High-performance Liquid Chromatography-inductively Coupled Plasma-mass Spectrometry Research Articles

High proportions of inorganic arsenic in Laminaria digitata but not in Ascophyllum nodosum samples from Ireland

Seaweed can accumulate inorganic arsenic (iAs) from seawater as hydrogen arsenate (HAsO42−) in place of the phosphate anion (HPO42−). While it is rapidly metabolised to organoarsenic species, predominantly arsenosugars and arsenolipids, iAs may be present in seaweed biomass and this poses a potential health concern for consumers of seaweed products. Here, the distribution of total (AsTOT) and iAs was determined in thallus parts of the kelp Laminaria digitata and the intertidal fucoid Ascophyllum nodosum (both Phaeophyceae) using inductively-coupled plasma mass spectrometry (ICP-MS) and high performance liquid chromatography – ICP-MS (HPLC-ICP-MS). AsTOT ranged from 36 to 131 mg kg−1 dry weight (DW) in L. digitata, and from 38 to 111 mg kg−1 DW in A. nodosum, with no statistically significant differences between different thallus parts. iAs was detected in all A. nodosum samples, comprising less than 1% of the AsTOT content. Concentrations of iAs in L. digitata were significantly higher, ranging from 2.2 to 87 mg kg−1, increasing through the thallus from the stipe to the decaying distal blades. iAs comprised more than 50% of AsTOT in the middle to decaying distal blades. This finding has potential implications for harvesting, processing and use of Laminaria digitata in agri-, food and health applications.

Investigations of chromium (VI) ion sorption and reduction on strongly basic anion exchanger

ABSTRACTRemoval of chromium(VI) ions and their reduction were studied on the anion exchanger Dowex PSR-2 in the pH range from 1.5 to 10. The parameters of Cr(VI) sorption process on the anion exchanger were calculated based on the most popular isotherm models such as: Freundlich, Langmuir, Temkin, and Dubinin–Radushkevich (D-R). The Langmuir isotherm was the most appropriate to describe Cr(VI) sorption. The Cr(VI) uptake by Dowex PSR-2 was found to follow the pseudo-second-order rate kinetics. Reduction of chromium(VI) in the pH range 1.5–10 was observed using the HPLC-ICP-MS (high-performance liquid chromatography–inductively coupled plasma-mass spectrometry) method. Oxidation of tri-n-butyl quaternary ammonium groups during the chromate (VI) removal process was observed.

Development of a simultaneous analytical method to determine arsenic speciation using HPLC-ICP-MS: Arsenate, arsenite, monomethylarsonic acid, dimethylarsinic acid, dimethyldithioarsinic acid, and dimethylmonothioarsinic acid

A simultaneous analytical method for six arsenic species was established using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). Arsenate (iAsV), arsenite (iAsIII), monomethylarsonic acid (MMAV), dimethylarsinic acid (DMAV), dimethyldithioarsinic acid (DMDTAV), and dimethylmonothioarsinic acid (DMMTAV) were separated with an isocratic elute. Additionally, DMDTAV and DMMTAV were synthesized by thiolation of DMAV and identified by electrospray ionization-mass spectrometry (ESI-MS). The developed method was based on a reversed phase C18 column and various eluents such as 50mM ammonium acetate, 15mM citric acid, 50mM formic acid, and 5.0mM TBAP (i.e., 5.0mM TBAP, 5.0mM TBAP with 5% methanol addition, and 5.0mM TBAP with 5% methanol addition adjusted to pH7.7) were tested. Six As species were successfully separated and detected in the order iAsIII<DMAV<MMAV<DMMTAV<iAsV<DMDTAV in 5.0mM TBAP solution with 5% methanol addition adjusted to pH7.7 within 65min. Furthermore, LODs and LOQs (μg-AsL−1) were determined as 0.22 and 0.65 for iAsV, 0.06 and 0.19 for iAsIII, 0.08 and 0.24 for MMAV, 0.04 and 0.12 for DMAV, 0.26 and 0.78 for DMDTAV, and 0.15 and 0.44 for DMMTAV, respectively. The method was validated using CRM-TWMW (Trace Metals in Drinking Water Standard) with a recovery of 85.1%. It is expected that the findings from the study will contribute towards the rapid, convenience and simultaneous determination of As species in speciation research.

