An evaluation of M2+ interference correction approaches associated with As and Se in ICP-MS using a multi-day dataset along with ICP-MS/MS/HR-ICP-MS based analysis and hierarchical modeling as a means of assessing bias in fortified drinking waters and single component matrices.

Three 1 2 mass oriented rare earth element (REE) M2+ correction approaches (fixed factor, a dual internal standard, and an in-sample) are evaluated for use in an ICP-MS environmental method update. The multi-variant-based evaluation includes analyzing the same 19 REE-fortified matrices on eight different days over a two-month period using two instrument tunes. These REE-fortified matrices were also analyzed using HR-ICP-MS and ICP-MS/MS to estimate the reference value for use in the principal component analysis (PCA) and hierarchical modeling evaluation. A fixed factor is unable to compensate for matrix and mass dependent drift and because of this it generates the largest across matrix, tune, and day 95th percent confidence bounds for the REE corrections on both As (1.1 ppb) and Se (23 ppb) using samples fortified with 100 ppb Nd, Sm & Gd. The PCA analysis indicated that M2+ ions cluster together across matrix, tune and day better than M1+ and these tighter correlations are reflected in reduced 95th percentile confidence bounds for dual M2+ internal standards (M2+; As = 0.3 ppb; Se = 5.4 ppb; n = 704) relative to M1+ internal standards (M1+; As = 0.6 ppb; Se = 12.0 ppb; n = 1056). The use of an in-sample M2+ correction produced comparable 95th percent confidence bounds (As = 0.2 ppb; Se = 3.4 ppb; n = 352) relative to the M2+ internal standard approaches. Finally, the hierarchical modeling indicated M2+ ions as internal standards tend to minimize the across day variability induced by cone changes and the daily reoccurring matrix shifts in the M2+/M1+ ratio associated with 250 ppm matrices of Na, Ca, and Mg. This internal standard driven reduction in variability can be beneficial in compliance monitoring methods.

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.

Analytical considerations associated with implementing M2+ correction factors to address false positives on As and Se within U.S. EPA method 200.8.

Rare earth elements (REE) can produce M2+ ions in ICP-MS and 150Nd2+, 150Sm2+, and 156Gd2+ can produce false positives on 75As and 78Se. Alternative instrumental tuning conditions, that utilize lower He flows within the collision cell, reduce these false positives by a factor of 2 (to 0.8 ppb As and 19 ppb Se in solutions containing 50 ppb Nd and Gd) with comparable 16O35Cl+ reduction (<100 ppt false 51V in 0.4% HCl) and Se sensitivity (DL < 1 ppb). Further reduction of these false positives is achieved by estimating the M2+ correction factors and utilizing them in the interference-correction software. Approaches to estimating the M2+ correction factor were evaluated with an emphasis on techniques that tolerate daily variability in end-user backgrounds and their ability to reduce the initial and ongoing purity requirements associated with the rare earth standards used to estimate the M2+ correction factor. The direct elemental and polyatomic overlaps associated with unit-mass approaches tend to overcorrect as non-rare-earth signals as small as 30 cps at the unit mass can induce bias relative to the <300 cps signals associated with the M2+ from a 50 ppb REE standard solution. Alternatively, shifting the M2+ estimate to a half mass (i.e., m/z 71.5: 143Nd2+) eliminates the direct overlap source of bias and allows the unit mass signal to approach 150000 cps before it bleeds over on the 1/2 mass because of abundance sensitivity limitations. The performance of the half-mass approach was evaluated in reagent water and regional tap waters fortified with Nd, Sm, and Gd at 2 ppb and 50 ppb. In addition, a half-mass in-sample approach was also evaluated. This approach was found to be beneficial relative to the external or fixed-factor half-mass approach as it could compensate for instrument drift and matrix-induced shifts in the M2+ factors. Finally, all results were evaluated relative to the As and Se concentrations determined using an ICP-QQQ in mass shift mode and a high-resolution ICP-MS.

