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Food Analysis / ICPMS-2030 Analysis of Trace Elements in Certified Fish Sample with ICP-MS Application News AD-0169 The sample used in this analysis was Fish Protein Certified Reference Material for Trace Metals (DORM-4) from National Research Council Canada. There were two sets of preparation. The sample, 0.5 g, was placed in a digestion vessel followed by addition of 5.0 mL of concentrated nitric acid, 2.0 mL of hydrogen peroxide and 1.0 mL of water. The mixture was digested using microwave- assisted digestion system based on AOAC 999.10 procedure. After the digestion process, deionized water was added to the digested sample to a final total volume of 200.0 mL. The calibration standards were prepared from 1000 ppm copper (Cu), iron (Fe) and zinc (Zn) standards, and 100 ppm ICP multi-element standard solution IX, which contains arsenic (As), cadmium (Cd), chromium (Cr), mercury (Hg), nickel (Ni), lead (Pb) and selenium (Se). The internal standards were prepared from 1000 ppm bismuth (Bi), germanium (Ge), indium (In) and scandium (Sc) standards and diluted to a concentration of 10 ppb with pure water. The standard solutions were purchased from Merck Millipore, Germany. Type E-1 ultra pure water with resistivity of 18 ΩW was used. Four different calibration ranges were prepared to cover the range of the elements based on the certified values. The calibration standards were acid matched to the digested samples. Table 1. Instrument and measurement conditions Instrument : ICPMS-2030 Radio Frequency Power : 1.20 (kW) Sampling Depth :6 (mm) Plasma Gas Flow Rate : 8.0 (L/min) Auxiliary Gas Flow Rate : 1.10 (L/min) Nebulizer Gas Flow Rate : 0.60 (L/min) Nebulizer : Coaxial Nebulizer Spray Chamber : Cyclone Chamber (electronic cooling) Plasma Torch : Mini-torch Collision gas : He Fish is one of the most important food resource that is widely consumed in many parts of the world due to its high protein content, low saturated fats and omega-3 fatty acid. However, because of industrial discharges from human activities, fish may have trace levels of heavy metals such as arsenic, cadmium, lead, mercury and nickel which are absorbed from the surrounding waters and the foods they eat. Not only do these heavy metals accumulate in organisms and circulate in food chain, they also remain in the sediments of the ecosystem in the long term [1]. The toxicity of these metals poses a concern to human health through the consumption of fish. Fish are the single largest sources of mercury and arsenic for man. Mercury is a known human toxicant and the primary sources of mercury contamination in man are through eating fish [2]. Minamata disease is a methylmercury poisoning associated with the daily consumption of large quantities of fish and shellfish heavily contaminated with the toxic chemical [3]. Here, Shimadzu ICPMS-2030, a inductively coupled plasma mass spectrometer (ICP-MS) was used to conduct a simultaneous analysis of elements in fish. In addition to being highly sensitive, the ICPMS-2030 uses a helium gas collision system that greatly reduces the spectral interference caused by argon and chlorine. Measurement was conducted using the Shimadzu ICPMS- 2030 ICP-MS spectrometer, equipped with the mini-torch and helium (He) gas collision system. The mini-torch reduces running cost associated with argon gas usage. The helium gas collision system reduces spectral interference caused by polyatomic ions, for example, 40 Ar 16 O that interferes with measurement of 56 Fe, 40 Ar 35 Cl that interferes with measurement of 75 As, and 40 Ar 38 Ar that interferes with measurement of 78 Se. The typical measurement conditions are shown in Table 1. The elements, mass, and calibration ranges used are shown in Table 2. Introduction Experimental
Application News AD-0169 SHIMADZU (Asia Pacific) Pte. Ltd 79 Science Park Drive, #02-01/08 Cintech IV, Singapore 118264 www.shimadzu.com.sg Tel: +65-6778 6280 Fax: +65-6778 2050 Copyright © 2017 SHIMADZU (Asia Pacific) Pte. Ltd. All rights reserved. No part of this document may be reproduced in any form or by any means without permission in writing from SHIMADZU (Asia Pacific) Pte. Ltd. Table 3. Quantitation results of Fish CRM DORM-4 Element Fish CRM DORM-4 Measured Value (mg/kg) (Duplicate) Measured Value (mg/kg) Certified Value (mg/kg) As 6.59 6.69 6.80 ± 0.64 Cd 0.299 0.298 0.306 ± 0.015 Cr 1.88 1.89 1.87 ± 0.16 Cu 15.6 15.5 15.9 ± 0.9 Fe 326 328 341 ± 27 Hg 0.415 0.360 0.410 ± 0.055 Ni 1.31 1.29 1.36 ± 0.22 Pb 0.388 0.389 0.416 ± 0.053 Se 3.44 3.51 3.56 ± 0.34 Zn 55.0 53.3 52.2 ± 3.2 The ICPMS-2030 can provide a sensitive multi-element analysis of the trace elements in fish accurately, even for low concentration of Cd, Hg and Pb. Table 2. Elements, mass and calibration ranges The quantitative results for the trace elements were within the certification range of Fish Protein CRM DORM-4 as shown in Table 3. The instrument detection limits (IDL) and the limits of quantitation (LOQ) are shown in Table 4. The IDL is calculated as three times the standard deviation of 10 replicate measurements of a calibration blank, and the LOQ is calculated as ten times the standard deviation of 10 replicate measurements of a calibration blank. Table 4. Detection Limits Element IDL (ppb) LOQ (ppb) As 0.003 0.0097 Cd 0.001 0.0044 Cr 0.005 0.018 Cu 0.02 0.065 Fe 0.06 0.20 Hg 0.003 0.011 Ni 0.01 0.040 Pb 0.004 0.014 Se 0.01 0.045 Zn 0.03 0.091 Results and Discussion Conclusions 1. Sreenivasa Rao. J., Vasudeva Rao. Y., Devindra. S and Longvah. T. (2014). Analysis of heavy metal concentrations in Indian marine fish using ICP-MS after closed vessel micro wave digestion method. International Journal of Analytical and Bioanalytical Chemistry 4(3): 67-73. 2. F. Emami Khansari, M. Ghazi-Khansari, M. Abdollahi (2005). Heavy metals content of canned tuna fish. Food Chemistry 93: 293-296. 3. Noriyuki Hachiya (2006). The history and the present of Minamata disease. Japan Medical Association Journal 49 (3): 112-118. References Element Mass Calibration Range As 75 0 to 20 ppb Cd 111 Cr 52 Hg 202 Ni 60 Pb 208 Se 78 Cu 65 0 to100 ppb Fe 56 0 to 2000 ppb Zn 66 0 to 200 ppb For Research Use Only. Not for use in diagnostic procedures.