Vivien F. Taylor

Arsenic, Organic Foods, and Brown Rice Syrup

Background: Rice can be a major source of inorganic arsenic (Asi) for many sub-populations. Rice products are also used as ingredients in prepared foods, some of which may not be obviously rice based. Organic brown rice syrup (OBRS) is used as a sweetener in organic food products as an alternative to high-fructose corn syrup. We hypothesized that OBRS introduces As into these products. Objective: We determined the concentration and speciation of As in commercially available brown rice syrups and in products containing OBRS, including toddler formula, cereal/energy bars, and high-energy foods used by endurance athletes. Methods: We used inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography coupled to ICP-MS to determine total As (Astotal) concentrations and As speciation in products purchased via the Internet or in stores in the Hanover, New Hampshire, area. Discussion: We found that OBRS can contain high concentrations of Asi and dimethyl-arsenate (DMA). An “organic” toddler milk formula containing OBRS as the primary ingredient had Astotal concentrations up to six times the U.S. Environmental Protection Agency safe drinking water limit. Cereal bars and high-energy foods containing OBRS also had higher As concentrations than equivalent products that did not contain OBRS. Asi was the main As species in most food products tested in this study. Conclusions: There are currently no U.S. regulations applicable to As in food, but our findings suggest that the OBRS products we evaluated may introduce significant concentrations of Asi into an individual’s diet. Thus, we conclude that there is an urgent need for regulatory limits on As in food.

Arsenic concentration and speciation in infant formulas and first foods

Arsenic (As) exposure to humans is pervasive, and, increasingly, studies are revealing adverse health effects at ever lower doses. Drinking water is the main route of exposure for many individuals; however, food can be a significant source of As to individuals, especially if their diet is rice-based. Infants are particularly susceptible to dietary exposure, since many first foods contain rice and infants have a low body mass. Here we report on As concentration and speciation in infant formulas and first foods. Speciation is essential for food analysis because of the much greater toxicity of inorganic As species and the possibility that As in food (unlike water) may be present in either inorganic or organic forms. Infant milk formulas were low in total As (2.2–12.6 ng g–1, n = 15). Non-dairy formulas were significantly higher in As than dairy-based formulas. Arsenic in formula was almost exclusively inorganic. Arsenic concentration in purees (n = 41) and stage 2/3 foods (n = 18) ranged from 0.3 to 22 ng g–1. Rice-fortified foods had significantly higher total As concentrations than non-rice-based foods. Again, As speciation was predominantly inorganic with lower concentrations of dimethylarsenic acid (DMA) also present. These data confirm that infants are exposed to As via diet, and suggest that careful attention to diet choices may limit this exposure.

Human exposure to organic arsenic species from seafood.

Seafood, including finfish, shellfish, and seaweed, is the largest contributor to arsenic (As) exposure in many human populations. In contrast to the predominance of inorganic As in water and many terrestrial foods, As in marine-derived foods is present primarily in the form of organic compounds. To date, human exposure and toxicological assessments have focused on inorganic As, while organic As has generally been considered to be non-toxic. However, the high concentrations of organic As in seafood, as well as the often complex As speciation, can lead to complications in assessing As exposure from diet. In this report, we evaluate the presence and distribution of organic As species in seafood, and combined with consumption data, address the current capabilities and needs for determining human exposure to these compounds. The analytical approaches and shortcomings for assessing these compounds are reviewed, with a focus on the best practices for characterization and quantitation. Metabolic pathways and toxicology of two important classes of organic arsenicals, arsenolipids and arsenosugars, are examined, as well as individual variability in absorption of these compounds. Although determining health outcomes or assessing a need for regulatory policies for organic As exposure is premature, the extensive consumption of seafood globally, along with the preliminary toxicological profiles of these compounds and their confounding effect on assessing exposure to inorganic As, suggests further investigations and process-level studies on organic As are needed to fill the current gaps in knowledge.