Using Liquid Chromatography-Isotope Ratio Mass Spectrometry for Detection of Economically Motivated Adulteration of Maple Syrup.

BACKGROUND: Maple syrup is a sought-after commodity, and used as a condiment and a sweetener. Also, it is an active target of economically motivated adulteration (EMA), similar to other foods such as lemon juice and honey. OBJECTIVE: This study is aimed to detect low cost sugar adulteration in maple syrup via an internal standard method using malic acid through solid-phase extraction (SPE) and LC with isotope ratio mass spectrometric detection (LC-IRMS). METHODS: In this work, an optimized SPE sample preparation procedure was used for the isolation of organic acids from maple syrup. Using LC-IRMS, malic acid was separated from other organic acids and the δ13C value of malic acid was determined. Eleven maple syrup samples, domestic or imported from Canada, were evaluated for 13C/12C ratios (δ13C values) using combustion module-cavity ring down spectrometry (CM-CRDS) and compared to the δ13C values obtained from well-established elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) methods. The δ13C values of isolated malic acid analyzed by SPE-LC-IRMS were used as internal standards and compared to the δ13C values of bulk maple syrup; difference (δ13Csugars - δ13Cmalic acid) values greater than 3.6‰ are indicative of low-cost sugar adulteration. RESULTS: Overall, the results obtained from SPE-LC-IRMS provided a faster, novel analysis approach for determining low-cost sugar adulteration in maple syrup for regulatory purposes. This method also provided lower detectable limits of adulteration versus current literature reports using bulk analysis and comparable detection limits to Tremblay and co-workers who utilized an internal standard method. CONCLUSION: SPE-LC-IRMS is a robust method that can be used for detecting adulteration in maple syrup samples for regulatory purposes. HIGHLIGHTS: SPE-LC-IRMS is a faster, novel analysis approach for determining C4 adulteration in maple syrup with lower detection limits.

Elemental Analysis of Tetrahydrocannabinol and Nicotine E-Liquids Related to EVALI.

During the e-cigarette, or vaping, product use-associated lung injury (EVALI) investigation, the U.S. FDA's Forensic Chemistry Center (FCC) received numerous sample submissions from various states and other sources. Many of these products were linked directly to patients, while others were not; both categories included used and unused products. Elemental analysis using inductively coupled plasma mass spectrometry (ICP-MS) preceded by microwave-assisted decomposition was carried out on the cartridge contents of 65 of these submitted samples. Challenges encountered included limited sample, high sample viscosity, and adhesion, which necessitated sample preparation techniques not commonly used during routine elemental analysis. The elemental concentrations of contaminants including Pb, As, Cd, Cr, Ni, Cu, and Sn in tetrahydrocannabinol (THC) e-liquids associated with EVALI were determined. Nicotine e-liquid samples collected alongside the THC e-liquid samples were analyzed in tandem during method development. Several THC e-liquid samples contained Pb greater than 0.5 µg/g, while others had part per million levels of Ni, Cu, and/or Cr. This study presents the first detailed report of elemental concentrations in multiple THC e-liquid samples including those from informal/illicit sources and also delves into the method considerations needed for testing a viscous, hydrophobic sample matrix in limited quantity.

Exploring the in vitro formation of trimethylarsine sulfide from dimethylthioarsinic acid in anaerobic microflora of mouse cecum using HPLC-ICP-MS and HPLC-ESI-MS.