Variability in inorganic As, Sb and Tl species concentrations in waters and bottom sediments of the Kłodnica River (Poland)

ABSTRACTThe study describes the application of new methodologies for the simultaneous determination of As(III)/As(V), Sb(III)/Sb(V) and Tl(I)/Tl(III) ions in waters and bottom sediments of the Kłodnica River (Poland) with the hyphenated technique of high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) . Time and spatial correlations were determined in the changes of total and speciation concentrations of the above-mentioned analytes in Kłodnica river in 2012. The developed methodologies demonstrate high selectivity and limits of quantification at the level of 0.009–0.120 µg/L. Their repeatability, precision and recovery are appropriate for trace analyses of environmental samples. Time and spatial correlations, and concentrations of inorganic As, Sb and Tl ions demonstrated high variability both in water and bottom sediments.

Total arsenic and speciation analysis of saliva and urine samples from individuals living in a chronic arsenicosis area in China

BackgroundIt is generally acknowledged that the determination of harmful chemical compounds excreted into saliva is useful for assessing their exposure levels. The aim of the present study was to compare the total arsenic and its species in saliva and urine samples collected from the people residing in an arsenic-contaminated area of China and to further verify the feasibility of using salivary arsenic as a new biomarker of arsenic exposure.MethodsTotal arsenic and speciation analyses in urine and saliva samples among 70 residents exposed to arsenic from drinking water in Shanxi, China were carried out by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP/MS).ResultsThe result showed that, total arsenic concentration in saliva was relatively lower than in urine samples, but it existed a strong positive correlation with total urinary arsenic, drinking water arsenic and different skin lesions. For arsenic metabolism analyses, AsIII, AsV, MMA, and DMA were detected in all of the urine samples with the dominating species of DMA (73.2%). Different with urinary arsenic species, most arsenic species in saliva were not methylated. The major species in saliva was iAs (AsIII + AsV, 76.18%), followed by DMA (13.08%) and MMA (9.13%). And the primary methylation index (PMI), second methylation index (SMI) and proportion of the four different species (AsIII, AsV, MMA, and DMA) in saliva showed no significant positive relationship with that of in urine.ConclusionsThese findings indicated saliva may be used as a useful tool for biological monitoring of total arsenic exposure in the crowd rather than an efficient tool for assessing arsenic metabolism in human body after exposed to arsenic.

Directly-thiolated graphene based organic solvent-free cloud point extraction-like method for enrichment and speciation of mercury by HPLC-ICP-MS

Directly-thiolated graphene (G-SH) was prepared by substitution of the epoxy and hydroxyl groups with mercapto on the bulk and edge of the graphene oxide. Cloud point extraction-like method (CPEL) was established for enrichment of divalent mercury (IHg) and monomethylmercury (MMHg) in the water samples, based on the prepared G-SH, with good hydrophilicity, strong affinity towards mercury species and huge surface area. The large amount of active adsorption sites, thiol groups, on the bulk and edge of the surface of the G-SH play a key role in extraction of mercury species. Under the optimal conditions, the enrichment factors were 78 and 77 based on only 40mL samples, the detection limits (3δ) by high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) were 3.8 and 1.3ngL−1 for IHg and MMHg with good recoveries, respectively. The proposed CPEL-HPLC-ICP-MS method was successfully applied for speciation of mercury in surface water, underground water, domestic sewage and even sea water; moreover, the results suggested that it is a simple, sensitive and environment-friendly technique for speciation of mercury at trace levels.

Abstract P5-08-11: Urinary arsenic metabolites and risk of breast cancer molecular subtypes in northern Mexican women

