Electronic Supplementary Material - Accred. Qual. Assur., 2017, Springer-Verlag, Berlin Heidelberg

ETV-ICP-OES: a useful technique for homogeneity study of trace element in metals. Application to the homogeneity study of 23 elements in electrolytic copper.

Electronic Supplementary Material

Accred. Qual. Assur., 2017, Springer-Verlag, Berlin Heidelberg

ETV-ICP-OES: a useful technique for homogeneity study of trace element in metals. Application to the homogeneity study of 23 elements in electrolytic copper.

Thomas Bacquart1, Juergen Hassler2, Thomas Vogt3, Peter Perzl4, Sascha Steigerwald5, Wieland Schmidt5, Marc Sterckx6, T.P.J. Linsinger1

1: JRC, Directorate F - Health, Consumers and Reference Materials, European Commission, Retieseweg 111, 2440 Geel, Belgium

2: Ifenstr. 16, 87471 Durach, Germany

3: Institute of Analytical Chemistry, TU Bergakademie Freiberg, Leipziger Strasse 29, 09599 Freiberg, Germany

4: SPECTRO Analytical Instruments GmbH, Boschstrasse 10, 47533 Kleve, Germany

5: Umicore AG & Co. KG, Rodenbacher Chaussee 4, 63403 Hanau-Wolfgang, Germany

6: Umicore Research, Watertorenstraat 33, B-2250, Olen, Belgium

Corresponding author email:

Instrument parameters for ETV-ICP-OES

Gas flow rates and temperature programs used for the three experimental setups are given in Table . All the ETV-ICP-OES analyses were performed using Spectra system ETV 4000 coupled with Spectro ARCOS EOP. The ETV-ICP-OES was calibrated using the certified reference materials (BAM-M382, BAM-M383 and ERM-EB385).

Table 1. Gas flow rates and temperature programs used for the ETV experiments: SF6 halogenation (SF6), H2 total evaporation (H2 tot) and, H2 partial evaporation (H2 part)

Gas-flow / Gas-flow-rate M I
(SF6) / Gas-flow-rate M II
(H2 tot) / Gas-flow-rate M III
(H2 part)
flow / Gas / Flow [ml.min-1] / Gas / Flow [ml.min-1] / Gas / Flow [ml.min-1]
Bypass gas / Ar / 400 / Ar / 400 / Ar / 400
Inner gas / Ar / 150 / Ar / 115 / Ar / 115
Modifier gas / SF6 / 1.2 / SF6 / 50 / SF6 / 50
Temperature program / Temperature program MI (SF6) / Temperature program MII (H2 tot) / Temperature program MIII (H2 part)
step / Time [s] / Temperature [°C] / Time [s] / Temperature [°C] / Time [s] / Temperature [°C]
Start / 0 / RT / 0 / RT / 0 / RT
Ramp 1 / 6 / RT à 400 / 7 / RT à 700 / 10 / RT à 700
Ramp 2 / 11 / 400 à 900 / 7 / 700 à 1050 / 10 / 700 à 1050
Ramp 3 / 5 / 900 à 930 / 10 / 1050 à 1650 / 10 / 1050 à 1700
Ramp 4 / 7 / 930 à 1240 / 9 / 1650 à 2350 / 2 / 1700 à 2300
Ramp 5 / 5 / 1240 à1550 / 20 / 2350 à 2450 / 3 / 2300 à 2320
Ramp 6 / 15 / 1550 à 1630 / 20 / cooling / 20 / cooling
Ramp 7 / 2 / 1630 à 1640
Ramp 8 / 20 / cooling

RT means room temperature

Table 2. Summary of the wavelengths used in this study. The wavelengths reported in bold and italic correspond to the wavelengths selected for the homogeneity study.