Trace-level automated mercury speciation analysis

An automated system for methyl Hg analysis by purge and trap gas chromatography (GC) was evaluated, with comparison of several different instrument configurations including chromatography columns (packed column or capillary), detector (atomic fluorescence, AFS, or inductively coupled plasma mass spectrometry, ICP-MS, using quadrupole and sector field ICP- MS instruments). Method detection limits (MDL) of 0.042 pg and 0.030 pg for CH(3)Hg(+) were achieved with the automated Hg analysis system configured with AFS and ICPMS detection, respectively. Capillary GC with temperature programming was effective in improving resolution and decreasing retention times of heavier Hg species (in this case C(3)H(7)Hg(+)) although carryover between samples was increased. With capillary GC, the MDL for CH(3)Hg(+) was 0.25 pg for AFS detection and 0.060 pg for ICP-MS detection. The automated system was demonstrated to have high throughput (72 samples analyzed in 8 hours) requiring considerably less analyst time than the manual method for methyl mercury analysis described in EPA 1630.

Spatial and temporal variation in mercury bioaccumulation by zooplankton in Lake Champlain (North America)

Trophic transfer of Hg across lakes within a region has been related to multiple environmental factors, but the nature of these relationships across distinct basins within individual large lakes is unknown. We investigated Hg bioaccumulation in zooplankton in basins of differing trophic status in Lake Champlain (Vermont, USA) to determine the strongest predictors of Hg bioaccumulation. Zooplankton were sampled in Malletts Bay (oligotrophic) and Missisquoi Bay (eutrophic) in 2005-2008. Zooplankton in the eutrophic basin had lower concentrations of total Hg and MeHg than those in the oligotrophic basin in all years but 2007, when no bloom occurred in Missisquoi. In addition, Hg concentrations in seston and small zooplankton, sampled during 2009 at 12 sites spanning the lake, decreased with increasing phytoplankton and zooplankton biomass. Thus, Hg bioaccumulation in zooplankton across basins in Lake Champlain is related to trophic status, as observed previously in multiple lake studies.

Arsenic speciation in food chains from mid-Atlantic hydrothermal vents

Arsenic concentration and speciation were determined in benthic fauna collected from the Mid-Atlantic Ridge hydrothermal vents. The shrimp species, Rimicaris exoculata, the vent chimney-dwelling mussel, Bathymodiolus azoricus, Branchipolynoe seepensis, a commensal worm of B. azoricus, and the gastropod Peltospira smaragdina showed variations in As concentration and in stable isotope (δ13C and δ15N) signature between species, suggesting different sources of As uptake. Arsenic speciation showed arsenobetaine to be the dominant species in R. exoculata, whereas in B. azoricus and B. seepensis arsenosugars were most abundant, although arsenobetaine, dimethylarsinate, and inorganic arsenic were also observed, along with several unidentified species. Scrape samples from outside the vent chimneys, covered with microbial mat, which is a presumed food source for many vent organisms, contained high levels of total As, but organic species were not detectable. The formation of arsenosugars in pelagic environments is typically attributed to marine algae, and the pathway to arsenobetaine is still unknown. The occurrence of arsenosugars and arsenobetaine in these deep sea organisms, where primary production is chemolithoautotrophic and stable isotope analyses indicate food sources are of vent origin, suggests that organic arsenicals can occur in a food web without algae or other photosynthetic life.

Influence of a chlor-alkali superfund site on mercury bioaccumulation in periphyton and low-trophic level fauna

In Berlin, New Hampshire, USA, the Androscoggin River flows adjacent to a former chlor-alkali facility that is a US Environmental Protection Agency Superfund site and source of mercury (Hg) to the river. The present study was conducted to determine the fate and bioaccumulation of methylmercury (MeHg) to lower trophic-level taxa in the river. Surface sediment directly adjacent to the source showed significantly elevated MeHg (10-40× increase, mean ± standard deviation [SD]: 20.1 ± 24.8 ng g(-1) dry wt) and total mercury (THg; 10-30× increase, mean ± SD: 2045 ± 2669 ng g(-1) dry wt) compared with all other reaches, with sediment THg and MeHg from downstream reaches elevated (3-7× on average) relative to the reference (THg mean ± SD: 33.5 ± 9.33 ng g(-1) dry wt; MeHg mean ± SD: 0.52 ± 0.21 ng g(-1) dry wt). Water column THg concentrations adjacent to the point source for both particulate (0.23 ng L(-1)) and dissolved (0.76 ng L(-1)) fractions were 5-fold higher than at the reference sites, and 2-fold to 5-fold higher than downstream. Methylmercury production potential of periphyton material was highest (2-9 ng g(-1) d(-1) dry wt) adjacent to the Superfund site; other reaches were close to or below reporting limits (0. 1 ng g(-1) d(-1) dry wt). Total Hg and MeHg bioaccumulation in fauna was variable across sites and taxa, with no clear spatial patterns downstream of the contamination source. Crayfish, mayflies, and shiners showed a weak positive relationship with porewater MeHg concentration.

