Determination of trace and ultra- trace elements …

1 RIGHT SOLUTIONS RIGHT PARTNER 1 RIGHT SOLUTIONS RIGHT PARTNER Determination of trace and ultra - trace elements by ICP-SFMS Ilia Rodushkin, Emma Engstr m, Douglas Baxter ALS Scandinavia AB Lule University of Technology RIGHT SOLUTIONS RIGHT PARTNER 2 Lule laboratory Part of ALS group (>300 laboratories worldwide) Focus areas: ultra - trace multi-elemental determinations and isotope ratio measurements >130 000 samples annually Close co-operation with LTU resulting in 200 publications RIGHT SOLUTIONS RIGHT PARTNER 3 3 ICP-OES 14 ICP-SFMS 3 AFS 1 ICP-QMS 2 MC-ICP-MS Instrumentation RIGHT SOLUTIONS RIGHT PARTNER 4 High ion transmission = high sensitivity Can be operated in high resolution mode(s)

2 Flat-top peaks in low resolution Instrumental dark current < cps Flexible introduction system Relatively low matrix tolerance Large and heavy Expensive Requires experienced operators ICP-SectorFieldMS = HighResolution-ICP-MS = Double Focusing ICP-MS RIGHT SOLUTIONS RIGHT PARTNER 5 Before MS Sample collection Homogenization representative sub-sample, contamination Digestion recovery from matrix, (co)precipitation and volatile losses, contamination Column separation purification efficiency, yield, contamination Evaporation/re-dissolution recovery, contamination RIGHT SOLUTIONS RIGHT PARTNER 6 The UltraCLAVE Principle The patented* Milestone UltraCLAVE achieves extraordinary performance capabilities by combining direct microwave heating in a high pressure reactor, which acts simultaneously as microwave cavity and vessel.

3 The next generation MW system The Milestone UltraCLAVE RIGHT SOLUTIONS RIGHT PARTNER 7 What a difference a droplet (10 l) HF RIGHT SOLUTIONS RIGHT PARTNER 8 What a difference a droplet (10 l) of HF 3600 RIGHT SOLUTIONS RIGHT PARTNER 9 Sensitivity Matrix tolerance Spectral interferences Instrumental background Analyte blank Accurate measurement - factors to consider Measured signal Signal from analyte presented in sample Unwanted contributions RIGHT SOLUTIONS RIGHT PARTNER 10 Sensitivity upper limit Analyte 239Pu Sample uptake ml/min Transport efficiency 100% Law of conservation of mass is still valid Highest possible sensitivity for 1 pg l-1 8400 counts s-1 RIGHT SOLUTIONS RIGHT PARTNER 11 Cell ICP-QMS.

4 ICP-SFMS, standard set-up: 2 ICP-SFMS, X skimmer, CH4: 5-8 ICP-SFMS, X skimmer, Aridus + N2: 20-30 MC-ICP-MS, Jet interface, APEX: 110-140 Record transport efficiency of ICP-MS is under 2% Sensitivity in LRM, counts s-1 per 1 pg l-1 238U RIGHT SOLUTIONS RIGHT PARTNER 12 High efficiency nebulizers Aridus II and Apex HF Intensity gain by efficient utilization of sample solution Dry plasma much lower O, H and OH interferences Great signal stability for low-matrix solutions Losses of volatile elements (Hg, Se, As, Os, B) Low matrix tolerance Long memory RIGHT SOLUTIONS RIGHT PARTNER 13 Sensitivity in LRM, counts s-1 per 1 pg l-1 RIGHT SOLUTIONS RIGHT PARTNER 14 BEC, ppq LOD, ppq LOQ, ppq Major interferences 226Ra WAr, ReArH, PbOH2, BaSr, BaCaCa 230Th Th, U tails, OsAr, PtO2, HgO2, IrCl, PtCl 232Th 44 11 36 OsAr, HgO2, AuCl, PtCl 234U ThH2, Th, U tails, PtAr, AuCl, PtCl 235U U tail, PtAr, HgCl, PtCl, HgO2 236U UH, U tail, PtAr, HgCl, HgO2 237Np U tail, UH2, AuAr, HgCl, HgO2 238U 30 7 23 PtAr, HgAr, HgCl, TlCl, PbO2 239Pu UH, U tail, HgAr, HgCl.

5 PbCl, PbO2 240Pu UH2, U tail, HgAr, TlCl, PbO2 241Am U tail, HgAr, HgCl, PbCl, BiO2 242Pu U tail, HgAr, TlCl, PbCl 243Am TlAr, PbCl Summary of BEC, limits and interferences RIGHT SOLUTIONS RIGHT PARTNER 15 BEC, ppq LOD, ppq LOQ, ppq Major interferences 226Ra WAr, ReArH, PbOH2, BaSr, BaCaCa 230Th Th, U tails, OsAr, PtO2, HgO2, IrCl, PtCl 232Th 44 11 36 OsAr, HgO2, AuCl, PtCl 234U ThH2, Th, U tails, PtAr, AuCl, PtCl 235U U tail, PtAr, HgCl, PtCl, HgO2 236U UH, U tail, PtAr, HgCl, HgO2 237Np U tail, UH2, AuAr, HgCl, HgO2 238U 30 7 23 PtAr, HgAr, HgCl, TlCl, PbO2 239Pu UH, U tail, HgAr, HgCl, PbCl, PbO2 240Pu UH2, U tail, HgAr, TlCl, PbO2 241Am U tail, HgAr, HgCl, PbCl, BiO2 242Pu U tail, HgAr, TlCl, PbCl 243Am TlAr, PbCl Summary of BEC, limits and interferences RIGHT SOLUTIONS RIGHT PARTNER 16 + + + + + + + + + + +10218220222224226228230232234236238240m /zIntensity.

