Enzyme-assisted extraction and liquid chromatography mass spectrometry for the determination of arsenic species in chicken meat

• Proteolytic enzymes enhance extraction of arsenic species from chicken meat.
• HPLC with simultaneous ICPMS and ESIMS detection improves arsenic speciation.
• Papain digestion of chicken meat increases the extraction efficiency of arsenic species.
• Ten arsenic species are detected in chicken breast meat at μg kg−1 concentrations.

Chicken is the most consumed meat in North America. Concentrations of arsenic in chicken range from μg kg−1 to mg kg−1. However, little is known about the speciation of arsenic in chicken meat. The objective of this research was to develop a method enabling determination of arsenic species in chicken breast muscle. We report here enzyme-enhanced extraction of arsenic species from chicken meat, separation using anion exchange chromatography (HPLC), and simultaneous detection with both inductively coupled plasma mass spectrometry (ICPMS) and electrospray ionization tandem mass spectrometry (ESIMS). We compared the extraction of arsenic species using several proteolytic enzymes: bromelain, papain, pepsin, proteinase K, and trypsin. With the use of papain-assisted extraction, 10 arsenic species were extracted and detected, as compared to 8 detectable arsenic species in the water/methanol extract. The overall extraction efficiency was also improved using a combination of ultrasonication and papain digestion, as compared to the conventional water/methanol extraction. Detection limits were in the range of 1.0–1.8 μg arsenic per kg chicken breast meat (dry weight) for seven arsenic species: arsenobetaine (AsB), inorganic arsenite (AsIII), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), inorganic arsenate (AsV), 3-nitro-4-hydroxyphenylarsonic acid (Roxarsone), and N-acetyl-4-hydroxy-m-arsanilic acid (NAHAA). Analysis of breast meat samples from six chickens receiving feed containing Roxarsone showed the presence of (mean ± standard deviation μg kg−1) AsB (107 ± 4), AsIII (113 ± 7), AsV (7 ± 2), MMA (51 ± 5), DMA (64 ± 6), Roxarsone (18 ± 1), and four unidentified arsenic species (approximate concentration 1–10 μg kg−1).

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