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User Benefits Application News Analysis of Trace Elements in Table Salt Using ICPMS-2050 Kosuke Naka Inductively Coupled Plasma Mass Spectrometer ICPMS-2050 Sample Preparation The robustness of the ICPMS-2050 to sample matrix effects was evaluated using table salt, a food with a particularly high matrix concentration. Unspiked Sample An unspiked sample was prepared by weighing out approx. 0.2 g of table salt, adding 2.5 mL of nitric acid, 0.25 mL of hydrochloric acid, and making the mixture up to 50 mL with pure water. The final concentration of table salt in the unspiked sample was approx. 0.4 %, the nitric acid concentration was 5 % v/v, and the hydrochloric acid concentration was 0.5 % v/v. Spiked Sample A spiked sample was prepared by weighing out approx. 0.2 g of table salt, adding 2.5 mL of nitric acid, 0.25 mL of hydrochloric acid, adding commercially available single-element standard solutions of Al, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Cd, Sn, Hg, Tl, and Pb, then making the mixture up to 50 mL with pure water. Method Blank A method blank was prepared by combining 2.5 mL of nitric acid with 0.25 mL of hydrochloric acid and making the mixture up to 50 mL with pure water. Fig. 1 ICPMS-2050 and AS-20 Equipment Table 1 Target Element Concentrations in Calibration Standards Elements Calibration Standard (µg/L) STD1 STD2 STD3 STD4 Cr, Ni, As, Se, Mo, Cd, Sn, Tl, Pb 0 1 5 10 Hg 0 0.1 0.5 1 Al, Mn, Cu, Zn, 0 10 50 100 Nitric acid 5 % v/v Hydrochloric acid 0.5 % v/v Standard Samples Calibration Standards Calibration standards were prepared by combining commercially available single-element standard solutions of Al, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Cd, Sn, Hg, Tl, and Pb and adding nitric acid and hydrochloric acid. The concentration of the target elements in each calibration standard is shown in Table 1. Internal Standard Solution An internal standard solution was prepared by combining commercially available single-element standard solutions of Sc, Ge, Rh, Ir, and Bi and adding nitric acid to 5 % v/v and hydrochloric acid to 0.5 % v/v. The final concentration of Sc, Ge, Rh, Ir, and Bi in the internal standard solution was 2 mg/L. Initial Calibration Verification (ICV) and Continuing Calibration Verification (CCV) Samples ICV and CCV samples were prepared with the same target element concentrations as STD3 in Table 1. Continuing Calibration Blank (CCB) Sample A CCB sample was prepared with the same target element concentrations as STD1 in Table 1. Equipment Configuration and Analytical Conditions The configuration of the ICP-MS system is shown in Table 2. To reduce running costs, analysis was performed with a mini-torch that consumes less argon gas than a typical plasma torch. To reduce the labor involved in sample preparation, the internal standard sample was added online using an online internal standard kit. The analytical conditions used are shown in Table 3. A complex investigation of conditions was avoided by using the analytical conditions from a preset method in LabSolutions™ ICPMS. Elements in table salt can be accurately analyzed over a long period of time. Reduced running costs due to a mini-torch that uses less argon gas Avoids a complex investigation of conditions by using the analytical conditions from preset methods. Introduction The Codex general standard for contaminants and toxins in food and feed (Codex) establishes requirements for levels of toxic metal elements in foods 1) . Inductively coupled plasma mass spectrometry (ICP-MS) systems can perform highly sensitive quantitative determination of multiple elements simultaneously, making them suited to the analysis of even trace amounts of toxic metal elements in foods. Food samples are typically high-matrix samples that can often impact the clogging of torch or interfaces such as skimmer cone, non-spectral interference, and long-term stability in ICP- MS analysis. This Application News uses the ICPMS-2050 (Fig. 1) to analyze table salt, a food with a particularly high matrix concentration. This analysis was performed using a mini-torch that features low argon gas consumption. The long-term stability and spike recovery were assessed based on the Food and Drug Administration (FDA) Elemental Analysis Manual (EAM) Section 4.7 2) .