Elements / Wavelengths used in this study [nm]
Ag / 243.779
338.290
Al / 308.215
394.401
As / 189.042
Au / 242.795
Bi / 190.241
Cd / 226.502
228.802
Co / 228.616
345.350
Cr / 206.542
267.716
Fe / 233.280
262.829
302.107
In / 325.609
451.131
Mg / 279.079
285.213
Mn / 293.306
Ni / 231.604
232.003
P / 178.287
185.939
Pb / 168.215
Sb / 206.833
Se / 196.090
Si / 288.158
Sn / 189.991
242.949
Te / 170.000
Ti / 190.646
316.257
Zn / 206.200
334.502
Zr / 273.272
274.051

Method performance of the modified ETV-ICP-OES method

Evaporation profiles

i)  ETV-ICP-OES using SF6 modifier

Figure 1. Method M I (SF6 halogenation): Time and temperature depending net spectral line intensities of Al ▬▬, As ▬▬, Cd ▬▬, Co ▬▬, Cu ▬▬, Fe ▬▬, Ni ▬▬, Sb ▬▬, Zn ▬▬ and Zr ▬▬ using test-sample 005 of copper crm ERM EB075 and SF6 as modifier gases; and temperature T versus time , according to the temperature program TP-M I (SF6) of Table

ii)  ETV-ICP-OES using total evaporation

Figure 2. Method M II (H2 total evaporation): Time and temperature depending spectral line intensities with H2 as modifier (concentration 30 %; inner gas flow rate 165 mL min-1) for Ag ▬▬, As ▬▬, Au ▬▬, Bi ▬▬, Cu ▬▬, Mg ▬▬, Pb ▬▬, Se ▬▬, Te ▬▬ and Zn ▬▬, using test-samples 175 of copper CRM ERM-EB075 and temperature T using temperature program TP-M II (H2 tot) of Table

iii)  ETV-ICP-OES using partial evaporation

Figure 3. Method M III (H2 part evaporation): Time and temperature depending spectral line intensities with H2 as modifier (concentration 30 %; inner gas flow rate 165 mL min-1) for Ag ▬▬, As ▬▬, Bi ▬▬, Cd ▬▬, Cu ▬▬, Mg ▬▬, Pb ▬▬, Se ▬▬, Te ▬▬ and Zn ▬▬, using test-samples 099 of copper ERM-EB075 and temperature T using temperature program TP-M III (H2 part) of Table 1

Figure 4: Representation of swb in ERM-EB074C (A) and in ERM-EB075C (B) in function of the chemical element. The results of each analytical method are represented by different symbols: ○: ETV-ICP-OES H2 and partial evaporation (sample intake: 20 – 45 mg); +: ETV-ICP-OES SF6 halogenation (sample intake: 20 – 45 mg); X: ETV-ICP-OES H2 and total evaporation (sample intake: 3 - 7 mg). The dashed line represents swb of the digestion methods (ICP-MS / ICP-OES) in ERM-EB074 and ERM-EB075 reported in the certification report.

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Electronic Supplementary Material - Accred. Qual. Assur., 2017, Springer-Verlag, Berlin Heidelberg

ETV-ICP-OES: a useful technique for homogeneity study of trace element in metals. Application to the homogeneity study of 23 elements in electrolytic copper.

Individual data per element

Summary of study setup, data treatment, results of analysis and final homogeneity uncertainty for each elements and each technique/wavelength. ETV SF6 stands for ETV-ICP-OES using SF6 modifier, ETV total stands for ETV-ICP-OES with total evaporation and ETV-part stands for ETV-ICP-OES with partial evaporation. The information for analytical trend, technical, individual and mean outlier is given with the number of it in bracket. The different components calculated as described in Material and Methods are the method repeatability (swb,rel), between–unit standard deviation (sbb,rel), the maximum inhomogeneity that could be hidden by method repeatability (u*bb,rel) and the rectangular distribution uncertainty (urec)when a mean outlier was detected. In the calculation of sbb, the mean square between groups (MSbetween) was often smaller than the mean squares within groups (MSwithin), resulting in the impossibility to calculate sbb. In this case, MSB<MSW was reported in the Table. The homogeneity uncertainty corresponds to the larger value of sbb, urec and u*bb. n.a.: not applicable.

Table 3. Results obtained on ERM-EB074C.

