenged nodule ontoMn-oxides with associated sediments (e.g., processe (1)diagenetic suchvariations: explain withothermetalisotopesystof nodules,compared tomechanismsinvolvedintheformation and indicatesthatNiisotopesareparticularly sensitive mass uni twonodulesislarger(per between these 2004) andCdisotopes. ofMo(Anbar exception Accepted holdtrueforMn-noduleCdisot The samemight seawater. of strength ionic high the because of probably Cd seawater with compared fractionated w thatCdisotopesincorporated (2010) argue (Gueguen onFe-Mn oxides results onnickeladsorption growth. Similarly, Niisotopes might be affectedthis mechanism by revealed as by experimental which in porewaters, developed closed system equilibrium fractionation during preferential adsorp Rehkämper intheNi responsible forvariations are whichoftheseprocesses to establish clearly areneeded dataset, nodules, aswellalarger theseme contribution ofeach of regarding the surfaces. entirenodule tocover observed have been Article et al et al et al . (2002) argue that variations in Tl argue thatvariations . (2002) . 2006), Zn and Cu (Bigalke (Bigalke Zn andCu . 2006), et al . 2009, Cloquet . 2002), highlighting differences in their isotopic composition withthe highlighting intheirisotopiccomposition . 2002), differences in situ organic matter) were released were organicmatter) isotopecompositionofFe-Mn nodules. et al biological activity, specifically that of microbial mats,which biological thatof activity, specifically . 2005),Mo(Barling ith Mn-oxides intoFe-Mn werenot crusts ith Mn-oxides et al chanisms tothecompositionchanisms ofpolymetallic cally laminated Fe-Mn oxyhydroxides precipitated s through which metals contained in subsurface insubsurface which metalscontained s through are an important source of metals forMn-nodule animportantsourceof are The difference inNi Thedifference other isotopic systems (Table 8) such as Fe 8)suchas isotopicsystems (Table other ope compositions thatprobably biotic reflect ope providing metalstopor t) than for any other studiedisotopesystem, other t) thanforany . 2010,Chapman . ctivity insurfacewhich could waters, result in isotope ratios of Mn-nodules reflect isotoperatiosofMn-nodulesreflect and Pacific oceans (Table 7 and Figure 5). 7andFigure (Table and Pacificoceans ems. Several processes ems. Severalprocesses tion ofheavy ina Tlisotopes ontoMn-oxides It investigations thatmoredetailed isclear et al . 2011). Alternatively, Horner Horner . 2011).Alternatively, et al into pore waters andthen intoporewaters . 2001) and Tl(Nielsen . 2001)and et al isotopecomposition . 2006), Cd (Horner . 2006),Cd(Horner e waters during organic- waters during e could be inferred to beinferred could et al et al et al . . . Table 5;2 Our values are also in full agreement with the range of range the with agreement full in also are Our values 2007, Regelous (B processes nucleosynthetic Since the firstNiisotope measurements onmeteoritic were made materials tostudy comp and to rocks Ni-rich on procedure analytical goalsOur main inmeasuring ironmeteorite were samples toimplement ourexperimental and ironmeteorites of Ni isotopecomposition (Table7). Niisotopesof+0.45‰ inheavy IF-Gan enrichment Formation sampledisplayed suggesting variabilityNi isotope ratios withincommon in continental Finally, rocks. Iron the Niisotopes heavy in significantly enriched was content nickel low very G-2with granite contrast, In (see above). clays deep-sea Pacific to Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards soil sampleNIST SRM2711(Table7a activity, biological by alt affected Niisotopesinprecipita that suggest therefore We intheirdepletion example, for (and zinc), (Schmitt fractionations rather micro-organisms by than with datainCook TheIron meteoritesNantan Gibeon and bothdisplayed fairly similar positive variations. w reservoirs extraterrestrial concerns mainly Accepted Articleriver sedimentwith to close, withinuncertainty, +0.14‰, whichisvery Other RMs corresponding to major terrestrial reservoirs: terrestrial tomajor RMscorresponding Other et al s calculated on duplicate analyses) of duplicateanalyses) on calculated . 