Abstract Background/Aim: For many years, the presence of arsenic (As) in drinking water of some areas in Northern Mexico has been a major concern. As levels have ranged from 71 to 600 μg/L. We have recently reported that women residing in Northern Mexico, with higher urinary monomethyl arsenic acid percentage (%MMA) had an increased breast cancer (BC) risk (MMA% ORQ5vs.Q1=2.63; 95%CI: 1.89, 3.66; p for trend &amp;lt;0.001) (López-Carrillo et al., 214). Breast tumor subtypes with distinctive biology and treatment responses are defined by the immunohistochemical expression of estrogen and progesterone receptors (HR) and human epidermal growth factor receptor 2 (HER2). Epidemiological evidence suggests that BC risk factors (i.e. breastfeeding, parity, menarche, etc.) may vary by tumor pathology.We assessed if %MMA is associated with a particular BC molecular subtype. Methods: A population based case–control study was performed from 2007 to 2011 in five states of Northern Mexico. Incident cases were identified from main public tertiary hospitals in the study area. A total of 499 patients with histopathologically confirmed BC and molecular subtype status available information were identified. Controls were healthy women, with no history of cancer, matched 1:1 by age. Tumor marker information for estrogen receptor (ER), progesterone receptor (PR) and HER2 was obtained from medical records. ER+ and PR+ was based on &amp;gt;=1% cell staining. HER2+ status was determined when at least 30% of protein overexpression was observed in the tumor cell. Cases were assigned to one of three tumor marker categories: HR+ (ER+ and/or PR+ and HER2-), HER+ (regardless of ER or PR status) and TNBC (ER-, PR-, and HER2-). Urinary concentrations (μg/L) of species As3+, As5+, MMA5+, DMA5+, and arsenobetaine (AsB) were determined by high-performance liquid chromatography ICP-MS. Detection limits were As3+: 0.12; As5+: 0.20; MMA5+: 0.12; DMA5+: 0.08; AsB: 0.08. Results were reported by g of creatinine. Total As was calculated by using both the sum of iAs, MMA, DMA plus or minus AsB concentration (TAs or TAs-AsB, respectively). iAs was calculated as the sum of trivalent (As3+) and pentavalent (As5+). %iAs, %MMA and %DMA species were estimated using TAs-AsB as denominator. Using logistic regression models, the associations between BC molecular subtypes and MMA% and DMA% was estimated according to the observed quintile distribution among controls. Based on the median value of each quintile a lineal trend was assessed accordingly. Results.The mean age of cases and controls was around 54 years with 51 years of residence in the study zone. In the entire population, TAs ranged from 0.47 to 303.29 μg/L (0.45 to 1683.83 μg/g creatinine). HR+ BC patients were 57%, HER2 23% and TNBC 20%. These figures are similar to those reported among other groups of Mexican cancer patients. After controlling by key BC factors, %MMA remained as a significant risk factor for BC only for HR+. HER2+ and TNBC tumors were not significantly associated with urinary As metabolites. Conclusion: Our results suggest that increased BC risk related to As exposure is not mediated by HER2 expression. This is the first report on As exposure and breast cancer subtypes which requires further confirmation. Citation Format: López-Carrillo L, Gamboa-Loira B, Cebrián ME. Urinary arsenic metabolites and risk of breast cancer molecular subtypes in northern Mexican women [abstract]. In: Proceedings of the 2016 San Antonio Breast Cancer Symposium; 2016 Dec 6-10; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2017;77(4 Suppl):Abstract nr P5-08-11.

Arsenic Methyltransferase is Involved in Arsenosugar Biosynthesis by Providing DMA.

Arsenic is an ubiquitous toxic element in the environment, and organisms have evolved different arsenic detoxification strategies. Studies on arsenic biotransformation mechanisms have mainly focused on arsenate (As(V)) reduction, arsenite (As(III)) oxidation, and arsenic methylation; little is known, however, about the pathway for the biosynthesis of arsenosugars, which are significant arsenic transformation products. Here, the involvement of As(III) S-Adenosylmethionine methyltransferase (ArsM) in arsenosugar synthesis is demonstrated for the first time. Synechocystis sp. PCC 6803 incubated with As(III) or monomethylarsonic acid (MMA(V)) produced dimethylarsinic acid (DMA(V)) and arsenosugars, as determined by high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC/ICPMS). Arsenosugars were also detected in the cells when they were exposed to DMA(V). A mutant strain Synechocystis ΔarsM was constructed by disrupting arsM in Synechocystis sp. PCC 6803. Methylation of arsenic species was not observed in the mutant strain after exposure to arsenite or MMA(V); when Synechocystis ΔarsM was incubated with DMA(V), arsenosugars were detected in the cells. These results suggest that ArsM is a required enzyme for the methylation of inorganic arsenicals, but not required for the synthesis of arsenosugars from DMA, and that DMA is the precursor of arsenosugar biosynthesis. The findings will stimulate more studies on the biosynthesis of complex organoarsenicals, and lead to a better understanding of the bioavailability and function of the organoarsenicals in biological systems.

