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Matrix Extension and Multi-laboratory Validation of the U.S. Food and Drug Administration Arsenic Speciation Method EAM §4.10 to Include Wine Courtney K. Tanabe, Helene Hopfer, Susan E. Ebeler, Jenny Nelson, Sean D Conklin, Kevin Kubachka, and Robert A Wilson J. Agric. Food Chem., Just Accepted Manuscript • Publication Date (Web): 01 May 2017 Downloaded from http://pubs.acs.org on May 3, 2017

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Journal of Agricultural and Food Chemistry

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Matrix Extension and Multi-laboratory Validation of the U.S. Food and Drug

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Administration Arsenic Speciation Method EAM §4.10 to Include Wine

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Courtney K. Tanabe1,2, Helene Hopfer3, Susan E. Ebeler1,2, Jenny Nelson1,2,4, Sean

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D. Conklin5, Kevin M. Kubachka6, and Robert A. Wilson6

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PA, 16802, USA

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Agilent Technologies, Inc., 5301 Stevens Creek Blvd, Santa Clara CA 95051, USA

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US FDA, Center for Food Safety and Applied Nutrition, College Park, MD 20866,

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USA

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Dept. Viticulture & Enology, University of California, Davis, CA, 95616, USA Food Safety & Measurement Facility, University of California, Davis, CA, 95616 Department of Food Science, The Pennsylvania State University, University Park,

US FDA, Forensic Chemistry Center, Cincinnati, OH 45237; USA

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Abstract

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A multi-laboratory validation (MLV) was performed to extend the U.S. Food and Drug

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Administration’s (FDA) analytical method EAM §4.10, High Performance Liquid

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Chromatography-Inductively Coupled Plasma-Mass Spectrometric Determination of

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Four Arsenic Species in Fruit Juice, to include wine. Several method modifications

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were examined to optimize the method for the analysis of dimethylarsinic acid

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(DMA), monomethylarsonic acid (MMA), arsenate (AsV), and arsenite (AsIII) in

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various wine matrices with a range of ethanol concentrations by liquid

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chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS). The

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optimized method was used for the analysis of five wines of different classifications

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(red, white, sparkling, rosé, and fortified), by three laboratories. Additionally, the

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samples were fortified in duplicate at levels of approximately 5, 10, and 30 µg kg-1

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and analyzed by each participating laboratory. The combined average fortification

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recoveries of DMA, MMA, and inorganic arsenic (iAs the sum of AsV and AsIII) in

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these samples were 101, 100, and 100%, respectively. To further demonstrate the

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method, 46 additional wine samples were analyzed. The total As levels of all the

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wines analyzed in this study were between 1.0 and 38.2 µg kg-1. The overall average

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mass balance based on the sum of the species recovered from the chromatographic

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separation compared to the total As measured was 89% with a range of 51-135%. In

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the 51 analyzed samples, the average percentage of As found in the form of iAs was

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91% with a range of 37-100%.

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Keywords: Arsenic, wine, ICP-MS, HPLC-ICP-MS, speciation

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1. Introduction

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Numerous metals commonly found in grapes play an important role in their

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growth and ultimately in the redox reactions that occur throughout the production of

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wine.1 The concentration of several metals has been shown to affect qualities of

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wine such as browning, turbidity, cloudiness, and astringency.2, 3 Although arsenic

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(As) generally has a minimal impact on wine production as a metabolic inhibitor4, 5

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and is also non-essential to plant growth6, the element can be taken up by the vine

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and detected in the finished wine.7,8 Previous studies have investigated the As concentration throughout the

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production of wine.4, 8, 9 Starting from the ground up, the investigation begins with

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understanding the possible sources of As in the environment, where the grapes are

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grown, then continues to the adsorption from the soil and storage in the plant.3, 7, 9

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Arsenic is present in the Earth’s crust, existing within a variety of rock types, and

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naturally occurs in the environment.10 Soil levels of As generally range from LOD in all five samples ranged from 2.3 – 12.3%, with only samples 4 and 5

