SUPPLEMENTAL INFORMATION. Fully Automated Total Metals and Chromium Speciation Single Platform Introduction System for ICP-MS

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1 Electronic Supplementary Material (ESI) for Journal of Analytical Atomic Spectrometry. This journal is The Royal Society of Chemistry 2018 SUPPLEMENTAL INFORMATION Fully Automated Total Metals and Chromium Speciation Single Platform Introduction System for P-MS C. Derrick Quarles, Jr. 1 *, Michael Szoltysik 2, Patrick Sullivan 1, Maurice Reijnen 3 1 Elemental Scientific, Inc., 7277 World Communications Dr., Omaha, NE, USA 2 Eurofins Environment Testing Sweden AB, Sjöhagsgatan 3, , Lidköping, Sweden 3 Inorganic Solutions, Philipsenstraat, 5371 CN, Ravenstein, The Netherlands

2 Table S1. Agilent calibration curve report obtained from Mass Hunter for all elements analyzed for in total metals mode. Tune Mode m/z Element R 2 m b DL Units NoGas 7 Li µg L -1 NoGas 9 Be µg L -1 NoGas 11 B µg L -1 He 23 Na mg L -1 He 24 Mg mg L -1 He 27 Al µg L -1 He 28 Si mg L -1 He 31 P mg L -1 He 32 S mg L -1 He 39 K mg L -1 He 44 Ca mg L -1 NoGas 45 Sc µg L -1 NoGas 47 Ti mg L -1 O 2 48 S mg L -1 O 2 50 S mg L -1 He 51 V µg L -1 He 52 Cr µg L -1 He 55 Mn µg L -1 He 56 Fe µg L -1 H 2 56 Fe µg L -1 He 59 Co µg L -1 He 60 Ni µg L -1 He 63 Cu µg L -1 He 66 Zn µg L -1 NoGas 71 Ga µg L -1 He 75 As µg L -1 H 2 78 Se µg L -1 NoGas 85 Rb µg L -1 He 88 Sr µg L -1 NoGas 89 Y µg L -1 NoGas 90 Zr µg L -1 O 2 91 As µg L -1 NoGas 93 Nb µg L -1 He 95 Mo µg L -1 NoGas 101 Ru µg L -1 NoGas 105 Pd µg L -1 NoGas 107 Ag µg L -1 He 111 Cd µg L -1 He 114 Cd µg L -1

3 Table S1 (continued). Agilent calibration curve report obtained from Mass Hunter for all elements analyzed for in total metals mode. Tune Mode m/z Element R 2 m b DL Units NoGas 115 In µg L -1 NoGas 118 Sn µg L -1 He 118 Sn µg L -1 He 123 Sb µg L -1 He 125 Te µg L -1 NoGas 133 Cs µg L -1 He 135 Ba µg L -1 He 139 La µg L -1 NoGas 140 Ce µg L -1 NoGas 141 Pr µg L -1 NoGas 146 Nd µg L -1 NoGas 147 Sm µg L -1 NoGas 153 Eu µg L -1 NoGas 157 Gd µg L -1 NoGas 159 Tb µg L -1 NoGas 163 Dy µg L -1 NoGas 165 Ho µg L -1 NoGas 166 Er µg L -1 NoGas 169 Tm µg L -1 NoGas 172 Yb µg L -1 NoGas 175 Lu µg L -1 NoGas 178 Hf µg L -1 NoGas 181 Ta µg L -1 He 182 W µg L -1 NoGas 185 Re µg L -1 NoGas 195 Pt µg L -1 NoGas 197 Au µg L -1 He 200 Hg µg L -1 H Hg µg L -1 He 201 Hg µg L -1 H Hg µg L -1 He 202 Hg µg L -1 H Hg µg L -1 He 205 Tl µg L -1 He 206 [Pb] µg L -1 He 207 [Pb] µg L -1 He 208 Pb µg L -1 He 209 Bi µg L -1 NoGas 232 Th µg L -1

4 Table S1 (continued). Agilent calibration curve report obtained from Mass Hunter for all elements analyzed for in total metals mode. Tune Mode m/z Element R 2 m b DL Units He 238 U µg L -1 NoGas 72 Ge ISTD ISTD ISTD ISTD ISTD He 72 Ge ISTD ISTD ISTD ISTD ISTD H 2 72 Ge ISTD ISTD ISTD ISTD ISTD NoGas 103 Rh ISTD ISTD ISTD ISTD ISTD He 103 Rh ISTD ISTD ISTD ISTD ISTD H Rh ISTD ISTD ISTD ISTD ISTD O Rh ISTD ISTD ISTD ISTD ISTD NoGas 193 Ir ISTD ISTD ISTD ISTD ISTD He 193 Ir ISTD ISTD ISTD ISTD ISTD H Ir ISTD ISTD ISTD ISTD ISTD m = slope, b = intercept, DL = (3 x σ blank )/m