Determination of Tributyltin in Seafood Based on Magnetic Molecularly Imprinted Polymers Coupled with High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

In this study, Fe3O4 was adopted as a carrier for surface molecular imprinting with two-stage polymerization. First, the functional monomer (methacrylic acid, MAA) was modified on the surface of Fe3O4, which was then polymerized with the template molecule (tributyltin, TBT), cross linking agent (ethylene glycol dimethacrylate, EGDMA), and porogen (acetonitrile), hereby successfully preparing Fe3O4@MIPs prone to specifically identify TBT. The physical properties of Fe3O4@MIPs were then characterized, and adsorption and selection capacities were also assessed. Compared with conventional imprinting polymers, this magnetic molecular imprinting polymer (MIP) displayed significantly increased and more specific adsorption. Meanwhile, its pretreatment was simpler and faster due to magnetic separation characteristics. Using magnetic MIPs as adsorbents for enrichment and separation, detection limit, recovery rate, and linear range were 1.0 ng g−1, 79.74–95.72%, and 5 ng g−1~1000 ng g−1, respectively, for a number of seafood samples. High-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was used to analyze Tegillarca granosa, mussels, large yellow croaker, and other specimens, with recovery rates of 79.74–95.72% and RSD of 1.3%–4.7%. Overall, this method has a shorter total analysis time, lower detection limit, and wider linear range and can be more effectively applied to determine MAA in seawater and seafood.

A microdialysis-based analytical system for dynamic monitoring of arsenic transformation under microbial activity.

In this study, a microdialysis (MD) technique was combined with high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for continuous monitoring of the dynamic variations of arsenic species in a microbe-inoculated culture broth. After optimizing the analytical system, retrodialysis was applied to assess the probe recovery and analytical performance of the proposed method. The mean probe recoveries of four arsenic species were in the range from 57.0 to 81.8%. The limit of detection (LOD) for arsenic was in the range of 0.6-1.8 ng mL-1 and 0.032 μM for MDA, respectively. The accuracy was assessed by an addition/recovery test with a satisfactory value of 98.07-109.08% for arsenic species and 93.57-108.15% for MDA, respectively. To evaluate the practical applicability of this method, we monitored, continuously for 72 h, the dynamic variations of the concentrations of the four arsenic species in a standardized bacterial sample (ATCC 25922). After adding the arsenic species into the bacteria-inoculated broth, we found that the concentration of As3+ decreased over time, whereas As5+ increased in concentration. In addition, malondialdehyde (MDA) was also monitored to evaluate the effect of oxidative damage of the arsenic species on the studied microbial system. Our analyses revealed that the dynamic variations of the arsenic species and MDA could be observed continuously during the microbial growth period. This economical and eco-friendly method might also be helpful for monitoring the transformations of other metal species, oxidation processes, and the bioremediation ability of microbial systems.

Determination of Arsenic Species in Edible Seaweeds by HPLC–ICP-MS After Pressurized Hot Water Extraction

Aqueous soluble arsenic species in Atlantic edible seaweeds have been quantified by high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A pressurized high-temperature water extraction (PHWE) method has been developed for arsenic species. The significance of several parameters involved in the arsenic species extraction by PHWE has been evaluated using a Plackett-Burman experimental design. The extraction temperature and modifier amounts were optimized by using the central composite design. The extraction procedure was completed within 7 minutes. The analytical performance of the method, such as limit of quantification (in the range of 47 to 101 ng g-1), repeatability (<18%), column recoveries (in the range of 44 to 99%), and extraction efficiency (in the range of 32 to 81%), was established. The developed method was applied to the arsenic speciation in several edible seaweeds such as Dulse, Nori, Kombu, Wakame, Sea Spaghetti, as well as canned seaweed, and verified by analyzing the certified reference material BCR-279 Sea Lettuce.

A rapid monitoring method for inorganic arsenic in rice flour using reversed phase-high performance liquid chromatography-inductively coupled plasma mass spectrometry

A new rapid monitoring method by means of high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) following the heat-assisted extraction was developed for measurement of total inorganic arsenic species in rice flour. As(III) and As(V) eluted at the same retention time and completely separated from organoarsenic species by an isocratic elution program on a reversed phase column. Therefore, neither ambiguous oxidation of arsenite to arsenate nor the integration of two peaks were necessary to determine directly the target analyte inorganic arsenic. Rapid injection allowed measuring 3 replicates within 6min and this combined with a quantitative extraction of all arsenic species from rice flour by a 15min HNO3-H2O2 extraction makes this the fastest laboratory based method for inorganic arsenic in rice flour.

