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(Figure daughter ratios radiogenic isotope of the determination of precise the requires tracers geochemical as ratios of application (MC)-ICP-MSThe multi-collector by ratios isotope of Determination 5 signal LA-ICP-MS on based grains mineral of maps distribution 7 REE of create resolution spatial [105] a al. with et intensities Cook mode. raster 0.001 100 a as of low diameter as beam a REEs pitandon For for instrument. limits laser the detection of the of reach sensitivity can size the is the systems to LA-ICP-MS LA-ICP-SFMS on next fs detection using depend for significantly dependency used LA-ICP-MS isotope matrix for overcome limits the Detection to to 104]. 51 as similar [103, well and Refs is as in 38 shown precision now improve of and to range 0.8 potential [94]) concentration The of (e.g. the analysis. External precision LA-ICP-MS 63]. in report by LA-ICP-SFMS [33, [102] analysis used ns al. REE are nm et standards of Jochum matched days solution-ICP-MS. matrix early of if the precision % since <5 improved to reduced has be precision may but applied. matching are matrix standards without matrix-matched if neglected be (particularly only fractionation can and element-dependent errors and aremin- these mass- LA-ICP-MS) types by factors ns rock affected correction for many system sensitivity element LA-ICP-MS constrained in standard a insufficiently internal abundant by using suitable caused When is as errors imized. recommended which case, be Ca, such can In standards, Therefore analysis. series [70]. REE 600 for NIST Ba the and in Sr as well Ca, as minerals Mg, elements earth alkaline the 8 hdoysbtrcacid/ -hydroxyisobutyric Lu ept hmclioain rc muiiscnocri h rcin faayeeeet,wihips the impose which elements, analyte of fractions the in occur can impurities trace isolation, chemical Despite stability signal optimize to helps which possible, as simple as elements the of matrix the keep to order In two involving ratios isotope step, one in determined be can element same the of isotopes two of ratios While sample MC-ICP-MS, by determination ratio isotope For MC-ICP-MS. on focus therefore, parts, following The as well asmost source the ICP in Hf and REEs of ionization best offers MC-ICP-MS task, analytical this For in operated if imaging chemical for tool a as used be also can LA analysis, concentration to addition In silicate minerals analysing % when be<10 to known is which of LA-ICP-MS, on accuracy effect an has This 144 – Sindern 178 mand Sm fand Hf 4 rHNO or 147 144 176 Sm/ d swl so oeua pce omn iheeet flwrmse n r ,No C, or N O, Ar, and masses lower of elements with forming species molecular of as well as Nd) 138 138 Lu 3 La, Ce/ , is performed using Teflon® vessels (with steel jacket if necessary) in cleanlaboratory air in ifnecessary) jacket steel (with vessels Teflon® using performed is , 144 – 180 147 dand Nd 142 faeaddt h apesolution. sample the to added are Hf α Sm, Ce, HB,Tfo®bsdrsn odtoe ihdi(2-ethylhexyl)orthophosphoric with conditioned resins Teflon®-based -HIBA, – iudetato aebe eeoe [106 developed been have extraction liquid 146 143 176 mor Sm Nd/ Lu/ 138 176 144 – 177 La/ 176 12 Yb Nd, f r eemndi w eaaeseso ocnrto analysis concentration of steps separate two in determined are Hf) udcyfrgo rcsohoooia tde rteueo isotope of use the or studies cosmochronological or geo- for decay Lu μ 142 – m. 176 Ce, 142 uand Lu Nd/ 147 Sm/ 144 144 Nd, 144 Sm Nd, – 176 144 μ Hf/ / nntrlgassadrsatrrepeated after standards glass natural in g/g 146 d.Creto fitreec-eae signal interference-related of Correction Nd). 