2009). The chemical behaviour of nickel in seawater is akin tothatofcadmium isakin nickel in seawater behaviourof . 2009).Thechemical et al et al δ . 2008,Chen 60/58 . (2008),whoobtaineda Ni values of +0.10 and +0.13‰, respectively (Cameron (Cameron respectively and +0.13‰, Ni valuesof+0.10 irck andLugmair Cook 1988, hough this remains to be demonstrated. hough tobedemonstrated. thisremains et al . 2009), the available dataset of available dataset . 2009),the nd Figure 5) was found to have a 5) wasfoundtohave Figure nd with a +0.43‰ value (Table 7 and Figure 5), Figure 7and +0.43‰ value(Table with a surface waters upon their uptake by upontheiruptake phytoplankton. waters surface ith themain focus onmass- fractionation during adsorption on Fe-Mn oxides onFe-Mn during oxides adsorption fractionation δ +0.26‰ and +0.31‰, respectively, consistent and+0.31‰, respectively, +0.26‰ 62/58 ted marine Fe-Mn oxides might have been also mightFe-Mn havebeen oxides ted marine are our data with results frompreviousstudies. withresults are ourdata lithogenic sedimentssu Ni valueof+0.37±Iron. 0.09‰on Gibeon δ 60/58 et al Ni valuesmeasurediniron . 2006,2007,Moynier The metal-contaminated Themetal-contaminated Ni isotope determinations Niisotope independent Niisotope independent δ 60/58 ch asloessandNile δ Ni valueof 60/58 et al Ni values (see values Ni . 2009)and et al . independently fractionated Niisot fractionated independently The chondrites. classes of different materialstothe precursor of region formed inarestricted (2011) andRegelous protosolar nebulaofmineralog mass-inde are and chondrites,which As discussedby Regelous mass unit. ICP-MS solutionbatc Nistandard the Aesar thatMoynier however importanttonote in meteorites few and +0.80‰(only atomic numberisot enriched inhigh are also meteorites analysedMoynier by Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Moynierdependent Niisotopecompositions, suggestive lateral of heterogeneity inthe Solar early System. Alternatively, based onmass- Ni of Inaddition, therange have alsooverlapped. bodies forthedifferen ofparent source regions meteorites by Cameron Accepted differentiation metallic of the core. Silicate Bulk the from differed may have Niisot andthat segregation during core Earth’s Altogether, these results suggest that significan magmatic temperature °C),withthe metal (800 being enriched number inlowatomic isotopes. demonstrated anisotopicfracti Huh Recently, solid-vapour,distinct phases(e.g., metal-silicate). vari interpretation, nickelisotope isotopicpool,whichwa acommon fractionation from meteorites followthe same mass-dependent line fractionation as terrestrial samples and indicate Article et al et al et . (2008)suggestthateachironme et al . (2009)andSteele ical phases with different withdifferent ical phases onation of at least -0.3‰ between at least-0.3‰ onation of . (2008), the observed isotopicva . (2008),theobserved the protosolar nebula aswas theprotosolarnebula et al ations in meteorites reflect ph reflect ations inmeteorites ope values of iron ope valuesofiron pendent, are likely to be the result of mixing withinthe result of likely tobethe are pendent, these datasets have negative havenegative these datasets . (2007) and Cameron . (2007)and et al Earth composition developed after the early theearly developed after composition Earth h No 066110910 and expressed theirresultsasper 066110910 andexpressed h No opes and have a range of a range opes andhave . (2007) report their isotopic ratios withrespectto reporttheirisotopicratios . (2007) et al et t classes of chondrites classes ofchondrites t t Ni isotope fractionations may have occurred isotopefractionationsmay occurred t Ni have ope composition of the Earth after its accretion afteritsaccretion