Dog 혈장 중 HPLC-ICP/MS를 이용한 비소 화학종 분석법 검증

비글견 혈장 중 arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA)와 monomethylarsonic acid (MMA)를 정량하기 위한 분석법의 유효성을 검증하기 위하여 본 연구를 수행하였다. 비소를 종 분리하기 위하여 액체크로마토그래피 (HPLC) 와 결합된 유도결합 플라즈마 질량분석기 (ICP/MS) 를 사용하였으며, 비소를 정량하는 검출기에서 스펙트럼 간섭을 최소화하기 위하여 산소(O₂)를 반응기체로 하는 DRC (dynamic reaction cell)모드를 이용하였다. 분석법의 유효성을 검증하는 항목으로 선택성, 직선성, 정확성, 정밀성, 생체시료효과, 회수율, 시스템 적합성, 희석의 타당성과 안정성 실험을 실시하였다. 선택성의 결과 정량에 방해되는 피크는 없는 것으로 확인 되었으며, 정량범위에서 평균 상관계수가 0.999 이상의 좋은 직선성을 보였다. 최저정량한계는 As(III), As(V)와 DMA는 5 ng/mL이였고, MMA는 20 ng/mL이였다. 생체시료의 영향, 시스템 적합성 과 회수율 항목을 통해 정량성에 대한 영향이 없음을 확인하여 비글견 혈장 중 비소 종을 분리하여 정량하는 분석법의 유효성을 검증하였다. 따라서 본 연구에서 제시한 분석법은 건강에 유해한 비소의 농도를 정량 및 평가하는데 적용될 것이다. The approach presented in this article refers to the bioanalytical method validation for the detection and quantitative determination of arsenic species including arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) in dog plasma by high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP/MS). The arsenic species were separated using an agilent As speciation column by a mobile phase of 2 mM sodium phosphate monobasic, 0.2 mM ethylenediaminetetraacetic acid disodium salt dehydrate, 10 mM sodium acetate, 3 mM sodium nitrate and 1 % ethyl alcohol at pH 11 (adjusted with 1M NaOH). The method validation experiment was obtained selectivity, linearity, accuracy, precision, matrix effect, recovery, system suitability, dilution integrity and various stabilities. All calibration curves showed good linearity (R²&#x3E;0.999) within test ranges. The lower limit of quantitation (LLOQ) was 5 ng/mL for As(III), As(V) and DMA, and 20 ng/mL for MMA. The system suitability and dilution values were within 6.5 % and 7.7 %. Subsequently, the developed and validated HPLC-ICP/MS method was also successfully applied to determine the arsenic speciation in dog plasma samples, and the recoveries for the spiked samples were in the range of 91.5&#x2013;102.2 %. Therefore, this method could be applied to the evaluation of arsenic exposure, health effect assessment and other bio-monitoring studies in biological samples.

Determination of Total Arsenic and Speciation in Apple Juice by Liquid Chromatography–Inductively Coupled Plasma Mass Spectrometry: An Experiment for the Analytical Chemistry Laboratory

A two-part laboratory experiment was designed for upper-level analytical chemistry students to provide hands-on experience in the use of high performance liquid chromatography (HPLC) for separation and inductively coupled plasma mass spectrometry (ICP-MS) for detection. In the first part of the experiment, the students analyze total arsenic in apple juice purchased from local grocery stores using direct injection ICP-MS. In the second part, different species of arsenic in the same apple juice samples are determined using HPLC–ICP-MS. Quantification is performed based on two methods, standard addition and external calibration curve, to demonstrate how sample matrix can affect the accuracy of the analysis. The experiments provide the opportunity to introduce and/or review several fundamental analytical chemistry concepts: chromatographic separations, mass spectrometry, inductively couple plasma, matrix effects, calibration methods, internal standard, and basic statistical tests. Undergraduate students enrol...