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TIMS by determined values to comparable is condi- MC-ICP-MS analytical of common precision be For to time. reported (2 analysis often precision or is external analysis, element solutions mineral analyte and the rock 121 for of [95, applied concentration common tions on are Ce as Ames-Nd for well Jolla, Ames-Ce as 304, La procedures JMC as or such Hf oxides for or 475 metals JMC pure Nd, for with JNdi-1 prepared or solutions standard 119]. ratios, [41, measurements isotope ratio radiogenic isotope reproducible runduring and accurate solution yield astandard to to applied normalization is final sessions a analytical often Thus, composition. isotopic known with solutions standard Lu and Yb mixed of the analysis to normalization systematic difference repeated the by Yb, evaluated and Lu externally solutions of is properties discrimination fractionation mass identical of in assumption incorrect the avoid To separation. (e.g. solution Lu/ Lu/ rcso fL-CIPM stp ai eemnto eed nsga nest,adtu ntecon- the on thus and intensity, signal on depends determination ratio isotope LA-MC-ICP-MS of Precision in caused fractionation to addition in occurs which 3), (see fractionation laser-induced to due general, In of signal The solution-ICP-MS. for than analysis situ in for crucial more are interferences Isobaric conve- the with resolution spatial high at analysis situ in of advantage the combines thus LA-MC-ICP-MS nmn aoaois ohisfiinl orce asba ofdaughter bias mass corrected insufficiently both laboratories, many In can beper- system ordetection ionsource ICP the in effects fractionation to due bias mass of Correction rcso fiooertodtriainb CIPM eed nisrmna rprisadcorrection and properties instrumental on depends MC-ICP-MS by the determination ratio of isotope of determination Precision for procedures correction and accuracy of evaluation general or normalization For standard of analysis the from derived factors using corrected be must fractionation mass-independent Any 142 177 175 eon Ce – f antawy dqaeyb orce sn tbeiooerto fol n element. one only of ratios isotope stable using corrected be adequately always cannot Hf) urtocnb vlae sn nitreec-reiooertoo nte E fe oigo the of doping after REE another of ratio isotope interference-free an using evaluated be can ratio Lu – eeec aisaecretduigmnrlsadrsotnaaye nasadr-apebracketing standard-sample a in analysed often standards mineral using corrected are ratios reference ehdas loigassmn fioai nefrneby interference isobaric of assessment allowing also method a 149 167 142 m n diinlcreto fms iso h ai.Hwvr tbennrdoei ratios non-radiogenic stable However, ratio. the on bias mass of correction additional and Sm) Er/ d htcnhv ihcnetain nusprtdsldmnrlmte.Dfeetproce- Different matter. mineral solid unseparated in concentrations high have can that Nd) 146 166 187 – Nd/ diooe ihL-CIPM a nraigybe ple omnrl htenrich that minerals to applied been increasingly has LA-MC-ICP-MS with isotopes Nd r[1] ruigY curn nteL rcindet nopeechromatographic incomplete to due fraction Lu the in occurring Yb using or [119]) Er Re/ 144 185 Nd, ertoo namxdsadr ouini sdfrcreto [120]. correction for used is solution standard admixed an of ratio Re 176 ≤ 144 147 0pmfor ppm 20 fi nst iea nlssta neeetlfatosatrceia sepa- chemical after fractions elemental in than analyses mineral situ in in Hf ma iha nmnzt eas hsmnrl ieohrlgtREE- light other like mineral, this because monazite in % 4 as high as Sm Sm/ 153 mand Sm 176 144 Hf/ m a epromduigisrtowt ninterference-free an with ratio its using performed be can Sm) 179 177 Hf/ for Hf 177 143 frto a eue o orcino unknown of correction for used be can ratios Hf – Nd/ fsse r anyaaye nzro.Such zircon. in analysed mainly are system Hf σ bandfo eetdaayi fstandard of analysis repeated from obtained ) 144 d[8 1,14.Frtelte element, latter the For 124]. 