Element / Method / Wavelength [nm] / Between day difference / Analytical Trend / Technical outlier / individual outlier / Mean outlier / Sbb [%] / Swb [%] / ubb* [%] / urec [%] / Homogeneity uncertainty [%] / number of replicates / Number of units
Ag / ICP-OES / 328 / 338 / No / No / No / No / No / MSB<MSW / 6.27% / 1.59% / - / 1.59% / 4 / 10
ETV total / Ag 243.779 / Yes / No / Yes (3) / No / No / MSB<MSW / 19.46% / 4.33% / - / 4.33% / 5 / 10
ETV total / Ag 338.290 / Yes / Yes (1) / Yes (3) / No / No / 3.84% / 9.24% / 2.06% / - / 3.84% / 5 / 10
ETV-part / Ag 243.779 / n.a. / Yes / Yes (1) / No / No / MSB<MSW / 18.97% / 6.35% / - / 6.35% / 3 / 10
ETV-part / Ag 338.289 / n.a. / Yes / Yes (1) / No / No / 1.70% / 5.28% / 1.77% / - / 1.77% / 3 / 10
Al / ICP-OES / 226/236/237/258/
308/309/394/396 / Yes / Yes (1) / No / No / No / MSB<MSW / 22.95% / 5.83% / - / 5.83% / 4 / 10
ETV SF6 / Al 308.215 / n.a. / No / Yes (1) / Yes (1) / No / MSB<MSW / 7.74% / 1.66% / - / 1.66% / 5 / 10
ETV SF6 / Al 394.401 / n.a. / No / Yes (1) / Yes (1) / No / MSB<MSW / 7.69% / 1.65% / - / 1.65% / 5 / 10
As / ICP-MS / n.a. / Yes / No / No / No / No / MSB<MSW / 6.30% / 1.60% / - / 1.60% / 4 / 10
ETV SF6 / As 189.042 / n.a. / No / Yes (1) / Yes (1) / No / MSB<MSW / 0.72% / 0.15% / - / 0.15% / 5 / 10
ETV total / As 189.042 / Yes / Yes (1) / Yes (2) / Yes (2) / No / MSB<MSW / 7.15% / 1.56% / - / 1.56% / 5 / 10
ETV-part / As 189.042 / n.a. / Yes / No / No / No / 1.86% / 5.67% / 1.84% / - / 1.86% / 3 / 10
Au / ICP-MS / n.a. / Yes / Yes (1) / No / No / No / MSB<MSW / 11.35% / 2.88% / - / 2.88% / 4 / 10
ETV total / Au 242.795 / Yes / Yes (1) / Yes (3) / Yes (1) / No / MSB<MSW / 4.79% / 1.07% / - / 1.07% / 5 / 10
Bi / ICP-MS / n.a. / Yes / Yes (1) / No / Yes (1) / No / 5.33% / 13.90% / 3.53% / - / 5.33% / 4 / 10
ETV SF6 / Bi 190.241 / n.a. / No / No / No / No / MSB<MSW / 1.68% / 0.36% / - / 0.36% / 5 / 10
ETV total / Bi 190.241 / Yes / Yes (1) / Yes (2) / No / No / 1.39% / 5.83% / 1.28% / - / 1.39% / 5 / 10
ETV-part / Bi 190.241 / n.a. / No / No / No / No / MSB<MSW / 6.38% / 2.07% / - / 2.07% / 3 / 10
Cd / ICP-MS / n.a. / No / Yes (1) / No / No / No / MSB<MSW / 8.07% / 2.05% / - / 2.05% / 4 / 10
ETV SF6 / Cd 228.802 / n.a. / No / No / No / No / 0.43% / 1.70% / 0.36% / - / 0.43% / 5 / 10
ETV SF6 / Cd 226.502 / n.a. / No / No / No / No / 0.46% / 2.29% / 0.49% / - / 0.49% / 5 / 10
ETV-part / Cd 228.802 / n.a. / Yes / No / Yes (1) / No / MSB<MSW / 5.22% / 1.70% / - / 1.70% / 3 / 10
ETV-part / Cd 226.502 / n.a. / Yes / No / No / No / MSB<MSW / 5.13% / 1.66% / - / 1.66% / 3 / 10
Co / ICP-MS / n.a. / Yes / No / No / No / No / MSB<MSW / 10.40% / 2.70% / - / 2.70% / 4 / 10
ETV SF6 / Co 345.350 / n.a. / No / No / Yes (1) / Yes (1) / 0.76% / 3.67% / 0.78% / 2.83% / 2.83% / 5 / 10
