CRM rapid response approach for the certification of arsenic species and toxic trace elements in baby cereal coarse rice flour certified reference material BARI-1.

With recently legislated maximum levels of inorganic arsenic (iAs) in white and brown rice in Canada, the regulatory bodies are evaluating the need for regulation of As levels in infant food products. Rice is a major part of infants' diet, and therefore, the presence of As in this staple food causes concerns. So far, the scientific community was lacking suitable certified reference material (CRM) which could be used to assess the accuracy of developed analytical methods for As speciation in infants' food products. As a result, we have developed BARI-1, a baby cereal coarse rice flour reference material which was certified for total arsenic (0.248 ± 0.018 mg kg-1), cadmium (0.0134 ± 0.0014 mg kg-1), mercury (0.0026 ± 0.0003 mg kg-1), lead (0.0064 ± 0.0016 mg kg-1), inorganic As (0.113 ± 0.016 mg kg-1) and dimethylarsinic acid (DMA) (0.115 ± 0.010 mg kg-1), and reference value for monomethylarsonic acid (MMA) (0.0045 ± 0.0008 mg kg-1) was reported. We also observed trace amounts of an unknown As compound, with chromatographic retention time close to DMA. Participating laboratories were allowed to use their in-house-validated extraction and/or digestion methods, and the detection of total metals was done by ICP-MS whereas HPLC-ICP-MS was used for As speciation. Despite the diversity in sample preparation and quantitation methods, reported values were in good agreement. For iAs measurement, the comparison between hydride generation ICP-MS and HPLC-ICP-MS found iAs overestimation with the former method, possibly due to interference from DMA. The certification was accomplished with a CRM rapid response approach in collaborative, focused effort completing the CRM development in few months instead of the typical multiyear project. This approach allowed to respond to measurement needs in a timely fashion. Graphical abstract.

Reduction of hexavalent chromium by fasted and fed human gastric fluid. II. Ex vivo gastric reduction modeling.

To extend previous models of hexavalent chromium [Cr(VI)] reduction by gastric fluid (GF), ex vivo experiments were conducted to address data gaps and limitations identified with respect to (1) GF dilution in the model; (2) reduction of Cr(VI) in fed human GF samples; (3) the number of Cr(VI) reduction pools present in human GF under fed, fasted, and proton pump inhibitor (PPI)-use conditions; and (4) an appropriate form for the pH-dependence of Cr(VI) reduction rate constants. Rates and capacities of Cr(VI) reduction were characterized in gastric contents from fed and fasted volunteers, and from fasted pre-operative patients treated with PPIs. Reduction capacities were first estimated over a 4-h reduction period. Once reduction capacity was established, a dual-spike approach was used in speciated isotope dilution mass spectrometry analyses to characterize the concentration-dependence of the 2nd order reduction rate constants. These data, when combined with previously collected data, were well described by a three-pool model (pool 1 = fast reaction with low capacity; pool 2 = slow reaction with higher capacity; pool 3 = very slow reaction with higher capacity) using pH-dependent rate constants characterized by a piecewise, log-linear relationship. These data indicate that human gastric samples, like those collected from rats and mice, contain multiple pools of reducing agents, and low concentrations of Cr(VI) (<0.7 mg/L) are reduced more rapidly than high concentrations. The data and revised modeling results herein provide improved characterization of Cr(VI) gastric reduction kinetics, critical for Cr(VI) pharmacokinetic modeling and human health risk assessment.

Risks associated with arsenic exposure resulting from the consumption of California wines sold in the United States.

Concerns have recently been raised about the presence of arsenic (As) in wine. In this analysis, 101 different California wines were evaluated for organic and inorganic As concentration. The average concentrations of total inorganic As in red, blush and white wines were 6.12µg/L (range: 0.40-20.5µg/L), 21.6µg/L (range: 0.92-41.2µg/L) and 9.5µg/L (0.57-30.4µg/L). The average concentrations of total organic As in red, blush and white wines were 0.64µg/L (0.10-2.74µg/L), 0.99µg/L (0.50-2.28µg/L), and 0.51µg/L (0.10-1.78µg/L). A screening level risk assessment was conducted to assess the potential non-carcinogenic risk resulting from wine consumption. The hazard quotient (HQ) for the inorganic As RfD and the As content of red, blush and white wines was each less than one; indicating that the non-cancer health risk was insignificant. Results indicate that ingestion of California wine does not pose a hazard due to inorganic As content.

Statistical analysis of causes of death (2005-2010) in villages of Simav Plain, Turkey, with high arsenic levels in drinking water supplies.

The purpose of this research was to compare the causes of death in 5 villages situated in Simav Plain, Turkey, during 2005-2010 where different arsenic levels were detected in drinking water supplies. Since groundwater in Simav Plain had arsenic concentrations that ranged between 7.1 and 833.9 ppb, a two-phase research was formulated. In the first phase, public health surveys were conducted with 1,003 villagers to determine the distribution of diseases. In the second phase, verbal autopsy surveys and official death records were used to investigate the causes of death. In total, 402 death cases were found in the study area where cardiovascular system diseases (44%) and cancers (15.2%) were major causes. Cancers of lung (44.3%), prostate (9.8%), colon (9.8%), and stomach (8.2%) were comparably higher in villages with high arsenic levels in drinking water supplies. Furthermore, the majority of cases of liver, bladder, and stomach cancers were observed in villages with high arsenic levels.

Hexavalent chromium reduction kinetics in rodent stomach contents.

Reduction of hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)) in the stomach prior to absorption is a well-recognized detoxification process thought to limit the toxicity of ingested Cr(VI). However, administration of high concentrations of Cr(VI) in drinking water cause mouse small intestinal tumors, and quantitative measures of Cr(VI) reduction rate and capacity for rodent stomach contents are needed for interspecies extrapolation using physiologically-based toxicokinetic (PBTK) models. Ex vivo studies using stomach contents of rats and mice were conducted to quantify Cr(VI) reduction rate and capacity for loading rates (1-400 mg Cr(VI)L(-1) stomach contents) in the range of recent bioassays. Cr(VI) reduction was measured with speciated isotope dilution mass spectrometry to quantify dynamic Cr(VI) and Cr(III) concentrations in stomach contents at select time points over 1 h. Cr(VI) reduction followed mixed second-order kinetics, dependent upon concentrations of both Cr(VI) and the native reducing agents. Approximately 16 mg Cr(VI)-equivalents of reducing capacity per L of fed stomach contents (containing gastric secretions, saliva, water and food) was found for both species. The second-order rate constants were 0.2 and 0.3 L mg(-1) h(-1) for mice and rats, respectively. These findings support that, at the doses that caused cancer in the mouse small intestine (≥ 20 mg Cr(VI)L(-1) in drinking water), the reducing capacity of stomach contents was likely exceeded. Thus, for extrapolation of target tissue dose in risk assessment, PBTK models are necessary to account for competing kinetic rates including second order capacity-limited reduction of Cr(VI) to Cr(III).