6 Counts s-1 Tailing RIGHT SOLUTIONS RIGHT PARTNER 17 Standard Aridus II Aridus II+RPQ* Th -2 amu *10-6 *10-6 *10-6 -1 amu 4*10-6 2*10-6 *10-6 +1 amu 65*10-6 16*10-6 5*10-6 +2 amu 10*10-6 2*10-6 *10-6 U -2 amu *10-6 *10-6 *10-6 -1 amu 4*10-6 2*10-6 *10-6 +1 amu 72*10-6 17*10-6 5*10-6 +2 amu 11*10-6 2*10-6 *10-6 Retarding Potential Quadrupole lense adjusted to provide >80% of original sensitivity RIGHT SOLUTIONS RIGHT PARTNER 18 Matrix separation/preconcentration 20-200 times improvement compared to direct analysis after dilution RIGHT SOLUTIONS RIGHT PARTNER 19 Memory effects (self aspiration, Aridus II) RIGHT SOLUTIONS RIGHT PARTNER 20 Memory effects (self aspiration, Aridus II) Blanks ( M HO3) 50 ng L-1 239Pu, 242Pu STDs Blanks with HF RIGHT SOLUTIONS RIGHT PARTNER 21 In tubing min.

7 Length and strong rinse solutions In spray chamber low-volume or DIN, matrix optimization (suppression of volatile species formation) On cones use Si-trick Inside MS Memory effects RIGHT SOLUTIONS RIGHT PARTNER 22 Why Lule ? October January April RIGHT SOLUTIONS RIGHT PARTNER 23 Ag Pt/Au Sn Si Torch and interface may release RIGHT SOLUTIONS RIGHT PARTNER 24 Personnel issues Spot the common denominator? Stibnite Antimonite Sb2S3 RIGHT SOLUTIONS RIGHT PARTNER 25 Al, Cl, Zr, Hf, Si Aluminium Chlorohydrate, Aluminium Zirconium Tetrachlorohydrex Gly, Silica, Silica Dimethyl Silyate, Hf Deodorants RIGHT SOLUTIONS RIGHT PARTNER 26 Faster and more convenient way to handle relatively large sample volumes (>5 ml)

8 Contaminates sample with Pt and Ir at ppt level, Pd and Au at ppq level because of Pt-Ir valve spring Metall-free dispenser RIGHT SOLUTIONS RIGHT PARTNER 27 Au0,00,20,40,60,81,01,2 RoadDomesticLaboratory 1 Laboratory 2 Concentration, g g-1 Concentrations of rare elements are enriched in laboratory dust RIGHT SOLUTIONS RIGHT PARTNER 28 Dedicated areas for ultra - trace preparations RIGHT SOLUTIONS RIGHT PARTNER 29 All labware in contact with samples is acid cleaned RIGHT SOLUTIONS RIGHT PARTNER 30 Applications dictate choice of tube materials RIGHT SOLUTIONS RIGHT PARTNER 31 ICP-SFMS offers instrumental LODs in sub-ppq range Ultimate technique for multi-element Determination in variety of matrices 232Th, 235U.

9 238U can be accurately measured almost in any matrices Analysis at endogenous levels of 226Ra, 230Th, Pu, Am will require matrix separation/pre-concentration and optimized introduction systems Conclusions RIGHT SOLUTIONS RIGHT PARTNER 32 Thank you for your attention! RIGHT SOLUTIONS RIGHT PARTNER 33 206Pb++ 87Rb16O+, 87Sr16O+, 86Sr16OH+ 63Cu40Ar+, 65Cu36Ar+, 67Zn36Ar+ 23Na40Ar40Ar+, 23Na40Ar40Ca+, 23Na40Ca40Ca+ 66Zn37Cl+, 68Zn35Cl+ 32S34S37Cl+, 33S33S37Cl+, 34S34S35Cl+, 34S34S34SH+ 96Mo7Li+, 97Mo6Li+, 40Ar35Cl12C16O+ Spectral interferences on 103Rh The majority of spectral interferences can be eliminated using high resolution capabilities of ICP-SFMS RIGHT SOLUTIONS RIGHT PARTNER 34 Interferences RIGHT SOLUTIONS RIGHT PARTNER 35 Why Lule ?

10 RIGHT SOLUTIONS RIGHT PARTNER 36 Determination of TCEs in environmental matrices Ga, Ge, In, Nb, Ta, Te, Tl Ir, Os, Pd, Pt, Rh Ce, Dy, Er, Eu, Gd, Ho, La, Lu, Nd, Pr, Sm, Tb, Y, Yb Quantitate recovery at preparation stages Preventing losses during analysis Optimization of instrumental conditions (low oxides) Right resolution settings Matrix separation if necessary Analyte specific introduction (Os, Ge)