ETV SF6 / Co 228.616 / n.a. / No / No / Yes (1) / Yes (1) / 0.61% / 3.24% / 0.69% / 2.27% / 2.27% / 5 / 10
ETV total / Co 228.616 / Yes / Yes (1) / Yes (2) / Yes (1) / No / 1.19% / 12.09% / 2.64% / - / 2.64% / 5 / 10
ETV-part / Co 228.616 / n.a. / Yes / No / No / No / MSB<MSW / 5.99% / 1.95% / - / 1.95% / 3 / 10
Cr / ICP-MS / n.a. / No / No / No / Yes (1) / No / MSB<MSW / 10.06% / 2.56% / - / 2.56% / 4 / 10
ETV SF6 / Cr 284.984 / n.a. / No / Yes (1) / Yes (1) / No / 1.30% / 17.65% / 3.79% / - / 3.79% / 5 / 10
ETV SF6 / Cr 267.716 / n.a. / No / Yes (1) / Yes (1) / No / 0.79% / 17.76% / 3.82% / - / 3.82% / 5 / 10
ETV SF6 / Cr 206.542 / n.a. / No / Yes (1) / Yes (1) / No / 1.07% / 16.71% / 3.59% / - / 3.59% / 5 / 10
ETV-part / Cr 284.984 / n.a. / Yes / No / No / No / MSB<MSW / 14.11% / 4.58% / - / 4.58% / 3 / 10
ETV-part / Cr 267.716 / n.a. / Yes / No / No / No / 2.07% / 8.06% / 2.62% / - / 2.62% / 3 / 10
ETV-part / Cr 206.542 / n.a. / Yes / No / No / No / 2.01% / 11.65% / 3.78% / - / 3.78% / 3 / 10
Fe / ICP-MS / n.a. / No / No / No / No / No / 1.74% / 4.35% / 1.13% / - / 1.74% / 4 / 10
ETV SF6 / Fe 262.829 / n.a. / No / No / Yes (1) / No / MSB<MSW / 5.82% / 1.23% / - / 1.23% / 5 / 10
ETV SF6 / Fe 302.107 / n.a. / No / No / Yes (1) / No / MSB<MSW / 5.25% / 1.11% / - / 1.11% / 5 / 10
In / ICP-MS / n.a. / No / No / No / No / No / MSB<MSW / 6.63% / 1.68% / - / 1.68% / 4 / 10
ETV SF6 / In 325.609 / n.a. / No / No / Yes (1) / No / 0.26% / 0.90% / 0.19% / - / 0.26% / 5 / 10
ETV SF6 / In 451.131 / n.a. / Yes / No / Yes (1) / Yes (1) / 0.06% / 1.01% / 0.21% / 0.70% / 0.70% / 5 / 10
Mg / ICP-MS / n.a. / No / No / No / Yes (1) / No / MSB<MSW / 15.86% / 4.03% / - / 4.03% / 4 / 10
ETV SF6 / Mg 279.079 / n.a. / Yes / Yes (1) / No / No / MSB<MSW / 2.75% / 0.59% / - / 0.59% / 5 / 10
ETV SF6 / Mg 285.213 / n.a. / Yes / Yes (1) / No / No / MSB<MSW / 2.81% / 0.60% / - / 0.60% / 5 / 10
ETV total / Mg 279.079 / Yes / Yes (1) / Yes (3) / No / No / 1.52% / 11.55% / 2.62% / - / 2.62% / 5 / 10
ETV total / Mg 285.213 / Yes / No / Yes (3) / Yes (2) / No / 2.39% / 12.36% / 2.75% / - / 2.75% / 5 / 10
ETV-part / Mg 279.079 / n.a. / Yes / No / No / No / 1.08% / 4.48% / 1.46% / - / 1.46% / 3 / 10
ETV-part / Mg 285.213 / n.a. / Yes / No / No / No / MSB<MSW / 4.26% / 1.38% / - / 1.38% / 3 / 10
Mn / ICP-MS / n.a. / Yes / No / Yes (1) / No / No / MSB<MSW / 7.18% / 1.86% / - / 1.86% / 4 / 10
ETV SF6 / Mn 293.306 / n.a. / No / No / Yes (1) / No / 0.37% / 1.23% / 0.26% / - / 0.37% / 5 / 10
Ni / ICP-MS / n.a. / Yes / No / No / No / No / MSB<MSW / 15.01% / 3.81% / - / 3.81% / 4 / 10
ETV SF6 / Ni 174.828 / n.a. / No / No / Yes (1) / Yes (1) / 14.90% / 18.99% / 4.02% / 24.40% / 24.40% / 5 / 10
ETV SF6 / Ni 231.604 / n.a. / No / No / Yes (1) / Yes (1) / 13.81% / 18.43% / 3.90% / 22.59% / 22.59% / 5 / 10