Dietary micronutrient intake and its relationship with arsenic metabolism in Mexican women

IntroductionConcentrations of inorganic arsenic (iAs) metabolites in urine present intra- and interindividual variations, which are determined not only by the magnitude of exposure to iAs, but also by differences in genetic, environmental and dietary factors. ObjectiveTo evaluate whether differences in dietary intake of selected micronutrients are associated with the metabolism of iAs. MethodsThe intake of 21 micronutrients was estimated for 1027 women living in northern Mexico using a food frequency questionnaire. Concentration of urinary metabolites of iAs was determined by high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) and the proportion of iAs metabolites was calculated (%iAs, monomethylarsonic acid [%MMA] and dimethylarsinic acid [%DMA]), as well as ratios corresponding to the first (MMA/iAs), second (DMA/MMA) and total methylation (DMA/iAs). ResultsAfter adjustment for covariates, it was found that methionine, choline, folate, vitamin B12, Zn, Se and vitamin C favor elimination of iAs mainly by decreasing the %MMA and/or increasing %DMA in urine. ConclusionsOur results confirm that diet contributes to the efficiency of iAs elimination. Further studies are needed to assess the feasibility of dietary interventions that modulate the metabolism of iAs and the consequent risk of diseases related to its exposure.

Determination of total arsenic and arsenic species in drinking water, surface water, wastewater, and snow from Wielkopolska, Kujawy-Pomerania, and Lower Silesia provinces, Poland.

Arsenic is a ubiquitous element which may be found in surface water, groundwater, and drinking water. In higher concentrations, this element is considered genotoxic and carcinogenic; thus, its level must be strictly controlled. We investigated the concentration of total arsenic and arsenic species: As(III), As(V), MMA, DMA, and AsB in drinking water, surface water, wastewater, and snow collected from the provinces of Wielkopolska, Kujawy-Pomerania, and Lower Silesia (Poland). The total arsenic was analyzed by inductively coupled plasma mass spectrometry (ICP-MS), and arsenic species were analyzed with use of high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Obtained results revealed that maximum total arsenic concentration determined in drinking water samples was equal to 1.01 μg L−1. The highest concentration of total arsenic in surface water, equal to 3778 μg L−1 was determined in Trująca Stream situated in the area affected by geogenic arsenic contamination. Total arsenic concentration in wastewater samples was comparable to those determined in drinking water samples. However, significantly higher arsenic concentration, equal to 83.1 ± 5.9 μg L−1, was found in a snow sample collected in Legnica. As(V) was present in all of the investigated samples, and in most of them, it was the sole species observed. However, in snow sample collected in Legnica, more than 97 % of the determined concentration, amounting to 81 ± 11 μg L−1, was in the form of As(III), the most toxic arsenic species.

Fast Determination of Toxic Arsenic Species in Food Samples Using Narrow-bore High-Performance Liquid-Chromatography Inductively Coupled Plasma Mass Spectrometry.

A new method for the speciation analysis of arsenic in food using narrow-bore high-performance liquid-chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) has been developed. Fast separation of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid was carried out in 7 min using an anion-exchange narrow-bore Nucleosil 100 SB column and 12 mM ammonium dihydrogen phosphate of pH 5.2 as the mobile phase, at a flow rate of 0.3 mL min(-1). A PFA-ST micronebulizer jointed to a cyclonic spray chamber was used for HPLC-ICP-MS coupling. Compared with standard-bore HPLC-ICP-MS, the new method has provided higher sensitivity, reduced mobile-phase consumption, a lower matrix plasma load and a shorter analysis time. The achieved instrumental limits of detection were in the 0.3 - 0.4 ng As mL(-1) range, and the precision was better than 3%. The arsenic compounds were efficiently (>80%) extracted from various food samples using a 1:5 methanol/water solution, with additional ultrasonic treatment for rice products. The applicability of this method was demonstrated by the analysis of several samples, such as seafood (fish, mussels, shrimps, edible algae) and rice-based products (Jasmine and Arborio rice, spaghetti, flour, crackers), including three certified reference materials.

Association of Cardiometabolic Genes with Arsenic Metabolism Biomarkers in American Indian Communities: The Strong Heart Family Study (SHFS).