ope compositionoftheEarth et al et isotope values among ir isotopevaluesamong . (2007)andCook . (2011),i.e.,0.24to0.36‰.Other meteorites and s homogenised in the solar nebula. Insolar nebula. this s homogenisedinthe nucleosynthetic origin. Steele et al teorite class had theirprotolith teorite classhad previously demonstrated forthe demonstrated previously overlap between mass- between overlap ysicochemical reactions between ysicochemical reactions . (2009), including chondrites, . (2009), riations among iron meteorites ironmeteorites riations among metallic andsilicatephasesat metallic et al Ni isotope values). ItNi isotopevalues). is chondrites suggeststhatthe chondrites et al values between +0.02‰ between values and iron meteoritesmightand iron . (2009) experimentally experimentally . (2009) . (2007) argue thatall . (2007)argue on meteoritesisalso on et al . new results for RMs and analytical methods pres analytical new resultsforRMsand ch through processed small amountsofNiwere small butmeaningful fractionations ofmoreten than times the analytical precision evenwhen c ofNi large range a including sulfides,and of samplemeasuring matrices range a broad Ni is demonstrated thatfor processes, while negative fracti isotope fractionations systematic, are fractionations i.e., positive characterise low-temperature theBSE value,and,more from significantly deviate andse magmatic (e.g., reservoirs materials, which show a range of range materials, whichshowa Ni isotopeco +0.05 ± herethe 0.05‰.Wereport sulfides withnegative somevariationsinthe explain thatfractionation from -0.10to-1.03‰,indicating nodules and organic matter-rich shales have positive have shales nodules andorganic matter-rich Mn oxides (Gueguen Mn oxides and, potentially, low- by processes abiotic producedby also 2009), buttheycan be are notanuniquebi Ni isotopefractionations value.This anearzero close tothatofBSE with otherwise, least as shownby the mineralised samples, komatiite have compositions Niisotope Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards crystals allowed the ustoestablish isotopi ultramaficand minerals and igneous alteredfresh rocks such as and komatiites basalts, olivine clays, ofdeep-sea In investigation thispaper, Conclusions Accepted Articlesamples ofkomatiites associated and Ni-sulfide mineralisation displaya range of inaqueous inorganic Niisotopefractionations et al et δ 60/58 . 2011). Therefore, the Ni isotope . 2011).Therefore,the otopes the double-spike correcti otopes thedouble-spike Ni values affectedNi isotope composition the of komatiites, which Ni isotopecompositionofnatural onations mark high-temperature onations markhigh-temperature dimentary rocks) relevant to the biogeochemical Ni cycle might might cycle Ni biogeochemical the to relevant rocks) dimentary δ temperature processes during co-precipitation ofNiwithFe- co-precipitation during processes temperature 60/58 Ni values more than 1‰. Interestingly,Ni valuesmorethan1‰. bothFe-Mn c composition of the Bulk Silicate Earth at at Earth Silicate Bulk ofthe c composition oncentrations. The method allowed us to measure ustomeasure Themethodallowed oncentrations. from silicatefrom rocks tometalliferous deposits, and mantle-derived rock osignature, as was recently inferred (Cameron inferred recently aswas osignature, environments. We alsofoundthatbulkrock environments.We emistry and determined byMC-ICP-MS.emistry The anddetermined processes such as high-temperature magmatic magmatic as high-temperature such processes is an important finding since itemphasisesthat animportantfinding since is ented hereshould help ented mposition ofselected in high-temperature magmatic systems can can systems in high-temperature magmatic importantly, our results demonstratethatNi results importantly, our δ 60/58 Ni values,suggesting eitherbioticor on method is appropriate for on methodisappropriatefor composition of speci processes. Finally, we processes. have samples. Wesamples. infer that Ni-rich s of RMs andmafic s of geological reference geological reference to make Niisotope to fic terrestrial fic terrestrial δ 60/58 δ 60/58 Ni values Ni = et al . Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Mineralogy andGeochemistry, 55 Observati Molybdenum stableisotopes: Anbar A.D.(2004) cyclothems. faciesinco redox and behavior Trace-element Algeo T.J.andMaynard J.B.(2004) 55 isotopes. Analytical methodsfornon-traditional F.Albarede andBeardB.(2004) References visiting scientist grant. by suppor Europôle Mer.Participation was AB ISOMAR European Marie-Curie to thismanuscript.Thestud and corrections comments constructive for their thanked gratefully are Meisel Thomas editor andthe reviewers commentsonthefi thoughtful Sorensen fortheir Aust andWestern mineralisation fromCanada meteorite samples,FiorentiniMarco and ofkomatiites forsamples and associated Ni-sulfide for andYoanGerman Liorzou thankCéline We Acknowledgements materials. and planetary measurements morefreque straightforward,and more

Accepted, 113–152. Article Chemical Geology, 206 project (European Reintegr project(European , 429–454. , 429–454. , 289–318. ons, interpretations and directions. anddirections. ons, interpretations y was supported by funding from Ifremer, the y from funding supported by was re shales of Upper Pennsylvanian Kansas-type Kansas-type Pennsylvanian ofUpper shales re ralia. We thank Harry Elderfield and Jeffrey andJeffrey thankHarry Elderfield We ralia. ted by NSERC Discovery Grant and IFREMER and byGrant NSERCDiscoveryted laboratory assistance, Jean-Alix Barrat for iron Barrat for Jean-Alix assistance, laboratory Reviews inMineralogyandReviews Geochemistry, rst draftofthismanus ntlystudies utilised ofterrestrial infuture ation grant#FP7#247837),and cript. Two anonymous Twoanonymous cript. Reviews in Reviews Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Atmospheric sulfurinArchaean komatiite-hostednickel deposits. (2009) M.L., Fiorentini A.,BarleyM.E., Bekker 193 Planetary ScienceLetters, vari Natural mass-dependent Barling J.,ArnoldG.L. and AnbarA.D.(2001) Analyst, 127 of Mn-Fenodulesby Multielemental analysis Axelsson M.D.,Rodushkin I.,Ingri J.andOhlander B.(2002) 35 Metal stable isotopes Anbar A.D.andRouxelO.(2007) Mo intercalibration. tr IC1 contamination-prone (BATS) GEOTRACES (2012) M., RouxelO.,Sohrin Y., St M.,LacanF.,GallonFornaceK.,Gault-Ringold C.,Galer RadicA.,Rehkämper A.R., S., Boyle E.A.,JohnS.Abouchami W.,AdkinsJ.F 131–143. isotopesin Allendeinclusions. Nickel andchromium Birck J.L.andLugmair G.W. (1988) soil. ofsour Stable CuandZn ratiosastracers isotope Bigalke M.,WeyerS.,Kobz

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Earth and , Cook D.L., Wadhwa M.,Cook D.L.,Wadhwa Janney P.E., Dauphas Science, 42 Mass-dependent fractionation ofnickel isotopes inmeteoritic metal. M.,Cook D.L.,Wadhwa ClaytonR.N.,Daupha doi: 10.1029/2007GL032431. Nickel isotopic anomalies introilite fromironmeteorites. M., Cook D.L.,ClaytonR.N.,Wadhwa MC-ICP-MS. by measured BCR 176,GSS-1,GXR-1,GXR-2,GSD-12,Nod-P-1, isotopicNatural cadmium variationsineight Cloquet C.,RouxelO.,CarignanJ.andLibourel G. (2005) 73 Cosmochimica Acta, isot fornickel A search Chen J.H.,Papanastassiou D.A.andWasserburg G.J. (2009) Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Articlematerials. isotopic and Chemical separation Chapman B.J.andWilkinson J.B.,MasonT.F.D.,Coles J.J. WeissD.J., (2006) United the of Sciences stableisotopesofnickel. onthe A biomarkerbased C. andHouseC.H.(2009) Archer D., Cameron V.,Vance black shaleformation. carbon organic recent metalcontentof The trace Brumsack H.J.