Speciated Arsenic Analysis in Wine Using HPLC-ICP-QQQ

Significance of the Topic

Arsenic contamination in wine is a growing concern due to the varying toxicity of its chemical species. Inorganic arsenic forms are classified as carcinogenic, and current regulations specify limits for total arsenic but not for individual species. Extending established methods for fruit juice analysis to wine allows accurate speciation, supports regulatory compliance, and protects consumer health.

Objectives and Study Overview

The primary goal was to adapt and validate the FDA Elemental Analysis Manual Method §4.10, originally developed for fruit juice, for speciation of As(III), As(V), DMA and MMA in wine. A multilaboratory validation (MLV) was conducted across three US labs. This application note supplements the published study with data on long-term stability and quantitative analysis of five commercially available wines, and includes additional market-basket testing of 60 wines.

Methodology

Sample preparation followed the EAM §4.10 protocol. Wine samples were diluted fivefold with deionized water, filtered through 0.45 μm PVDF syringe filters, and standardized with 3% ethanol to match carbon matrix effects. Calibration standards ranged from 0.1 to 40 μg/kg. A NIST 1643e water SRM, diluted 15‐fold, assessed recovery and stability.

Instrumentation

• Agilent 1260 Infinity HPLC with binary pump, autosampler and vacuum degasser
• Hamilton PRP-X100 anion exchange column (4.1×250 mm) with matching guard column
• Agilent 8800 Triple Quadrupole ICP-MS operated in MS/MS mode with helium cell gas

Main Results and Discussion

Calibration curves for all four arsenic species exhibited excellent linearity (0.1–40 μg/kg). Limits of quantification were 1.2–1.4 μg/kg for DMA, MMA and total inorganic As. Analysis of five wine styles (Cabernet, Chardonnay, Rosé, sparkling and Port) yielded total As between 3.8 and 15.2 μg/kg after dilution, with mass balances of 91–107%. Extended stability testing over 96 hours demonstrated consistent sensitivity without recalibration. Market-basket analysis of five additional wines confirmed the predominance of inorganic As, with four samples exceeding the FDA’s 10 μg/kg action level for iAs in juice but remaining below Canadian (100 μg/kg) and European (200 μg/kg) total As limits. Spike recovery averaged 99% for DMA, 92% for MMA and 104% for iAs, meeting FDA acceptability criteria.

Practical Benefits of the Method

• High sensitivity and low detection limits for all target species
• Robust, long-term stability suitable for high-throughput testing
• Mass balance approach ensures accurate quantification of total and speciated arsenic
• Adaptable to single-quadrupole ICP-MS platforms for broader accessibility

Future Trends and Applications

Routine implementation in wine quality control and regulatory monitoring is anticipated. Further interlaboratory studies could broaden method acceptance. Integration with other speciation techniques and automation could enhance throughput. Application to other food and beverage matrices will expand the method’s utility.

Conclusion

This study successfully extended the FDA HPLC-ICP-MS arsenic speciation method to wine, yielding reliable, sensitive, and stable measurements of both inorganic and organic arsenic species. The validated approach supports regulatory compliance and consumer safety, and is suitable for routine laboratory use.

Reference

• Conklin SD, Kubachka K, Shockey N, Elemental Analysis Manual for Food and Related Products, 2013, EAM §4.10.
• Tanabe CK, Hopfer H, Ebeler SE, Nelson J, Conklin SD, Kubachka KM, Wilson RA, J Agric Food Chem, 2017, 65(20):4193–4199.
• Tanabe CK, Ebeler SE, Nelson J, Agilent publication 5991-8454EN, 2017.
• US EPA, National Primary Drinking Water Regulations, 2014.
• Bertoldi D et al., J Agric Food Chem, 2011, 59:7224–7236.
• Aguilar MV et al., Lebensm-Forsch, 1987, 185:185–187.
• VQA Ontario Wine Standards, 1999.
• OIV Compendium, 2011.
• FDA Guidance for Industry Arsenic in Apple Juice, 2013.