Although metabolism of arsenicals to form methylated oxoarsenical species has been extensively studied, less is known about the formation of thiolated arsenical species that have recently been detected as urinary metabolites. Indeed, their presence suggests that the metabolism of ingested arsenic is more complex than previously thought. Recent reports have shown that thiolated arsenicals can be produced by the anaerobic microflora of the mouse cecum, suggesting that metabolism prior to systemic absorption may be a significant determinant of the pattern and extent of exposure to various arsenic-containing species. Here, we examined the metabolism of 34S labeled dimethylthioarsinic acid (34S-DMTA(V)) by the anaerobic microflora of the mouse cecum using HPLC-ICP-MS and HPLC-ESI-MS/MS to monitor for the presence of various oxo- and thioarsenicals. The use of isotopically enriched 34S-DMTA(V) made it possible to differentiate among potential metabolic pathways for production of the trimethylarsine sulfide (TMAS(V)). Upon in vitro incubation in an assay containing anaerobic microflora of mouse cecum, 34S-DMTA(V) underwent several transformations. Labile 34S was exchanged with more abundant 32S to produce 32S-DMTA(V), a thiol group was added to yield DMDTA(V), and a methyl group was added to yield 34S-TMAS(V). Because incubation of 34S-DMTA(V) resulted in the formation of 34S-TMAS(V), the pathway for its formation must preserve the arsenic-sulfur bond. The alternative metabolic pathway postulated for formation of TMAS(V) from dimethylarsinic acid (DMA(V)) would proceed via a dimethylarsinous acid (DMA(III)) intermediate and would necessitate the loss of 34S label. Structural confirmation of the metabolic product was achieved using HPLC-ESI-MS/MS. The data presented support the direct methylation of DMTA(V) to TMAS(V). Additionally, the detection of isotopically pure 34S-TMAS(V) raises questions about the sulfur exchange properties of TMAS(V) in the cecum material. Therefore, 34S-TMAS(V) was incubated and the exchange was monitored with respect to time. The data suggest that the As-S bond associated with TMAS(V) is less labile than the As-S bond associated with DMTA(V).

Disruption of the arsenic (+3 oxidation state) methyltransferase gene in the mouse alters the phenotype for methylation of arsenic and affects distribution and retention of orally administered arsenate.

The arsenic (+3 oxidation state) methyltransferase (As3mt) gene encodes a 43 kDa protein that catalyzes methylation of inorganic arsenic. Altered expression of AS3MT in cultured human cells controls arsenic methylation phenotypes, suggesting a critical role in arsenic metabolism. Because methylated arsenicals mediate some toxic or carcinogenic effects linked to inorganic arsenic exposure, studies of the fate and effects of arsenicals in mice which cannot methylate arsenic could be instructive. This study compared retention and distribution of arsenic in As3mt knockout mice and in wild-type C57BL/6 mice in which expression of the As3mt gene is normal. Male and female mice of either genotype received an oral dose of 0.5 mg of arsenic as arsenate per kg containing [(73)As]-arsenate. Mice were radioassayed for up to 96 h after dosing; tissues were collected at 2 and 24 h after dosing. At 2 and 24 h after dosing, livers of As3mt knockouts contained a greater proportion of inorganic and monomethylated arsenic than did livers of C57BL/6 mice. A similar predominance of inorganic and monomethylated arsenic was found in the urine of As3mt knockouts. At 24 h after dosing, As3mt knockouts retained significantly higher percentages of arsenic dose in liver, kidneys, urinary bladder, lungs, heart, and carcass than did C57BL/6 mice. Whole body clearance of [(73)As] in As3mt knockouts was substantially slower than in C57BL/6 mice. At 24 h after dosing, As3mt knockouts retained about 50% and C57BL/6 mice about 6% of the dose. After 96 h, As3mt knockouts retained about 20% and C57BL/6 mice retained less than 2% of the dose. These data confirm a central role for As3mt in the metabolism of inorganic arsenic and indicate that phenotypes for arsenic retention and distribution are markedly affected by the null genotype for arsenic methylation, indicating a close linkage between the metabolism and retention of arsenicals.

Quantitative Determination of Arsenic Species from Fruit Juices Using Acidic Extraction with HPLC-ICPMS.