Background:Metabolism of inorganic arsenic (iAs) is subject to inter-individual variability, which is explained partly by genetic determinants.Objectives:We investigated the association of genetic variants with arsenic species and principal components of arsenic species in the Strong Heart Family Study (SHFS).Methods:We examined variants previously associated with cardiometabolic traits (~ 200,000 from Illumina Cardio MetaboChip) or arsenic metabolism and toxicity (670) among 2,428 American Indian participants in the SHFS. Urine arsenic species were measured by high performance liquid chromatography–inductively coupled plasma mass spectrometry (HPLC-ICP-MS), and percent arsenic species [iAs, monomethylarsonate (MMA), and dimethylarsinate (DMA), divided by their sum × 100] were logit transformed. We created two orthogonal principal components that summarized iAs, MMA, and DMA and were also phenotypes for genetic analyses. Linear regression was performed for each phenotype, dependent on allele dosage of the variant. Models accounted for familial relatedness and were adjusted for age, sex, total arsenic levels, and population stratification. Single nucleotide polymorphism (SNP) associations were stratified by study site and were meta-analyzed. Bonferroni correction was used to account for multiple testing.Results:Variants at 10q24 were statistically significant for all percent arsenic species and principal components of arsenic species. The index SNP for iAs%, MMA%, and DMA% (rs12768205) and for the principal components (rs3740394, rs3740393) were located near AS3MT, whose gene product catalyzes methylation of iAs to MMA and DMA. Among the candidate arsenic variant associations, functional SNPs in AS3MT and 10q24 were most significant (p < 9.33 × 10–5).Conclusions:This hypothesis-driven association study supports the role of common variants in arsenic metabolism, particularly AS3MT and 10q24.Citation:Balakrishnan P, Vaidya D, Franceschini N, Voruganti VS, Gribble MO, Haack K, Laston S, Umans JG, Francesconi KA, Goessler W, North KE, Lee E, Yracheta J, Best LG, MacCluer JW, Kent J Jr., Cole SA, Navas-Acien A. 2017. Association of cardiometabolic genes with arsenic metabolism biomarkers in American Indian communities: the Strong Heart Family Study (SHFS). Environ Health Perspect 125:15–22; http://dx.doi.org/10.1289/EHP251

Variability in different antimony, arsenic and chromium species in waters and bottom sediments of three water reservoirs in Upper Silesia (Poland): a comparative study

ABSTRACTMigration of metals/metalloids and their inorganic forms from bottom sediments into waters and from waters into bottom sediments is a complex process. Understanding this mechanism is essential for recognising transformations that occur in water reservoir ecosystems. The following research was conducted in 2012–2014. The aim was to define the time and spatial correlations in the changes of total and ionic antimony, arsenic and chromium concentrations in waters and bottom sediments of three water reservoirs located in Upper Silesia (Poland), i.e. Pławniowice, Rybnik and Goczałkowice. The ionic form contents were determined with high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). The research was carried out to verify whether the bottom sediments deposited in the discussed reservoirs could have posed an environmental threat due to the possible release of toxic ionic forms (i.e. As(III), Sb(III) and Cr(VI)) into the pelagic zone. The comparison of the research results obtained for three reservoirs (being under different anthropopressure influence) enabled the researchers to describe the bioavailability of specific elements and their species. It also helped to discern the existing environmental threats for such water reservoirs and their users.

Urinary arsenic profiles reveal exposures to inorganic arsenic from private drinking water supplies in Cornwall, UK.

Private water supplies (PWS) in Cornwall, South West England exceeded the current WHO guidance value and UK prescribed concentration or value (PCV) for arsenic of 10 μg/L in 5% of properties surveyed (n = 497). In this follow-up study, the first of its kind in the UK, volunteers (n = 207) from 127 households who used their PWS for drinking, provided urine and drinking water samples for total As determination by inductively coupled plasma mass spectrometry (ICP-MS) and urinary As speciation by high performance liquid chromatography ICP-MS (HPLC-ICP-MS). Arsenic concentrations exceeding 10 μg/L were found in the PWS of 10% of the volunteers. Unadjusted total urinary As concentrations were poorly correlated (Spearman’s ρ = 0.36 (P < 0.001)) with PWS As largely due to the use of spot urine samples and the dominance of arsenobetaine (AB) from seafood sources. However, the osmolality adjusted sum, U-AsIMM, of urinary inorganic As species, arsenite (AsIII) and arsenate (AsV), and their metabolites, methylarsonate (MA) and dimethylarsinate (DMA), was found to strongly correlate (Spearman’s ρ: 0.62 (P < 0.001)) with PWS As, indicating private water supplies as the dominant source of inorganic As exposure in the study population of PWS users.