5 Table S2. Limits of detection (LOD) and limit of quantification (LOQ) for total metals mode. Tune Mode m/z Element LOD LOQ Units NoGas 7 Li mg L -1 NoGas 9 Be µg L -1 NoGas 11 B µg L -1 He 23 Na mg L -1 He 24 Mg mg L -1 He 27 Al µg L -1 He 28 Si mg L -1 He 39 K mg L -1 He 44 Ca mg L -1 NoGas 45 Sc µg L -1 NoGas 47 Ti mg L -1 O 2 48 S mg L -1 O 2 50 S mg L -1 He 51 V µg L -1 He 52 Cr µg L -1 He 55 Mn µg L -1 He 56 Fe µg L -1 H 2 56 Fe µg L -1 He 59 Co µg L -1 He 60 Ni µg L -1 He 63 Cu µg L -1 He 66 Zn µg L -1 NoGas 71 Ga µg L -1 He 75 As µg L -1 H 2 78 Se µg L -1 NoGas 85 Rb µg L -1 He 88 Sr µg L -1 NoGas 89 Y µg L -1 NoGas 90 Zr µg L -1 O 2 91 As µg L -1 NoGas 93 Nb µg L -1 He 95 Mo µg L -1 NoGas 101 Ru µg L -1 NoGas 105 Pd µg L -1 NoGas 107 Ag µg L -1 He 111 Cd µg L -1 He 114 Cd µg L -1 NoGas 118 Sn µg L -1 He 118 Sn µg L -1

6 Table S2 (continued). Limits of detection (LOD) and limit of quantification (LOQ) for total metals mode. Tune Mode m/z Element LOD LOQ Units He 123 Sb µg L -1 He 125 Te µg L -1 NoGas 133 Cs µg L -1 He 135 Ba µg L -1 He 139 La µg L -1 NoGas 140 Ce µg L -1 NoGas 141 Pr µg L -1 NoGas 146 Nd µg L -1 NoGas 147 Sm µg L -1 NoGas 153 Eu µg L -1 NoGas 157 Gd µg L -1 NoGas 159 Tb µg L -1 NoGas 163 Dy µg L -1 NoGas 165 Ho µg L -1 NoGas 166 Er µg L -1 NoGas 169 Tm µg L -1 NoGas 172 Yb µg L -1 NoGas 175 Lu µg L -1 NoGas 178 Hf µg L -1 NoGas 181 Ta µg L -1 He 182 W µg L -1 NoGas 185 Re µg L -1 NoGas 195 Pt µg L -1 NoGas 197 Au µg L -1 He 201 Hg µg L -1 H Hg µg L -1 He 205 Tl µg L -1 He 208 Pb µg L -1 He 209 Bi µg L -1 NoGas 232 Th µg L -1 He 238 U µg L -1 LOD = 3 x σ blank concentration LOQ = 10 x σ blank concentration

7 Table S3. Sample comparison results from the old method and the new method ( in total metals mode). Waste Water 1 Waste Water 2 Waste Water 3 Industrial Water 1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 9 Be [ NoGas ] B [ NoGas ] Na [ He ] Mg [ He ] Al [ He ] K [ He ] Ca [ He ] Ti [ NoGas ] V [ He ] Cr [ He ] Mn [ He ] Fe [ H2 ] Co [ He ] Ni [ He ] Cu [ He ] Zn [ He ] As [ He ] Se [ H2 ] Sr [ He ] Y [ NoGas ] Ag [ NoGas ] Cd [ He ] Sn [ NoGas ] Sb [ He ] Ba [ He ] La [ He ] W [ He ] Hg [ He ] Tl [ He ] [Pb] [ He ] [Pb] [ He ] Pb [ He ] Bi [ He ] U [ He ]

8 Table S3 (continued). Sample comparison results from the old method and the new method ( in total metals mode). Waste Water 4 Sludge 1 Soil 1 Sand 1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 9 Be [ NoGas ] B [ NoGas ] Na [ He ] Mg [ He ] Al [ He ] K [ He ] Ca [ He ] Ti [ NoGas ] V [ He ] Cr [ He ] Mn [ He ] Fe [ H2 ] Co [ He ] Ni [ He ] Cu [ He ] Zn [ He ] As [ He ] Se [ H2 ] Sr [ He ] Y [ NoGas ] Ag [ NoGas ] Cd [ He ] Sn [ NoGas ] Sb [ He ] Ba [ He ] La [ He ] W [ He ] Hg [ He ] Tl [ He ] [Pb] [ He ] [Pb] [ He ] Pb [ He ] Bi [ He ] U [ He ]

9 Table S3 (continued). Sample comparison results from the old method and the new method ( in total metals mode). Soil 2 Soil 3 Soil 4 Sludge 2 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 9 Be [ NoGas ] B [ NoGas ] Na [ He ] Mg [ He ] Al [ He ] K [ He ] Ca [ He ] Ti [ NoGas ] V [ He ] Cr [ He ] Mn [ He ] Fe [ H2 ] Co [ He ] Ni [ He ] Cu [ He ] Zn [ He ] As [ He ] Se [ H2 ] Sr [ He ] Y [ NoGas ] Ag [ NoGas ] Cd [ He ] Sn [ NoGas ] Sb [ He ] Ba [ He ] La [ He ] W [ He ] Hg [ He ] Tl [ He ] [Pb] [ He ] [Pb] [ He ] Pb [ He ] Bi [ He ] U [ He ]

10 Table S3 (continued). Sample comparison results from the old method and the new method ( in total metals mode). Soil 2 Soil 3 Soil 4 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 µg L -1 9 Be [ NoGas ] B [ NoGas ] Na [ He ] Mg [ He ] Al [ He ] K [ He ] Ca [ He ] Ti [ NoGas ] V [ He ] Cr [ He ] Mn [ He ] Fe [ H2 ] Co [ He ] Ni [ He ] Cu [ He ] Zn [ He ] As [ He ] Se [ H2 ] Sr [ He ] Y [ NoGas ] Ag [ NoGas ] Cd [ He ] Sn [ NoGas ] Sb [ He ] Ba [ He ] La [ He ] W [ He ] Hg [ He ] Tl [ He ] [Pb] [ He ] [Pb] [ He ] Pb [ He ] Bi [ He ] U [ He ]

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