Application News Element Cell Gas Internal Standard Element IDL (µg/L) DL in Table Salt (mg/kg) Codex Reference Level (mg/kg) 27 Al H2 45 Sc 0.09 0.02 – 52 Cr He 74 Ge 0.1 0.03 – 55 Mn He 74 Ge 0.07 0.02 – 60 Ni He 74 Ge 0.09 0.02 – 65 Cu He 74 Ge 0.09 0.02 – 66 Zn He 74 Ge 0.2 0.04 – 75 As He 74 Ge 0.08 0.02 0.5 78 Se H2 74 Ge 0.04 0.009 – 95 Mo He 103 Rh 0.02 0.005 – 111 Cd He 103 Rh 0.03 0.007 0.5 118 Sn He 103 Rh 0.07 0.02 – 202 Hg He 193 Ir 0.009 0.002 0.1 205 Tl He 209 Bi 0.009 0.002 – sum Pb He 209 Bi 0.008 0.002 1 Table 3 Analytical Conditions RF Power: 1.20 kW Plasma Gas Flowrate: 9.0 L/min Auxiliary Gas Flowrate: 1.10 L/min Carrier Gas Flowrate: 0.35 L/min Dilution Gas Flowrate: 0.55 L/min Cell Gas: He/H 2 Evaluation of Long-Term Stability The long-term stability was assessed by the analysis for around 10 hours. The analytical sequence used was the calibration standards followed by the ICV sample, method blank, then test samples. The CCV sample and CCB sample were assayed every 10 test samples to confirm the validity of the calibration curve over the course of the evaluation. The analytical sequence is shown in Fig. 2. Recovery rates from the ICV samples and CCV samples are plotted in Fig. 3. Recoveries from all ICV and CCV samples were within 90 and 110 % (red dashed lines) as required by EAM Section 4.7. All elements in the CCB sample were also assayed below the analytical solution quantification level (ASQL, 30σ × calibration curve slope 3) ). The change in signal intensity of the internal standard elements over the course of the evaluation is shown in Fig. 4, where the signal intensity of internal standard elements in STD1 is taken as 100 %. The change in signal intensity of the internal standard elements during the evaluation spanning around 10 hours remained within 60 to 120 % (red dashed lines) as required by EAM Section 4.7. Calibration Standards ICV Sample Method Blank Test Sample Assay the CCV and CCB sample every 10 test samples Fig. 2 Analytical Sequence Spike Recovery Test A spike recovery test was performed to assess the effect of the sample matrix on analysis. The results are shown in Table 5. Good recovery of between 95 and 106 % was achieved for all elements, showing the sample matrix effect on the analysis remained allowably small. All recovery levels remained within 80 to 120 % as required by EAM Section 4.7. Element Unspiked Sample (µg/L) Spiked Conc. (µg/L) Spiked Sample (µg/L) Spike Recovery (%) 27 Al N.D. 10 10.5 105 52 Cr N.D. 1 0.99 99 55 Mn 5.47 10 15.5 100 60 Ni N.D. 1 1.05 105 65 Cu N.D. 10 9.68 97 66 Zn N.D. 10 9.5 95 75 As N.D. 1 1.05 105 78 Se 0.12 1 1.09 97 95 Mo 0.05 1 1.10 105 111 Cd N.D. 1 0.96 96 118 Sn N.D. 1 0.98 98 202 Hg N.D. 0.1 0.106 106 205 Tl N.D. 1 1.01 101 sum Pb 0.741 1 1.77 103 Spike recovery (%) = (Spiked sample - Unspiked sample) / Spiked concentration × 100 N.D.: Below instrument detection limit (IDL) Table 5 Spike Recovery Test Detection Limits (DLs) Detection limits are shown in Table 4. The detection limits were calculated using the standard deviation (σ) of the calibration blank (STD1). Detection limits for the target elements in table salt were all at least one order of magnitude below the reference levels listed in the Codex. Table 4 Detection Limits IDL: Instrument detection limit (3σ × calibration curve gradient) sum Pb: Measured as the sum of 206 Pb, 207 Pb, and 208 Pb Quantitative Analysis A calibration curve was prepared using the calibration standards shown in Table 1. The unspiked sample, spiked sample, method blank, ICV sample, CCV sample, and CCB sample were quantitatively analyzed by this calibration curve. Table 2 ICP-MS System Configuration System: ICPMS-2050 Nebulizer: Nebulizer DC04 Chamber: Cyclone Chamber Torch: Mini-Torch Sampling Cone: Nickel Skimmer Cone: Nickel Autosampler: AS-20 Internal Standard Elements Online Internal Standard Kit (sample: internal standard = about 9 :1)
Application News www.shimadzu.com/an/ Shimadzu Corporation © Shimadzu Corporation, 2023 For Research Use Only. Not for use in diagnostic procedures. This publication may contain references to products that are not available in your country. Please contact us to check the availability of these products in your country. The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu. See http://www.shimadzu.com/about/trademarks/index.html for details. Third party trademarks and trade names may be used in this publication to refer to either the entities or their products/services, whether or not they are used with trademark symbol “TM” or “”. Shimadzu disclaims any proprietary interest in trademarks and trade names other than its own. The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject to change without notice. 0 20 40 60 80 100 120 140 0:00 2:00 4:00 6:00 8:00 10:00 Sc (H₂) Ge (He) Ge (H₂) Rh (He) Ir (He) Bi (He) 70 80 90 100 110 120 130 Al (H₂) Cr (He) Mn (He) Ni (He) Cu (He) Zn (He) As (He) Se (H₂) Mo (He) Cd (He) Sn (He) Hg (He) Tl (He) Pb (He) ICV CCV CCV CCV CCV CCV CCV CCV CCV CCV CCV LabSolutions is a trademark of Shimadzu Corporation and its affiliates in Japan and other countries. Fig. 4 Change in Signal of Internal Standard Elements during Approx. 10 Hours of Analysis * Matrix-free samples (calibration standards, etc.) ▲ Matrix-containing samples (0.4 % table salt solution) <References> 1) Codex general standard for contaminants and toxins in food and feed (CODEX STAN 193-1995) 2) U.S. Food and Drug Administration Elemental Analysis Manual 4.7 Inductively Coupled Plasma-Mass Spectrometric Determination of Arsenic, Cadmium, Chromium, Lead, Mercury, and Other Elements in Food Using Microwave Assisted Digestion, Version 1.2 (February 2020) 3) U.S. Food and Drug Administration Elemental Analysis Manual 3.2 Terminology, Version 3.0 (December 2021) Fig. 3 ICV and CCV Sample Recovery * * * * * * * * * * * ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Conclusion This Application News describes the use of the the ICPMS-2050 with a mini-torch to measure trace elements in table salt. The detection limits were sufficient to measure trace elements in table salt. Spike recovery testing showed good results even with high matrix concentration samples, confirming the accuracy of the analysis. The stability was also confirmed over the course of 10 hours of analysis. The ICPMS-2050 performs highly sensitive, accurate, and stable analysis. The ICPMS-2050 can also reduce running costs by using a mini-torch that consumes less argon gas. Analytical conditions can also be entered from preset methods, simplifying analysis by avoiding a complex investigation of conditions. Time ICV and CCV Sample Recovery (%) Change in Internal Standard Signal (%) First Edition: Jul. 2023 01-00574-EN
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