Chronic exposure to arsenic (As) threatens human health. To systematically understand the health risks induced by As ingestion, we explored water and diet contributions to As exposure, and compared As in biomarkers and the arsenicosis in a geogenic As area in China. In this study, high percentages of water (77% of n = 131 total samples), vegetables (92%, n = 120), cereals (32%, n = 25), urine (70%, n = 99), nails (76%, n = 176), and hair (62%, n = 61) contained As higher than the acceptable levels. Dietary As contributed 92% of the average daily dose (ADD) when the water As concentration was less than 10 μg/L, for which 5 out of 30 examined participants were diagnosed with arsenicosis symptoms. The distinct positive correlation between ADD and As concentrations in urine, nails, and hair suggests different applicability for these biomarkers. Methylated As as the predominant urinary As species confirms that the ingested inorganic As is methylated and is excreted through urine. In situ microdistribution and speciation analysis indicates that As is mainly associated with sulfur in nails and hair. Nails, rather than hair and urine, could be used as a proper biomarker for arsenicosis. High ADD from the environment and low excretion could result in As toxicity to humans.
■ INTRODUCTIONArsenic (As) poses a severe threat to human health through exposure pathways mainly including water and diet. 1,2 Drinking water with elevated As levels is the primary source of As ingestion. 1,3 Moreover, As-laden groundwater, if used for irrigation, can lead to appreciable amounts of As accumulation in vegetables and cereals. 4−6 Extensive research demonstrates that rice and rice products could be another As source. 7,8 However, not much attention has been paid to other cereals like wheat, which are important staple foods worldwide, that could lead to significant As ingestion. 9 The intake of As results in its detection in noninvasive human biomarkers such as urine, nails, and hair. 10−12 Urine has frequently been used as a biomarker for short-term exposure because most As metabolites are excreted within 3−4 days through urine. 12,13 Nails and hair indicate long-term exposure for 2−12 months, 10 as As can be accumulated in these structures rich in keratin. 14 Thus, the association of As levels in biomarkers and groundwater has been recently studied to evaluate its health risks. 11,15 The speciation of As in biomarkers is crucial to understand the transformation, metabolism, and toxicity of ingested As. 12,16 As species in hair and nails are traditionally determined by chemical extraction, where inorganic and methylated As are detected. 14,17 No As−S species have been reported using indirect chemical extraction methods, even though As readily bonds to sulphydryl groups. 14 In contrast, As−S species have been detected in nail and hair samples using in situ X-ray absorption near-edge structure (XANES) spectroscopy. 15 Unfortunately, methylated As species are not distinguished from the As−S form in nails, 18 which deserves further...