1 National Food Institute, Technical University of Denmark2 Division of Food Chemistry, National Food Institute, Technical University of Denmark
Arsenic (As) is a trace element present in the environment and consequently in various food items, e.g. rice, which may contain relatively high concentration of arsenic compared to other foodstuffs of plant origin. Rice contains most often three forms of arsenic; inorganic arsenic (iAs) and the methylated species monomethylarsonic acid (MA) and dimethylarsinic acid (DMA). Dietary intake of iAs is of special concern due to its carcinogenicity to humans, whereas DMA and MA are considered of less toxicological importance. Rice grains and rice-based products are staple foods in many countries and is one of the major contributors to the iAs exposure in many countries. The work presented here describes the development, validation and application of a simple and inexpensive method for inorganic arsenic (iAs) determination in rice samples. The separation of iAs from organoarsenic compounds (MA and DMA) was done by off-line solidphase extraction (SPE) followed by hydride generation atomic absorption spectrometry (HG-AAS) detection. Water bath heating (90 °C, 60 min) of samples with dilute nitric acid and hydrogen peroxide solubilised and oxidized all iAs to arsenate (AsV). Loading of buffered sample extracts (pH 6±1) followed by selective elution of arsenate from a strong anion exchange SPE cartridge enabled the selective iAs quantification by HG-AAS, measuring total arsenic (As) in the SPE eluate. The in-house validation gave mean recoveries of 101–106 % for spiked rice samples and in two reference samples. The limit of detection was 0.02 mg/kg, and repeatability and intra-laboratory reproducibility were less than 6 and 9 %, respectively. The SPE HG-AAS method produced similar results compared to parallel high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (ICP-MS) analysis. The SPE separation step was tested collaboratively, where the laboratories (N=10) used either HG-AAS or ICPMS for iAs determination in a wholemeal rice powder. The trial gave satisfactory results (HorRat value of 1.6) and did not reveal significant difference (t test, p>0.05) between HG-AAS and ICP-MS quantification. The iAs concentration in 36 rice samples purchased on the Danish retail market varied (0.03–0.60 mg/kg), with the highest concentration found in a red rice sample.