(2006) Geostandards andGeoanalytical 30 Research, , 2067–2077. , 2067–2077. Palaeogeography, Palaeoclimatology, Palaeoecology, 232 Palaeogeography, Palaeoclimatology, Palaeoecology, opic anomaliesinironme States of America, 106 Statesof , 1461–1471. Geostandards andGeoanalytical 29 Research, variations of Cu and Zn fro variations ofCuandZn Janney P.E. andDavis A.M. (2008) geological reference materials (NIST SRM2711, materials geological reference , 10944–10948. , 10944–10948. -rich sediments: Implications sediments: forCretaceous -rich teorites and s N.,Janney P.E. andDavisA.M. (2007) N., ClaytonR.N.andDavis A.M. (2006) Proceedings of the National Academy of Academy of National the of Proceedings Nod-A-1) and anthropogenic samples, andanthropogenic Nod-A-1) Geophysical Research Letters, 35, Geophysical ResearchLetters, , 5–16. , 5–16. m five geological reference reference geological m five chondrites. chondrites. Meteoritics andPlanetary Meteoritics Geochimica et Geochimica , 95–106. , 344–361. Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards ofnon-mass-dependent High measurements precision Geophysical Monograph Series,188 of Anewtype mineralization: along processes ofhydrothermal Geodiversity Rouxel O.(2010) Cherkashov G., T.,Poroshina Semkova I.,Bohn M.,DonvalJ.P.,P. K., Henry Murphy and FouquetP., Etoubleau Y.,Cambon J.,Charlou J.L., Ondréas H.,Barriga F.J.A.S., Geochemistry, 43 Oxygen isotope ofbasaltic variations mantleand lavas upper rocks. Eiler J.M.(2001) double spike. Iron isotopesinnaturalcarbona andStippDideriksen K., S.L.S. BakerJ.A. (2006) 831–832. Mass spectrometryand va natural Dauphas N.and Rouxel O.(2006) results. measurement expressi termsfor Guidelines andrecommended Coplen T.B.(2011) metal via multicollectorICP-MS. Accepted at 5000moffHawaii. Fe-o venting supports hydrothermal Ultra-diffuse Chan C.S.,TeboB.M., Staudi RouxelO.J.,Bach K.J.,Edwards B.T., Glazer Article Geochimica et Cosmochimica Acta, 70 Acta, etCosmochimicaGeochimica , 319–364. , 319–364. Rapid Communications in Mass Spectrometry, 25 The ISME Journal ISME The oceanic Cu-Zn-Co-Au volcanogenic massive sulfidedeposit. massive volcanogenic Cu-Zn-Co-Au oceanic te minerals determined by determined te minerals MC-ICP-MS withaFe-58-Fe-54 gel H. and Moyer C.L. (2011) gel H.and MoyerC.L.(2011) riations ofironisotopes. riations Analytical Chemistry, 78 , 444pp. , 1–11. the mid-atlantic ridge on ofstable-isotope-r W., EmersonR.E., TonerB.M., D.,Davis xidizing bacteria and massive umberdeposition and massive bacteria xidizing effects innickel effects , 118–132. Mass Spectrometry Reviews, 25 Reviews, Mass Spectrometry , 8477–8484. , 8477–8484. Reviews inMineralogy and Reviews and ultramafic-hosted and ultramafic-hosted atio and gas-ratio atio andgas-ratio isotopes inmeteoritic isotopes , 2538–2560. , me marine and ancient Ni biogeochemicalcyclethroughgeological time: Insightsvariations fromNiisotope inmodern Y. (2011) Gueguen B.,Rouxel O.,Ponzevera E.,Sorensen J.V., Toner B.M., Bekker A. andFouquet theNa Researchof of atomic ratiosand Absolute isotopicabundance Gramlich L.A.,BarnesI.L.and J.W.,Machlan PaulsenP.J. (1989) 18(SpecialIssue) Geostandards Newsletter, and sa 1994 compilationofworking values Govindaraju K. (1994) 847-877. Green Mount Keith,Agnew–Wiluna andgenesisof Controls ontheemplacement N.,Beresford M.,Rosengren Fiorentini 83–94. chondrites, ironmeteor Application ofMC-ICP-MS totheprecisedeter Fehr M.andHallidayM.A., Rehkämper A.N.(2004) and MC-ICP-MS. Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted ArticleDetermination ofma Gall L.,Williams H.,SiebertC.andHallidayA.(2012) oceans. modern andancient investigation isotopicfrac ofnickel andexperimental Theoretical Fujii T.,MoynierF., N.and Abe Dauphas M. (2011) Journal of Analytical Journal of ss-dependent variations innickelis variations ss-dependent tallifereous deposits. tallifereous tional Institute of St Instituteof tional ites andsulfides. ites Geochimica Acta, et 75 Cosmochimica stone Belt, Australia. stone Western International Journal International Atomic Spectrometry, 27 S., Grguric B. and BarleyM.