Pathways of CH3Hg and Hg ingestion in benthic organisms: an enriched isotope approach.

Mercury is a widespread contaminant in marine food webs, and identifying uptake pathways of mercury species, CH3Hg+ and Hg2+, into low trophic level organisms is important to understanding its entry into marine food webs. Enriched stable isotope tracers were used to study benthic vs. pelagic pathways of CH3Hg+ and Hg2+ uptake via food to the infaunal estuarine amphipod, Leptocheirus plumulosus. Algal cells differentially labeled with isotopically enriched CH3Hg+ or Hg2+ were added simultaneously to the sediment and water column of microcosms, and Hg species were monitored in amphipods and in sediment and water compartments. Methylation of Hg2+ occurred during the course of the experiment, enhancing the uptake of Hg2+ spikes. Trophic transfer of Hg from algae added to the water column was determined to be the major uptake route for amphipods, suggesting inputs of contaminated organic matter from the pelagic zone are important to mercury bioaccumulation even in organisms living in sediments.

Monomethylarsonous Acid (MMAIII) Has an Adverse Effect on the Innate Immune Response of Human Bronchial Epithelial Cells to Pseudomonas aeruginosa.

Arsenic is the number one contaminant of concern with regard to human health according to the World Health Organization. Epidemiological studies on Asian and South American populations have linked arsenic exposure with an increased incidence of lung disease, including pneumonia, and chronic obstructive pulmonary disease, both of which are associated with bacterial infection. However, little is known about the effects of low dose arsenic exposure, or the contributions of organic arsenic to the innate immune response to bacterial infection. This study examined the effects on Pseudomonas aeruginosa (P. aeruginosa) induced cytokine secretion by human bronchial epithelial cells (HBEC) by inorganic sodium arsenite (iAsIII) and two major metabolites, monomethylarsonous acid (MMAIII) and dimethylarsenic acid (DMAV), at concentrations relevant to the U.S. population. Neither iAsIII nor DMAV altered P. aeruginosa induced cytokine secretion. By contrast, MMAIII increased P. aeruginosa induced secretion of IL-8, IL-6 and CXCL2. A combination of iAsIII, MMAIII and DMAV (10 pbb total) reduced IL-8 and CXCL1 secretion. These data demonstrate for the first time that exposure to MMAIII alone, and a combination of iAsIII, MMAIII and DMAV at levels relevant to the U.S. may have negative effects on the innate immune response of human bronchial epithelial cells to P. aeruginosa.

Distinct arsenic metabolites following seaweed consumption in humans

Seaweeds contain arsenic primarily in the form of arsenosugars, which can be metabolized to a wide range of arsenic compounds. To characterize human exposure to arsenic from seaweed consumption, we determined concentrations of arsenic species in locally available seaweeds, and assessed urinary arsenic compounds in an experimental feeding study. A total of 11 volunteers consumed 10 g per day of three types of seaweeds (nori, kombu, and wakame) for three days each, while abstaining from rice and seafood following a three-day washout period. Urinary arsenosugars and their metabolites (including dimethyl arsenate (DMA), thio-dimethylarsinoylethanol (thio-DMAE), thio-dimethylarsinoylacetate (thio-DMAA), and thio-DMA) were measured in spot urine samples prior to seaweed consumption, and in 24-hour urine samples while consuming seaweed. Commercial products made from whole seaweed had substantial concentrations of arsenic (12–84 µg/g), dominated by arsenosugars. Intact arsenosugars along with DMA, thio-DMAA, thio-DMAE all increased in urine after ingesting each type of seaweed, and varied between seaweed types and between individuals. Only trace levels of the known toxic metabolite, thio-DMA, were observed, across individuals. Thio-DMAE and thio-DMAA are unique products of arsenosugar breakdown, thus assessment of these compounds may help to identify dietary intake of arsenic from seaweed from other exposure pathways.