119, [68, Nd 176 – eeec ais(e.g. ratios reference – bon Yb 176 eeec aisadfractionation and ratios reference ’ – rsa vlto 5,127]. [57, evolution crustal s uand Lu b )dt bandfo the from obtained data O) Pb, 176 – 123]. u[5 1.Alternatively, 41]. [15, Lu 175 u asba fthe of bias Mass Lu. 176 147 uand Lu Sindern Sm/ 144 dcan Nd 144 176 Nd, Yb 9 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd 1]Bihr-otJ laèeF h uH stp eceityo hnrtsadteeouino h atecutsse.ErhPae Sci Planet Earth system. mantle-crust the of evolution the and chondrites of geochemistry isotope Lu-Hf The F. Albarède Blichert-Toft J, [16] F. P, Albarède Télouk M, Boyet Blichert-Toft J, River [15] Rhine the in gadolinium and lanthanum samarium, colloid/nanoparticle-bound and dissolved Anthropogenic M. Bau S, Kulaksiz [14] Par- lanthanum. and Gadolinium rivers: in elements earth rare P. Anthropogenic Négrel E, Petelet-Giraud I, Bakker M, Verheul agricul- G, by Germany, Klaver River, Havel [13] lowland the in distribution yttrium and earths rare of variations P. Seasonal and Dulski elements A, earth P, Knappe rare Möller of [12] distribution the from Evidence oxide: Fe hydrous on cerium of scavenging Oxidative A. Koschinsky M, iso- Bau Nd [11] and element earth Rare seawater: Archean shallow in solutes P. Continentally-derived P, Dulski Andersson 1989. M, Hall, Bau & B, Chapman Alexander London, [10] Approach. Tectonic Global A Petrogenesis, Igneous Mongolia) M. (Western Wilson Buregte [9] Khalzan at mineralization Zr-Nb-REE of genesis The E. Dombon J, Kynicky (peri- T, PCC-1 Graupner and R, (dunite) Möckel DTS-1 U, materials Kempe reference [8] geological in REE the of Determination RM. Sherrell JC, 53 Ely 231, CR, 2005, MP, Neal Lett Field Sci JC, Planet Jain Earth [7] (DMM). mantle MORB depleted the of composition element trace and 223 Major 120, SR. 1995, Hart Geol RK, Workman Chem Earth. [6] the of composition 1991. Company, The SS. Publishing Sun Macmillan WF, York, McDonough New [5] Geochemistry. Inorganic of Applications and Principles 1995. G. Inc., Faure McGraw-Hill, York, [4] New Geochemistry. to lan- Introduction and DK. Zr/Hf, Bird Y/Ho, KB, from Krauskopf Evidence [3] systems: aqueous and magmatic in elements trace isovalent of fractionation 1217 the 59, on 1995, Controls Acta M. Cosmochim Bau Geochim [2] crust. continental the of composition The KH. Wedepohl [1] References 978 isbn (2016), Gruyter De Elements. Earth Rare of Handbook Golloch, in: 036523 available also is article This Lu Acknowledgment and geosciences. Sm in La, step of important decay an the considered the of be on can capability based ICP-MS ionization geochronometers of advent REEs excellent as of the and the role consideration, processes the into to Taking isotopes geological cosmochemistry. due and for geochemistry and elements isotope minerals, indicator in step as and major a rocks marked of also ICP-MS analyses source REE of availability thetechnical andmulti- the that (single collector shows and MC-ICP-MS, fs LA-ICP-MS configurations ongoing of withdifferentMSs still detector is wellas field evolution at various as methodological the input and in flight) example sample for of of advance, systems Recent time collector). and allows SF withdifferent source ICP magnetic versatile becombined and (quadrupole, robust can The and technique. developing rapidly ionization a been efficient has ICP-MS years, 30 last the In remarks Concluding 6 and the zircon (e.g. of minerals precision natural to internal applicable report [126] 50 McCulloch of diameter and McFarlane 129]. [65, precision 143 control also procedures 10 Cam- Paulo, Sao Singapore, Town, Cape Madrid, Melbourne, York, New Cambridge, edition. 2nd Geology, Isotope AP. Radiogenic Dickin [17] Nd/ et19,18 243 148, 1997, Lett 167 204, 43 2002, 362, Lett 2013, Sci Lett Planet Sci Planet Earth rivers. in distribution element earth rare natural the of destruction impeding the and (the Delta Rhine-Meuse the through propagation 186 spatial 47, and 2014, River Geochem Rhine Appl the Netherlands). in phases particulate and dissolved the between titioning 62 41, 2014, Geochem Appl plants. treatment sewage of effluents and fertilization tural 37 43, 2009, J Geochem crusts. ferromanganese hydrogenetic in oxides Mn and oxides Fe 378 between 72, yttrium 2008, Acta Cosmochim Geochim Africa. South Supergroup, Pongola Ga 2.9 the from formation iron in evidence tope 602 64, 2015, Rev Geol Ore reconsidered. 65 24, 2000, Newsl Geostand ICP-MS. nebulisation desolvating microconcentric and ultrasonic by dotite) 72. 