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STEP Temperature (˚C) Time (min) Power (W) 1 50 2 1000 2 30 3 0 3 180 25 1000 4 150 1 0 5 180 4 1000 6 180 15 1000 Application News No.J123 Inductively Coupled Plasma Mass Spectrometry Analysis of Toxic Elements in Supplements as per USP 2232 Using the ICPMS-2030 LAAN-A-CP-E036 Q Introduction The United States Pharmacopeia (USP) 2232 designates permitted daily exposure (PDE) levels for four elements for which toxicity is a concern in dietary supplements. PDE values need to be converted to concentrations when evaluating metallic impurities in formulations or their structural components. Compliance with these regulations is also obligatory for supplements imported to the U.S. from other nations. Here, we introduce a quantitative analysis performed on arsenic, cadmium, mercury, and lead in supplements using the Shimadzu ICPMS-2030 ICP mass spectrometer. Q Sample Four commercially available supplements (1) One 0.331 g tablet (three tablets/day) (2) One 0.350 g tablet (one tablet/day) (3) One 0.201 g tablet (one tablet/day) (4) One 0.380 g tablet (six tablets/day) Q Sample Preparation We used the microwave digestion method that could decompose samples faster than the typically used wet digestion method. Since this method uses a closed vessel, it also has the advantage that loss of volatile elements such as arsenic is minimal. In this study, the sample was decomposed using the Milestone General ETHOS-One. One tablet sample, 0.5 mL of hydrochloric acid, and 6.5 mL of nitric acid were added to a quartz vessel of the microwave digestion system for sample preparation. The mixture was then decomposed by the microwave digestion system. After sample decomposition, pure water was added to bring the measurement solution to a volume of 30 mL. At this point, Ga, In, and Bi (at a 10 μg/L concentration in measurement solution) were added as the internal standard elements. Table 1 shows the sample decomposition conditions using the microwave digestion system for sample preparation. Table 1 Sample Decomposition Conditions Using the Microwave Digestion System for Sample Preparation Q Instrument and Analytical Conditions The Shimadzu ICPMS-2030 mass spectrometer with standard attachments as shown in Table 2 was used for measurements. In addition to providing high sensitivity, the ICPMS-2030 is equipped with a collision system using helium gas, which reduces interference from argon and chlorine signiﬁcantly. Instrument : ICPMS-2030 High-frequency output : 1.2 kW Plasma gas ﬂowrate : 8.0 L/min Auxiliary gas ﬂowrate : 1.10 L/min Carrier gas ﬂowrate : 0.65 L/min Nebulizer : Nebulizer 10 Chamber : Cyclone chamber (electronically cooled) Plasma torch : Mini torch Collision gas : He Table 2 Analytical Conditions

Name of Element As Cd Hg Pb PDE (μg/day) 15 5 15 10 Maximum Permitted Concentration *1 (μg/g) 1.5 0.5 1.5 1 Maximum Permitted Concentration in Measurement Solution *2 (μg/g) 3 1 3 2 Detection Limit *2 (μg/L) 0.009 0.003 0.003 0.001 *1: When the maximum intake per day is 10 g *2: When a 0.2 g sample is pretreated and diluted to a volume of 100 mL Name of Element Sample name As Cd Hg Pb ① 0.21 0.029 N.D. 0.035 ② 0.08 0.018 N.D. 0.009 ③ 0.11 0.008 N.D. 0.037 ④ 0.29 0.071 N.D. 0.095 Recovery rate (%) 97 98 92 101 N.D.: Not detected Spike recovery rate (%) = { (Analysis value for the spike recovery test sample − Analysis value) / Spike concentration} × 100 Application News No. © Shimadzu Corporation, 2016 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. Company names, product/service names and logos used in this publication are trademarks and trade names of Shimadzu Corporation or its affiliates, whether or not they are used with trademark symbol “TM” or “®”. Third-party trademarks and trade names may be used in this publication to refer to either the entities or their products/services. 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. www.shimadzu.com/an/ J123 First Edition: Aug. 2016 p Analysis The calibration curve method was used for quantitative analysis of the elements arsenic, cadmium, mercury, and lead. To verify the analysis results, a spike recovery test sample was created by adding a standard solution of measurement elements after the sample decomposition. Quantitative analysis was performed in the same way using this sample. p Analytical Results Table 3 shows the permitted daily exposure (PDE) levels, maximum permitted concentrations, and detection limits. The analysis results and spike recovery rates are shown in Table 4. These show favorable recovery rates and conﬁrm that the results obtained were appropriate. The sensitivity was also evidently sufﬁcient, even at the maximum intake of 10 g per day. p Conclusion Using the ICPMS-2030, it is possible to perform an analysis for controlling the heavy metals arsenic, cadmium, mercury, and lead in supplements. [Reference] USP 2232 Elemental Contaminants in Dietary Supplements Table 3 PDE Levels, Maximum Permitted Concentrations, and Detection Limits for Elemental Impurities Speciﬁed in USP 2232 Table 4 Analytical Results for Supplements (concentration in solid sample, μg/g)