(2007) B.and Grguric S., mple description for 383 geostandards. for383 mple description AGU Fall 2011 Meeting AGU andards andTechnology,94 the MKD5 and Sarah’s Find Ni–Cu–PGE deposits, Find MKD5 andSarah’s the , 158pp. , 158pp. weight of a reference sample ofnickel. sample reference ofa weight mination oftelluriumisotope compositionsin otope compositionsusing doublespiking of Mass Spectrometry, 232 MassSpectrometry, of tionation in species relevant to speciesrelevant tionation in Mineralium Deposita, 42 Deposita, Mineralium , 137–145. , 137–145. , 469–482. , 469–482. , San Francisco, USA. USA. Francisco, , San , 347-356. Journal , , Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Xue Z. and HeinJ.R.(2010 M., Horner T.J.,SchönbächlerM.,Rehkämper deposits inZimbabweand nickel multiple-sulfur, using iron isotope data. Comparing orthomagmatic and mineralization hydrothermal models ofkomatiite-hosted nickel Deposita) Mineralium Hofmann A.,Bekker A.,Dirks P.,Gueguen B., Moynier F., Blichert-Toft J.,TéloukP.,F., Moynier Blichert-Toft AcceptedNickel isotopicstudiesinmeteorites. Morand P.C.J. (1983) andAllegre Chemical Geology,156 copper and of Precise analysis C.N.,TéloukP.F. Marechal andAlbarède (1999) 66 Earth andPlanetary Letters, Science Helium isotopicvariationsinvolcanicrocksfr M.D., JenkinsW.J.,HartS.R.andClague D.(1983) Kurz at 800°Cand10kbar. study from experimental ofNistableis fractionation High temperature E.D.and ManningHuh M.C.,LazarC.,Young C.E. (2009) 105–128. Articlethe genesisofkomatiite-associat Thermomechanical erosionat Mine, the Abitibigreenstone Alexo Implications Ontario: belt, for and DavisP. Houlé M.,LesherC.M. (2012) Geophysics 11 Geosystems, archivesof as crusts Ferromanganese , 251–273. , 1525–2027. )

zinc isotopiccompositionsby pl ed Ni–Cu–(PGE) mineralization. ed Ni–Cu–(PGE) deep water Cd isotopecompositions. water deep Earth andPlanetary , 388–406. , 388–406. Luck J.M. and AlbarèdeF. (2007) otopes between metal andsilicates:Constraints otopes betweenmetal om Loihi seamount and the island of Hawaii. om Loihi islandofHawaii. seamountandthe EOS TransactionsAGU, 90 EOS Rouxel O.J.andRumble D.(Submitted to Nielsen S.G., Williams H.,HallidayA.N., Science Letters, 63 Science Letters, asma-source massspectrometry. Mineralium Deposita, 47 Deposita, Mineralium Mineralium Deposita. Mineralium Geochemistry Geochemistry . , 167–176. ,

The Dundonald deposit: An example ofvolcan An example The Dundonalddeposit: Muir J.E.andComba C.D.A.(1979) 71 Acta, Geochimicaet Cosmochimica Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Comparative stableisotopegeoche metals and no trace of metals andnotrace Nickel isotopes inironmeteorites-nucleosynthetic M., LatkoczyC., Quitté G., Meier Site 1149. Plank T.,Ludden J.N. water samples by MC-ICP-MS. The precise anddetermination accurate ofthallium isotope compositions and concentrations for Nielsen S.G., M.,BakerJ.andHallidayA.N.(2004) Rehkämper Canadian Journal of Earth Sciences,5 bodies ultramaficigneous Contrasting Archaean G.D. (1968) Naldrett A.J.andMason Mineralogist, 17 Accepted deposits. ferromanganese Thallium isotope variations inseawater and hydrogenetic, diagenetic, and hydrothermal (2002) RehkämperFrank M.,M., Hein J.R.,PorcelliD., HallidayA.,Ingri J. andLiebetrau V. 272 SolarSystem. intheearly Nickel isotopeheterogeneity Regelous M.,ElliottT. Article , 330–338. Proceedings ofthe Ocean Drilling Progr , 351–359. 60 et al Fe. Fe. and CoathC.D.(2008) Earth andPlanetary Earth and Planetary Science Letters, 242 Letters, Science Planetary and Earth . (2000) Chemical Geology, 204 mistryNi, Cu,Zn, Fein of and Halliday A.N.andGünther D.(2006) , 4365–4379. , 4365–4379. , 111–143. , 111–143. ic-type nickel-sulfi ic-type in Dundonald and Clergue Townships,Ontario. inDundonaldandClergue Science Letters, 197 Letters, Science anomaliesinsulphide am, Partam,A: InitialReports, 185 Earth and Planetary Science Letters, Letters, Science Planetary and Earth , 109–124. chondrites and chondrites de mineralization. , 65–81. , 65–81. , 16–25. , 16–25. s withnoeffects in iron meteorites. Canadian . New measurement of the ofthe New measurement Günther-Leopold I.,Weinreich Tracing the stepwise oxygenation of the Proterozoic ocean. oftheProterozoic oxygenation thestepwise Tracing Scott C.,LyonsT.W.,BekkerA.,ShenY.,Po environment. isotopic cadmium Mass-dependent Galer Schmitt andAbouchami S.J.G. A.D., (2009) W. Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards T.,KnieKorschinek K.,Faestermann Rugel G., The doublespiketoolbox. Rudge J.F., B.C. Reynolds andBourdon B.(2009) Economic Geologists, 99 fields ontheMid-AtlanticRidge. Copper isotopesystematics ofth Rouxel O.,Fouquetand Ludden Y. J.N.(2004) alteration crust during oceanic fractionation Iron isotope Rouxel O.,Dobbek N.,Ludden J.and Fouquet Y.(2003) Western Australia. komatiite-hosted MtKeithnick Reconstructionextensive ofan dacitic Archaean submarine volcaniccomplex associated withthe S.W.and PalichRosengren N.,CasR.A.F., Beresford B.M.(2008) Accepted (2011) Reinhard Scott C.T.,BekkerA., Article Earth and Planetary Science Letters, 277 Earth andPlanetary ScienceLetters, Precambrian Research, 161 Research, Precambrian 60 , 585–600. Chemical Geology,265 Fe half-life. el deposit, Agnew-Wiluna Greenstone Belt, Yilgarn Craton, Belt,Yilgarn Greenstone el deposit,Agnew-Wiluna Craton, e Lucky Strike, Rainbow, and Loga and Lucky Strike,Rainbow, e Economic Geology andtheBullEconomic R. and Wohlmuther M. (2009) R. andWohlmutherM.(2009) C.T.,SchnetgerB.,Krapez B variations innaturew Physical Review Letters,103 Physical Review ulton S.W.,ChuX.and AnbarA.D.(2008) ulton , 34–52. G., Poutivtsev M., , 420–431. . Chemical Geology, 202 . Chemical ith emphasis on the marine ith emphasisonthe , 262–272. Nature, 452 ., Rumble D.andLyonsT.W. ., Rumble etin of etin of the Societyof tchev sea-floor hydrothermal hydrothermal sea-floor tchev , 072502. , 072502. Schumann D.,Kivel N., , 456-U5. , 456-U5. , 155–182. 72 Bulletin, America Distribution ofthe elements in some major unitsof the Earth's crust. Turekian K.K. andWe 12–32. and metalsaspaleoredox Trace Tribovillard N.,AlgeoT.J.,Lyons 320 durin Iron isotope fractionation Teng F.Z., DauphasN.and Helz R.T.(2008) Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Acceptedspectrometry. Determination ofnatura Tanimizu M.andHirataT.(2006) 75 Cosmochimica Acta, ArticleConfirmation ofmass-independent Niis M.(2011) CoathC.D.andRegelous Steele R.C.J.,ElliottT., coupled plasma-massspectrometry. Determination ofmolybdenum T.F.and KramersSiebert C.,Nägler J.D.(2001) Letters, 63 Ni isotopiccompositions inA Shimamura T.andLugmair (1983) G.W. conditionsbefore euxinic Late Archean , 1620–1622. , 177–188. , 177–188. Journal of Analytical Journal of , 175–192. l isotopic variationinnickelus l depohl K.H. (1961) , 7906–7925. llende andothe g magmatic inKilaueaIki differentiation LavaLake. isotope fractionation byisotope fractionation double-sp paleoproductivity proxies: Anupdate. proxies: paleoproductivity Geochemistry Geophysics Geosystems, 2 T. and Riboulleau A.(2006) Atomic Spectrometry, 21 Atomic Spectrometry, the rise of atmospheric oxygen. atmospheric oxygen. theriseof otopic variability inironmeteorites. r meteorites. ing inductively coupled plasma-mass ing coupled inductively Earth andPlanetary Science , 1423–1426. , 1423–1426. ike multicollectorinductively Geological Society of Geological Societyof Chemical Geology, 232 Geology, 39 Geochimica et Geochimica , 1032. , 1032. , 119–122. Science, , terrestrial materials are repr are terrestrial materials closed byandclays symbols,both extraterrestrialand literature are shown and deep-sea for data the literature.RMs,koma Figure 5.Plotshowing isotopecompositionin Ni oneachmethod). fordetails text measured (see massbiaswhenNiisotoperatiosare ofinstrumental correction double-spike methodfor thetwomethods theconsistency of It indicates wasplotted onthefigure methods. The1:1lineartrend values obtainedw Figure 4.Comparisonof fresh dunite, deep-sea