Throughout the US Food and Drug Administration's routine monitoring of various juice samples for elemental contaminants, a limited number of samples exhibited unexpected behavior related to the arsenic content. Juice samples were subjected to total arsenic determination and those containing arsenic > 10 µg kg-1 were subjected to arsenic speciation analysis using FDA Elemental Analysis Manual (EAM) 4.10 method (AOAC First Action Method 2016.04) to determine the concentration of iAs and other common organic arsenicals. For a subset of samples, the sum of the arsenic species was significantly less than the total arsenic value (i.e., mass balance < 65%), which is uncommon for a liquid-based matrix. Juice types that have exhibited this behavior include pomegranate, prune, and cherry juices. Causes for this issue were explored which ultimately led to an alternate sample preparation technique, extraction with 0.28 M HNO3 along with heat, which resulted in drastically improved mass balances approaching 100%. The method proved robust, with both accurate and precise measurements for multiple juice samples analyzed by a total of four laboratories. Two laboratories performed a level 3 multilaboratory validation. This work discusses various issues that were encountered, attempts to determine the source of the problem, the eventual solution in the form of a modified extraction procedure, and the multilaboratory validation results.

Economically Motivated Adulteration of Lemon Juice: Cavity Ring Down Spectroscopy in Comparison with Isotope Ratio Mass Spectrometry: Round-Robin Study.

Background: Economically motivated adulteration (EMA) of foods has become an increasing concern in recent years, with lemon juice as a popular target. Objective and Method: In this work, an optimized preparation procedure for the isolation of citric acid from lemon juice was validated using elemental analyzer-isotope ratio MS (EA-IRMS) to detect adulteration with exogenous citric acid. Additionally, 69 imported lemon juice samples were evaluated using combustion module-cavity ring down spectrometry (CM-CRDS) and compared with the well-established EA-IRMS. Equivalency of CM-CRDS to EA-IRMS was further demonstrated by conducting a round-robin study involving eight laboratories throughout the United States, Canada, and New Zealand. Results: Overall, the results obtained for CM-CRDS were statistically indistinguishable from the results obtained using EA-IRMS for EMA lemon juice analysis. Conclusions: Therefore, CM-CRDS is a viable option for this application. Highlights: The CM-CRDS instrumentation is easy to operate, robust, and provides δ13C values comparable to EA-IRMS for citrate analysis. Through a multi-laboratory exercise, CM-CRDS was shown to be an alternative to EA-IRMS in the detection of economic adulteration of lemon juice.

Simultaneous characterization of selenium and arsenic analytes via ion-pairing reversed phase chromatography with inductively coupled plasma and electrospray ionization ion trap mass spectrometry for detection applications to river water, plant extract and urine matrices.

With an increased awareness and concern for varying toxicities of the different chemical forms of environmental contaminants such as selenium and arsenic, effective methodologies for speciation are paramount. In general, chromatographic methodologies have been developed using a particular detection system and a unique matrix for single element speciation. In this study, a routine method to speciate selenium and arsenic in a variety of "real world" matrices with elemental and molecular mass spectrometric detection has been successfully accomplished. Specifically, four selenium species, selenite, selenate, selenomethionine and selenocystine, and four arsenic species, arsenite, arsenate, monomethlyarsonate and dimethylarsinate, were simultaneously separated using ion-pairing reversed phase chromatography coupled with inductively coupled plasma and electrospray ionization ion trap mass spectrometry. Using tetrabutylammonium hydroxide as the ion-pairing reagent on a C(18) column, the separation and re-equilibration time was attained within 18min. To illustrate the wide range of possible applications, the method was then successfully applied for the detection of selenium and arsenic species found naturally and spiked in river water, plant extract and urine matrices.

Detection of chemical warfare agent degradation products in foods using liquid chromatography coupled to inductively coupled plasma mass spectrometry and electrospray ionization mass spectrometry.