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being >4.2% (12.6% (LOQ

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in sample 4, and the RSDr and RSDR were 5.2% and 6.7%, respectively. These

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results indicate excellent within-laboratory and among-laboratory precision for iAs

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and DMA determinations using this method. The mass balance of the sum of the species compared to the total As present

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in each sample was calculated. The average mass balance for samples 1-4 was

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97% with a range of 87-107% for all laboratories. The average mass balance was

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significantly lower for sample 5 (71% with a range of 54-91%). This was most likely

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due to the levels of DMA and iAs in the sample at or near the limit of quantitation and

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not the sample matrix because low level fortifications of DMA, MMA, As(III), and


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As(V) (approximately 5 µg kg-1) in this sample provided an average fortification

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recovery of 107% for DMA, 106% for MMA, and 100% for iAs from the three

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laboratories. Table 2 shows the average percent recovery from each laboratory for the

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MLV samples fortified at levels of approximately 5, 10, and 30 µg kg-1. The average

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recovery of DMA, MMA, and iAs among all the laboratories and fortification levels

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was 101% (range of 99-106%), 100% (range of 92-110%), and 100% (range of 93-

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105%), respectively. However, within those averages were individual recoveries that

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exceeded 115% for MMA, and a single recovery for DMA was > 115%. Laboratories

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2 and 3 had average spike recoveries of 115 and 116%, respectively, for MMA in

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wine sample 4. Wine sample 4 had the highest alcohol content (20% v/v) of the

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validation wine samples. Only one MMA spike recovery was above the 120% upper

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limit for fortification recoveries established in EAM §4.10. Given the range of alcohol

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in these samples, the different types of wine, and the various levels of fortification,

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these averages suggest the optimized method does not suffer from excessive matrix

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interferences in a variety of wine samples. For all laboratories the average r2 value

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for the calibration curves of DMA, MMA, As(III), As(V), and the sum of iAs was

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0.9999 with a range of 0.9989 to 1.0000. All of the calculated r2 values met the

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minimum requirement established in EAM §4.10.

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3.4 Additional Wine Samples A total of 51 additional wine samples were purchased and analyzed to provide

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additional validation data. Of these samples, five were found to have As totals less

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than 1 µg kg-1 and therefore not analyzed further. The total and species specific

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concentrations for the remaining 46 wine samples can be found in Supplementary



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Table 1. The total As concentrations found in the 46 additional wine samples were

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between 1.0 and 38.2 µg kg-1. These values were within previously recorded As

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concentrations seen in wine from around the world.8, 9, 15-27 The average mass balance, based on the sum of the species recovered from

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the chromatographic separation compared to the total As measured, was 89% with a

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range of 51-135%. Inorganic arsenic was found to be the most prominent species in

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the wine samples analyzed accounting for an average of 91% of the sum of the

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species. This is in good agreement with the percentage of iAs typically expected in

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beverages.33 However, in some samples the percent of iAs was as low as 37% of

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the sum of the species. The highest concentration of iAs found in any of the samples

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was 37.6 µg kg-1. MMA was the least prevalent species and was found above the

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LOD in only 6 of the 46 samples. The highest concentration of MMA found in any of

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the samples was 1.0 µg kg-1. This accounted for only 6% of the sum of the As

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species present in the sample. Similarly, the highest concentration of DMA found in

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any of the additional samples was 1.8 µg kg-1. However, this accounted for 52% of

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the sum of the As species present in the sample.

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Acknowledgements

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The Food Safety and Measurement Facility is supported by loans and gifts

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from Agilent Technologies, Inc., Gerstel U.S., Inc., and Constellation Brands

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U.S. The authors would like to thank Michael Yee for his help and

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contributions in the preparation of this manuscript.

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Table 1: Comparison of multi-laboratory validation (MLV) results for five samples from three laboratories. Sum of DMA MMA iAs Total As % Mass Wine % EtOH Species -1 -1 -1 (µg kg ) (µg kg ) (µg kg ) (µg kg-1) Balance -1 Lab Sample (v/v) (µg kg ) a 0.46 ± 0.2

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