323 123, 1996, Petrol Mineral Contrib effect. tetrad thanide data. bibliographical with assistance for Voß M.-A. and Günther G. Mrs. thanks author The enhanced significantly laboratories geochemical in instrument standard a as ICP-MS of introduction The rdeUiest rs,2005. Press, University bridge Sindern – 144 8. drtoa oda nTM ntuet <0pm 2 ppm, (<10 instruments TIMS in as good as ratio Nd μ .Etra rcso ece etvle ewe 0ad9 p (2 ppm 95 and 60 between values best reaches precision External m. – 58. – 81. – 25. – 97. 147 Sm- 143 dand Nd – 176 etil lodie yteaayia ed ftegeosciences. the of needs analytical the by driven also certainly – Hf/ 33. 176 Lu- 177 176 f[7 129]). [57, Hf fi urtsadtedfeetaino h E aetbd.Earth body. parent HED the of differentiation the and eucrites in Hf σ o oaiewt da t n crater a and % wt. 9 at Nd with monazite for ) – 53. – 72. – 32. σ o nltclconditions analytical for ) – – 72. 47. – 50. EGRUYTER DE – 94. – 3 – 11 – – Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd 5]LneihH.Lsralto-nutvl ope lsams pcrmty(AIPM) nitouto,i:SletrP(d)Laser (ed.) P Sylvester in: introduction, (LA-ICP-MS); an spectrometry deposit. plasma-mass gold Jewel coupled Crown ablation-inductively the HP. Laser from Longerich garnets [51] of LA-ICP-MS study A systems: skarn in REE R. Moretti LD, Meinert C, Knaack Spectrom- M, Mass Gaspar Plasma [50] Coupled Ablation-Inductively Laser by Samples Geological in Elements Earth Rare of Analyses R. Klemd H, direct, Brätz the [49] for technique rapid (LA-ICP-MS): A spectrometry mass plasma coupled inductively ablation Laser JG. 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English Chinese, in 42, 17. – ’ ate aue19,30 728 360, 1992, Nature mantle. s 35. – – 91. 18. ’ ate eci omci ca20,7,164 70, 2006, Acta Cosmochim Geochim mantle. s – 23. – 501. – – 32. – – – 50. urn rcie n usadn sus ieaoia soito fCnd hr Course Short Canada of Association Mineralogical Issues. Outstanding and Practices Current 205. rnilsadApiain.Cihse,Jh ie os 2007. Sons, & Wiley John Chichester, Applications. and Principles – 33. 147 – Sm- 44. – 143 oeflto o ihpeiintaeeeetaayi nerhsine:Evi- sciences: earth in analysis trace-element high-precision for tool powerful a – 142 – dand Nd 86. rfc,i:SletrP(d)LsrAlto-CM nteErhSciences Earth the in Laser-Ablation-ICPMS (ed.) P Sylvester in: preface, Nd/ ’ nlCe 94 5,194 350, 1994, Chem Anal J 144 – 39. 146 dmaueet ntretilrcs osrit nteerydifferen- early the on Constraints rocks: terrestrial in measurements Nd Sm- – 91. 142 dsseaisfrvr al 45Gr ifrnito fthe of differentiation (4.5-Gyr) early very for systematics Nd – 807. – 82. – 48. – – 19. 6. – 203. – – iv. 94. – – – 15. 36. 24. – 64. – – – 8. 30. 62. Sindern – Principles – Prin- – 6. 11 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd 8]Fdrwc S ihrsJ,Ji C erc ,FnJ ai ehdfrREadtaeeeetaayi sn ae apigIPM on ICP-MS sampling laser using analysis trace-element and REE for method rapid A J. Fan R, Kerrich JC, JP, Jain Richards JS, Fedorowich [82] An spectrometry: plasma-mass coupled ablation-inductively Laser IA. Nicholls WW, Ahlers RJS, Morrison ICP- DD, and Lambert digestion CA, acid Morrison microwave [81] by samples geological in elements trace other and REEs of determination Rapid TG. Rao V, Balaram [80] of melting partial and metamorphism during U and Th, Y, REE, Zr, of redistribution and phases accessory of P. Behavior Montero F, Bea coupled [79] ablation-inductively laser in fractionation elemental ICP-induced on distribution size particle of Effect D. Günther laser UV-femtosecond M, using Guillong determination [78] ratio isotope iron situ In G. Markl G, Steinhoefel R, Schoenberg F, Blanckenburg von I, Horn laser [77] femtosecond UV using silicates in determination ratio isotope Fe Matrix-independent F. Blanckenburg von I, Horn G, Steinhoefel [76] of determination accurate and Precise GE. Mortimer LPJ, Kinsley MT, McCulloch SM, Eggins T, Iizuka [75] ablation- laser by systematics isotope HP. Sm-Nd Longerich R, Lam