The following work presents the exploration of three chromatographic separations in combination with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of chemical warfare agent degradation products (CWADPs). The robust ionization of ICP is virtually matrix independent thus enabling the examination of sample matrices generally considered too complicated for analysis by electrospray ionization (ESI) or atmospheric pressure chemical ionization MS with little to no sample preparation. The analysis was focused on detecting CWADPs in food matrices, as they present possible vehicles for terrorist contamination. Due to the specific detection of (31)P by ICP-MS, resolution of analytes of interest from other P-containing interferences (H(3)PO(4)) was a crucial part of each separation. Up to 10 CWADPs were separated in the presence of H(3)PO(4) with detection limits in the low part per billion levels using the methods described. Additionally, one method was tailored to be compatible with both ICP-MS and ESI-MS making structural verification possible.

Complementary molecular and elemental detection of speciated thioarsenicals using ESI-MS in combination with a xenon-based collision-cell ICP-MS with application to fortified NIST freeze-dried urine.

The simultaneous detection of arsenic and sulfur in thioarsenicals was achieved using xenon-based collision-cell inductively coupled plasma (ICP) mass spectrometry (MS) in combination with high-performance liquid chromatography. In an attempt to minimize the (16)O(16)O(+) interference at m/z 32, both sample introduction and collision-cell experimental parameters were optimized. Low flow rates (0.25 mL/min) and a high methanol concentration (8%) in the mobile phase produced a fourfold decrease in the m/z 32 background. A plasma sampling depth change from 3 to 7 mm produced a twofold decrease in background at m/z 32, with a corresponding fourfold increase in the signal associated with a high ionization surrogate for sulfur. The quadrupole bias and the octopole bias were used as a kinetic energy discriminator between background and analyte ions, but a variety of tuning conditions produced similar (less than twofold change) detection limits for sulfur ((32)S). A 34-fold improvement in the (32)S detection limit was achieved using xenon instead of helium as a collision gas. The optimized xenon-based collision cell ICP mass spectrometer was then used with electrospray ionization MS to provide elemental and molecular-based information for the analysis of a fortified sample of NIST freeze-dried urine. The 3sigma detection limits, based on peak height for dimethylthioarsinic acid (DMTA) and trimethylarsine sulfide (TMAS), were 15 and 12 ng/g, respectively. Finally, the peak area reproducibilities (percentage relative standard deviation) of a 5-ppm fortified sample of NIST freeze dried urine for DMTA and TMAS were 7.4 and 5.4%, respectively.

Direct Comparison of Cavity Ring Down Spectrometry and Isotope Ratio Mass Spectrometry for Detection of Sugar Adulteration in Honey Samples.

In the last several years, economically motivated adulteration (EMA) of foods including honey has received increased attention. The addition of inexpensive sweeteners such as high fructose corn syrup or cane sugar to honey is still encountered despite scientific methods that can routinely detect this type of adulteration. The standard method for detection of these adulterants utilizes isotope ratio mass spectrometry (IRMS); however, this technique requires an elevated degree of technical knowledge for operation as well as a high cost for purchase and maintenance. Cavity ring down spectroscopy (CRDS) has demonstrated potential for this type of analysis and is less expensive with simpler operation. This study evaluates CRDS for the detection of low-cost sweeteners added to honey and compares the performance of CRDS to IRMS. Several honey samples were analyzed, and the advantages and limitations specific to CRDS were evaluated. Overall, the results indicate that CRDS provides a performance comparable to the benchmark technique IRMS for EMA honey analysis.

Multilaboratory Validation of First Action Method 2016.04 for Determination of Four Arsenic Species in Fruit Juice by High-Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry.

Before being designated AOAC First Action Official MethodSM 2016.04, the U.S. Food and Drug Administration's method, EAM 4.10 High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometric Determination of Four Arsenic Species in Fruit Juice, underwent both a single-laboratory validation and a multilaboratory validation (MLV) study. Three federal and five state regulatory laboratories participated in the MLV study, which is the primary focus of this manuscript. The method was validated for inorganic arsenic (iAs) measured as the sum of the two iAs species arsenite [As(III)] and arsenate [As(V)], dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) by analyses of 13 juice samples, including three apple juice, three apple juice concentrate, four grape juice, and three pear juice samples. In addition, two water Standard Reference Materials (SRMs) were analyzed. The method LODs and LOQs obtained among the eight laboratories were approximately 0.3 and 2 ng/g, respectively, for each of the analytes and were adequate for the intended purpose of the method. Each laboratory analyzed method blanks, fortified method blanks, reference materials, triplicate portions of each juice sample, and duplicate fortified juice samples (one for each matrix type) at three fortification levels. In general, repeatability and reproducibility of the method was ≤15% RSD for each species present at a concentration >LOQ. The average recovery of fortified analytes for all laboratories ranged from 98 to 104% iAs, DMA, and MMA for all four juice sample matrixes. The average iAs results for SRMs 1640a and 1643e agreed within the range of 96-98% of certified values for total arsenic.