basalts, peridotite, clays olivine crystals. and forfurther See details. text variousigneous andvolca 0.05‰, determinedusing Cameron of NIST SRM 986, still correctly (see fordetails). black determined text The the line isotopic stands composition for deltavalues),wher andnon-zero bars (wide error f were samples (ratiosbelow0.6) Figure 3.PlotofNIST SRM986de de Ni of mean for the calculated were processed. The dashed lines indicate the range of 2 of range the indicate lines Thedashed were processed. themeasur This figure showstheconsistency of standard This chemistry. through was processed Figure 2. Figure forfurtherdetails). (see text grey band the by shown onthefigure <0.06‰ i.e.,2SE to obtain satisfactory precision, during wasnecessary analysis MC-ICP-MS of precision ofthedetermination to done NISTmeasurements were SRM986.These Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article (2SE)of errors Figure 1.Plotoftwostandard captions Figure Geochemistry, 55 co The isotopegeochemistryand Young E.D.andGaly A. (2004)

Isotopic composition of the mono-elemental standard solutionNi standard Isotopiccomposition ofthemono-elemental et al . 2009,Steele , 197–230. , 197–230. δ 60/58 Ni =0.00‰. tiites and associated Ni-sulfide min tiites andassociatedNi-sulfide esented by open symbols (Cook opensymbols by esented et al lta values of Ni PlasmaCal®. lta valuesof . 2011). The grey bar stands for the BSE barstandsforthe grey . 2011).The Ni isotopes. Nickel concentration in solution above 40 ng g insolutionabove40ng Niisotopes.Nickelconcentration smochemistry ofmagnesium. ound not to be correctly calculated by the double-spike method the by calculated ound nottobecorrectly lta values versus differentsp lta valuesversus ith the Cu-doping and double-spike correction correction Cu-doping anddouble-spike ith the delta values versus Ni concentration (in ng g (inng valuesversusNiconcentration delta , but moreimportantly useofthe it validates , but solution was run along with each sample batch. batch. eachsample with wasrunalong solution ed value even when diff valueeven ed eas over-spiked samples up to a ratio of 7 were toaratioof7were up over-spikedsamples eas ‰ of terrestrial sample ‰ ofterrestrial nic rocks and minerals such as altered and asaltered and mineralssuch nic rocks assess the effect of Ni concentration onthe Ni concentration of assess theeffect to show that data points followthisline. toshowthatdatapoints s (2 s et al eralisation, mantle-derived rocks eralisation, mantle-derived = 0.07‰ for 24 datapoints) for =0.07‰ Reviews in Reviews Mineralogy and ike/sample ratios. Under-spiked ratios.Under-spiked ike/sample . 2007,Moynier erent amountsofnickel erent s from thisstudys from and δ 60/58 PlasmaCal® afterit Ni valueof0.05± et al . 2007, -1 ) of -1 -1 Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted60/58 Article60/58 δ Ni (± 2SE, ‰) 2SE of δ Ni NIST SRM 986 (‰) 0.5 1.0 1.5 -0.05 0.05 0.15 -0.1 0 0.1 0 0 0 10 20 5 30 Ni Pcalsolutionbatch# Ni concentration (ngg 10 40 50 15 60 2 standarddeviation Mean deltaNivalueforPCal -1 ) 70 20 80 90 25

100

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards

Accepted60/58 Article60/58 δ Ni (‰ ± 1s) Cu-doping method δ Ni (‰ ± 2SE) -0.60 -0.40 -0.20 0.00 0.20 0.40 -0.4 -0.3 -0.2 -0.1 -0.6 -0.5 0.1 0.2 0.3 0.4 0.5 0.6 0 -0.60 0 0.5 δ -0.40 60/58 Ni (‰±2SE)double-spike method 1 -0.20 1.5 spike/sample ratio 1:1 Line 2 0.00 2.5 0.20 3 3.5 0.40

4 8

Association of Geoanalysts Association of Geoanalysts International ©2013 Research and Geoanalytical © 2013The Authors. Geostandards Accepted Article 1 0.8 0.6 0.4 0.2 0 -0.2 -0.4 -0.6 -0.8 -1 -1.2 Chondrites Serpentinite Dunite δ 60/58 Komatiites andassociatedNi-sulfidemineralisation Ni (‰) Olivine crystals Contaminated soil sediments Deep-sea surfaceclaysandlithogenic Altered andfreshbasalts Pacific Peridotite Iron meteorites Granite Iron Formation Coal Mn-nodules Devonian shale Devonian Atlantic 1.2