PJ, Sylvester MD, Schmitz JM, Hanchar CRM, McFarlane CM, Fisher [74] mass for Evidence spectrometry: plasma-mass laser coupled for ablation-inductively laser Nd:YAG laser state in solid fractionation single Elemental D. a Günther from I, produced Kroslakova nm [73] 193 and nm 213 nm, 266 of comparison A D. to Günther I, tube Horn transport M, the Guillong in [72] deposited particles aerosol ablation laser of composition Elemental K. Niemax N, Jakubowski I, Feldmann J, Koch Sciences [71] Earth the in Ablation-ICP-MS Laser (ed.) P Sylvester LA-ICP-MS, in: by analysis elemental for strategies Calibration S. Jackson [70] 227 185, 2002, Geol Chem isotopes. Nd using MC-ICPMS in d discrimination [69] mass of assessment An spectrome- M. mass Thirlwall source D, Vance plasma [68] by measurements ratio isotope in accuracy and Precision J. Vogl G, Rädlinger SM, Gallus KG, Heumann [67] Spectrometry. Mass Plasma Coupled Inductively (ed.) 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Datas R, Wirth FX, Abzac 30. – – 80. 85. – – 10. 49. – 7. – 102. – 57. – – 44. 78. – – 92. 79. – 1 260 31, – 97. – 347A. – 73. 147 Sm/ – – urn rcie n outstand- and practices current 62. 144 dand Nd – 88. – – 88. 116. 143 – Nd/ 40. – 29. 144 EGRUYTER DE din Nd – Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd 14 i ,Sno adeu F eunilsprto flgtrr-at lmns hru n rnu ymnauiainextraction miniaturization by uranium and thorium elements, light-rare-earth MC- of for separation samples Sequential JF. rock Zalduegui from Santos Lu C, and Pin Hf) [114] Zr, Ta, (Nb, elements strength field high of Separation K. Mezger E, Scherer S, MC-ICP-MS. Geo- Weyer by C, rutile Münker and [113] ilmentite in isotopes hafnium of application and Methodology A. Rahier D, Weis JS, Scoates compounds: CE, Ti Morisset with [112] coprecipitation employing W and Ta Hf, Mo, Nb, Zr, of technique preconcentration New E. Nakamura A, Makishima [111] J O meteorites. 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Willbold K, Herwig B, KP, Stoll Jochum acquisition [102] data signal transient spectrometric mass plasma coupled inductively ablation Laser D. spectrometry Günther mass SE, HP, Jackson plasma Longerich coupled [101] inductively ablation laser in calibration solution of strategy new A HJ. Dietze by JS, microanalysis Becker situ C, in Pickhardt for [100] material calibration glass titanite synthetic a of Preparation NJ. Pearson H, Schiellerup Ø, Skårr M, Ødegård [99] 9 28, 2004, Res Geoanal Geostand crystal. zircon 91500 the Ko of J, characterization Further Sláma al. [98] et WH, Peck JM, Hanchar M, Wiedenbeck [97] in: needs, outstanding and LA-(MC)-ICP-MS: Success by analyses isotopic and elemental for materials iso- Reference B. and KP, Stoll materials Jochum reference [96] for database geochemical new A GeoReM: AW. Hofmann B, Stoll E, Lammel K, Herwig U, KP, Nohl calibration. Jochum external [95] with elements earth rare of analysis ablation-ICP-MS laser of accuracy and Precision B. 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Sindern – 70. – 209. – 39. 13 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd 19 odedJ,HrtJ,SelyM gisS epR icnH-stp nlsswt necmrlsr et rfiig bainof ablation profiling, depth laser, excimer an with analysis Hf-isotope Zircon R. Kemp S, MC-ICP-MS. Eggins by M, 91500 Shelley standard JM, zircon Hergt the JD, Woodhead for [129] values reference isotopic Lu and Hf JS. Scoates D, Weis J, Jong 2003, de Geochem N, Mineral Mattielli Rev A, Zircon. Goolaerts (eds.) [128] PWO Hoskin JM, Hanchar in: zircon, in systems isotope Sm-Nd and Lu-Hf R. Maas PD, Kinny [127] (ed.) P Sylvester LA-MC-ICP-MS, in: using minerals accessory LREE-rich in systematics isotope Sr and Sm-Nd M. McCulloch (1 C, aliquots McFarlane small [126] very of analysis isotope neodymium precision high TIMS for method improved An EF. Baxter J, Harvey [125] cou- inductively multi-collector by solutions standard mixed of analysis isotope Hafnium HS. 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