Matrix Extension and Multilaboratory Validation of Arsenic Speciation Method EAM §4.10 to Include Wine.

A multilaboratory validation (MLV) was performed to extend the U.S. Food and Drug Administration's (FDA) analytical method Elemental Analysis Manual (EAM) §4.10, High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometric Determination of Four Arsenic Species in Fruit Juice, to include wine. Several method modifications were examined to optimize the method for the analysis of dimethylarsinic acid, monomethylarsonic acid, arsenate (AsV), and arsenite (AsIII) in various wine matrices with a range of ethanol concentrations by liquid chromatography-inductively coupled plasma-mass spectrometry. The optimized method was used for the analysis of five wines of different classifications (red, white, sparkling, rosé, and fortified) by three laboratories. Additionally, the samples were fortified in duplicate at levels of approximately 5, 10, and 30 µg kg-1 and analyzed by each participating laboratory. The combined average fortification recoveries of dimethylarsinic acid, monomethylarsonic acid, and inorganic arsenic (iAs the sum of AsV and AsIII) in these samples were 101, 100, and 100%, respectively. To further demonstrate the method, 46 additional wine samples were analyzed. The total As levels of all the wines analyzed in this study were between 1.0 and 38.2 µg kg-1. The overall average mass balance based on the sum of the species recovered from the chromatographic separation compared to the total As measured was 89% with a range of 51-135%. In the 51 analyzed samples, iAs accounted for an average of 91% of the sum of the species with a range of 37-100%.

Estimating Inorganic Arsenic Exposure from U.S. Rice and Total Water Intakes.

