Malaysian Journal of Analytical Sciences Vol 25 No 6 (2021): 1042 - 1055

 

 

 

 

OPTIMIZATION AND DETERMINATION OF INORGANIC ARSENIC BY LIQUID EXTRACTION AND INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY IN FOOD MATRIX

 

(Pengoptimuman dan Penentuan Arsenik Tak Organik Melalui Pengekstrakan Cecair dan Spektrometri Jisim-Plasma Gadingan Aruhan dalam Sampel Makanan)

 

Le Nhon-Duc¹, Nguyen Thanh-Nho², Le-Thi Anh-Dao², Nguyen Cong-Hau²*, Nguyen Van-Dong³

 

¹Warrantek Joint Stock Company-Testing Center,

Can Tho City, Vietnam

²Faculty of Environmental and Food Engineering,

Nguyen Tat Thanh University, Ho Chi Minh City, Vietnam

³Department of Analytical Chemistry, Faculty of Chemistry,

University of Science, Vietnam National University Ho Chi Minh City (US-VNU HCMC), Vietnam

 

*Corresponding author:  nchau@ntt.edu.vn

 

 

Received:  28 August 2021; Accepted: 28 October 2021; Published:  27 December 2021

 

 

Abstract

Various kinds of food are at risk of arsenic exposure and this can lead to potential influences on human health. However, the toxicity of arsenic depends on its different forms, i.e., inorganic arsenic species (i.e., arsenite and arsenate) are more toxic than organic compounds (i.e., monomethylarsonic acid, dimethylarsinic acid, etc.), and total arsenic contents may provide limited information. In this study, a low-cost analytical method for analyzing inorganic arsenic (iAs) in various food matrices was optimized and validated. The sample preparation was conducted by acidic hydrolysis, arsenic reduction, extraction to the organic phase, then back-extraction to the aqueous phase to obtain the solutions prior to measurement on the inductively coupled plasma mass spectrometry (ICP-MS). The food matrices were hydrolyzed by 30% (v/v) HCl at 90 ^oC within 120 minutes to obtain the sample liquid containing iAs. The inorganic species in the sample liquid were reduced by N₂H₄/HBr, then extracted by CHCl₃ to organic phase, back-extracted into 2% HNO₃ solution, and quantified by ICP-MS with He as the collision gas. Various parameters related to the sample preparation were investigated and evaluated by different food matrices as well as the rice proficiency testing scheme 07273 provided by Fapas. The results showed no significant interconversion between inorganic and organic arsenic species when HCl was utilized as the hydrolysis agent. The limit of detection (LOD) and limit of quantification (LOQ) values were estimated as 1.7 and 5.0 µg kg^–1, respectively. The repeatability and reproducibility were assessed by calculating RSD_r (below 4.4%) and RSD_R (below 10%), favorable with Appendix F. AOAC (2016). The recoveries for all spiked samples ranged from 88 to 115%. The analytical method was applied to determine and assess the variations of iAs contents in anchovy, herring, white rice, brown rice, and fish sauce. All available samples met the requirements performed in Codex Stan 1993-1995, Amended in 2015, Commission Regulation (EU) 2015/1006, and Vietnam National technical regulation 8-2:2011.

 

Keywords: inorganic arsenic, inductively coupled plasma mass spectrometry, food matrices, extraction

 

Abstrak

Pelbagai jenis makanan boleh berisiko terhadap kehadiran arsenik dan ia akan membawa kesan terhadap kesihatan manusia. Namun, ketoksikan arsenik bergantung kepada spesies yang berbeza seperti spesies arsenik tak organik (i.e. arsenit dan arsenat) lebih toksik berbanding sebatian organik (i.e. asid monometilarsonik, asid dimetilarsinik dan lain-lain), dan kandungan jumlah arsenik juga mempunyai maklumat yang terhad. Melalui kajian ini, kaedah analisis kos rendah bagi analisa arsenik tak organik (iAs) di dalam pelbagai matriks makanan telah di optimum dan di tentusahkan. Penyediaan sampel dijalankan melalui hidrolisis berasid, penurunan arsenik, pengekstrakan pada fasa organik, kemudian pengekstrakan semula pada fasa akues untuk mendapatkan larutan sebelum pengukuran menggunakan spektrometri jisim plasma gandingan aruhan (ICP-MS). Matriks makanan telah di hidrolisis menggunakan 30% (v/v) HCl pada 90 ^oC selama 120 minit untuk mendapatkan sampel cecair mengandungi iAs. Spesies tak organik di dalam sampel cecair kemudian diturunkan oleh N₂H₄/HBr, dan diekstrak mengunakan CHCl₃ pada fasa organik, kemudian pengekstrakan semula ke dalam larutan 2% HNO₃, dan pengkuantitian oleh ICP-MS bersama He sebagai gas pelanggaran. Pelbagai parameter yang berkaitan penyediaan sampel dikaji dan dinilai mengunakan matriks makanan berbeza dan skim 07273 ujian kemahiran terhadap beras oleh Fapas. Hasil kajian menunjukkan tiada perbezaan diantara spesies organik dan tak organik apabila HCl digunakan sebagai agen hidrolisis. Nilai had pengesanan (LOD) dan pengkuantitian (LOQ) masing-masing ialah 1.7 dan 5.0 µg kg^–1. Kebolehulangan dan penghasilan semula dinilai melalui pengiraan RSDr (di bawah 4.4%) dan RSD_R (di bawah 10%), sesuai berdasarkan Apendiks F. AOAC (2016). Perolehan semula bagi semua sampel dipaku pada julat 88 hingga 115%. Kaedah analisis kemudian digunapakai bagi penentuan dan penilaian variasi kandungan iAs di dalam ikan bilis, hering, beras putih, beras perang dan sos ikan. Semua sampel mematuhi keperluan di bawah Codex Stan 1993-1995, Pindaan 2015, Peraturan Suruhanjaya (EU) 2015/1006, dan peraturan teknikal Kebangsaan Vietnam 8-2: 2011.

 

Kata kunci: arsenik tak organik, spektrometri jisim plasma gandingan aruhan, matriks makanan, pengekstrakan

 

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