BACKGROUND: Among nonoccupationally exposed U.S. residents, drinking water and diet are considered primary exposure pathways for inorganic arsenic (iAs). In drinking water, iAs is the primary form of arsenic (As), while dietary As speciation techniques are used to differentiate iAs from less toxic arsenicals in food matrices. OBJECTIVES: Our goal was to estimate the distribution of iAs exposure rates from drinking water intakes and rice consumption in the U.S. population and ethnic- and age-based subpopulations. METHODS: The distribution of iAs in drinking water was estimated by population, weighting the iAs concentrations for each drinking water utility in the Second Six-Year Review data set. To estimate the distribution of iAs concentrations in rice ingested by U.S. consumers, 54 grain-specific, production-weighted composites of rice obtained from U.S. mills were extracted and speciated using both a quantitative dilute nitric acid extraction and speciation (DNAS) and an in vitro gastrointestinal assay to provide an upper bound and bioaccessible estimates, respectively. Daily drinking water intake and rice consumption rate distributions were developed using data from the What We Eat in America (WWEIA) study. RESULTS: Using these data sets, the Stochastic Human Exposure and Dose Simulation (SHEDS) model estimated mean iAs exposures from drinking water and rice were 4.2 µg/day and 1.4 µg/day, respectively, for the entire U.S. population. The Tribal, Asian, and Pacific population exhibited the highest mean daily exposure of iAs from cooked rice (2.8 µg/day); the mean exposure rate for children between ages 1 and 2 years in this population is 0.104 µg/kg body weight (BW)/day. CONCLUSIONS: An average consumer drinking 1.5 L of water daily that contains between 2 and 3 ng iAs/mL is exposed to approximately the same amount of iAs as a mean Tribal, Asian, and Pacific consumer is exposed to from rice. https://doi.org/10.1289/EHP418. BACKGROUND: Among nonoccupationally exposed U.S. residents, drinking water and diet are considered primary exposure pathways for inorganic arsenic (iAs). In drinking water, iAs is the primary form of arsenic (As), while dietary As speciation techniques are used to differentiate iAs from less toxic arsenicals in food matrices. OBJECTIVES: Our goal was to estimate the distribution of iAs exposure rates from drinking water intakes and rice consumption in the U.S. population and ethnic- and age-based subpopulations. METHODS: The distribution of iAs in drinking water was estimated by population, weighting the iAs concentrations for each drinking water utility in the Second Six-Year Review data set. To estimate the distribution of iAs concentrations in rice ingested by U.S. consumers, 54 grain-specific, production-weighted composites of rice obtained from U.S. mills were extracted and speciated using both a quantitative dilute nitric acid extraction and speciation (DNAS) and an in vitro gastrointestinal assay to provide an upper bound and bioaccessible estimates, respectively. Daily drinking water intake and rice consumption rate distributions were developed using data from the What We Eat in America (WWEIA) study. RESULTS: Using these data sets, the Stochastic Human Exposure and Dose Simulation (SHEDS) model estimated mean iAs exposures from drinking water and rice were [Formula: see text] and [Formula: see text], respectively, for the entire U.S. population. The Tribal, Asian, and Pacific population exhibited the highest mean daily exposure of iAs from cooked rice ([Formula: see text]); the mean exposure rate for children between ages 1 and 2 years in this population is [Formula: see text] body weight (BW)/day. CONCLUSIONS: An average consumer drinking 1.5 L of water daily that contains between 2 and [Formula: see text] is exposed to approximately the same amount of iAs as a mean Tribal, Asian, and Pacific consumer is exposed to from rice. https://doi.org/10.1289/EHP418.

Evaluation of selenium in dietary supplements using elemental speciation.

Selenium-enriched dietary supplements containing various selenium compounds are readily available to consumers. To ensure proper selenium intake and consumer confidence, these dietary supplements must be safe and have accurate label claims. Varying properties among selenium species requires information beyond total selenium concentration to fully evaluate health risk/benefits A LC-ICP-MS method was developed and multiple extraction methods were implemented for targeted analysis of common "seleno-amino acids" and related oxidation products, selenate, selenite, and other species relatable to the quality and/or accuracy of the labeled selenium ingredients. Ultimately, a heated water extraction was applied to recover selenium species from non-selenized yeast supplements in capsule, tablet, and liquid forms. For selenized yeast supplements, inorganic selenium was monitored as a means of assessing selenium yeast quality. A variety of commercially available selenium supplements were evaluated and discrepancies between labeled ingredients and detected species were noted.

Selenium speciation in Agaricus bisporus and Lentinula edodes mushroom proteins using multi-dimensional chromatography coupled to inductively coupled plasma mass spectrometry.

In this study, selenium species from Se containing proteins in mushrooms (Agaricus bisporus and Lentinula edodes) were investigated with size-exclusion liquid chromatography coupled to UV and inductively coupled plasma mass spectrometry (ICP-MS). Different protein extraction protocols were investigated. Variability of the fractionation patterns with three extraction media (0.1M NaOH, 30 mM Tris-HCl, and enzymatic digestions) was evaluated for both mushroom types. A 24 h Tris-HCl extraction followed by acetone addition was found to be optimal for protein precipitation. Presumably protein bound selenoamino acids were released using enzymes (proteinase K, protease XIV and trypsin). The selenium speciation of the proteolytic extract of the water soluble proteins fraction was carried out by using reversed-phase ion-pairing high performance liquid chromatography (RP-HPIPC) coupled on-line to ICP-MS for selenium specific detection. Selenocystine, selenomethionine, methylselenocysteine and inorganic selenium were established in both samples utilizing retention time standards and standard additions to the sample.