Formation Of Arsenobetaine Research Articles

Microplastics and arsenic speciation in edible bivalves from the coast of China: Distribution, bioavailability, and human health risk

Bivalves, such as oysters and mussels, are exposed to environmental pollutants, like microplastics (MPs) and arsenic (As). This study investigated co-existence and interaction of MPs and As (total As and As species) in two bivalve species from the Chinese coastline. Smaller MPs (20–100 μm) averaged 30.98 items/g, while larger MPs (100–500 μm) averaged 2.98 items/g. Oysters contained more MPs (57.97 items/g) in comparison to mussels (11.10 items/g). In Contrast, mussels had a higher As concentrations (8.36–23.65 mg/kg) than oysters (4.97–11.02 mg/kg). The size and composition of MPs influenced As uptake and speciation in bivalves, with inorganic arsenic (iAs) and methylated arsenic (MMA and DMA) correlating with larger-sized MPs. Polyethylene (PE) may interact with the formation of arsenobetaine (AsB) in oyster. This study provides valuable insights into the interaction of MPs and As in marine ecosystems and highlights their implications for food safety.

Arsenic Metabolism, Toxicity and Accumulation in the White Button Mushroom Agaricus bisporus.

Mushrooms have unique properties in arsenic metabolism. In many commercial and wild-grown mushrooms, arsenobetaine (AsB), a non-toxic arsenical, was found as the dominant arsenic species. The AsB biosynthesis remains unknown, so we designed experiments to study conditions for AsB formation in the white button mushroom, Agaricus bisporus. The mushrooms were treated with various arsenic species including arsenite (As(III)), arsenate (As(V)), methylarsenate (MAs(V)), dimethylarsenate (DMAs(V)) and trimethylarsine oxide (TMAsO), and their accumulation and metabolism were determined using inductively coupled mass spectrometer (ICP-MS) and high-pressure liquid chromatography coupled with ICP-MS (HPLC-ICP-MS), respectively. Our results showed that mycelia have a higher accumulation for inorganic arsenicals while fruiting bodies showed higher accumulation for methylated arsenic species. Two major arsenic metabolites were produced in fruiting bodies: DMAs(V) and AsB. Among tested arsenicals, only MAs(V) was methylated to DMAs(V). Surprisingly, AsB was only detected as the major arsenic product when TMAsO was supplied. Additionally, AsB was only detected in the fruiting body, but not mycelium, suggesting that methylated products were transported to the fruiting body for arsenobetaine formation. Overall, our results support that methylation and AsB formation are two connected pathways where trimethylated arsenic is the optimal precursor for AsB formation.

Uptake and transformation of arsenic during the reproductive life stage of Agaricus bisporus and Agaricus campestris

Fruiting bodies from the Agaricus genus have been found to contain non-toxic arsenobetaine (AB) as a major compound. It is unknown whether AB is formed during the vegetative or reproductive life stages of the fungus, or by the surrounding microbial community, but AB's structural similarity to glycine betaine has led to the hypothesis that AB may be adventitiously accumulated as an osmolyte. To investigate the potential formation of AB during the reproductive life stage of Agaricus species, growth substrate and fungi were collected during the commercial growth of Agaricus bisporus and analyzed for arsenic speciation using HPLC-ICP-MS. AB was found to be the major arsenic compound in the fungus at the earliest growth stage of fruiting (the primordium). The growth substrate mainly contained arsenate (As(V)). The distribution of arsenic in an A. bisporus primordium grown on As(V) treated substrate, and in a mature Agaricus campestris fruiting body collected from arsenic contaminated mine tailings, was mapped using two dimensional XAS imaging. The primordium and stalk of the mature fruiting body were both found to be growing around pockets of substrate material containing higher As concentrations, and AB was found exclusively in the fungal tissues. In the mature A. campestris the highest proportion of AB was found in the cap, supporting the AB as an osmolyte hypothesis. The results have allowed us to pinpoint the fungus life stage at which AB formation takes place, namely reproduction, which provides a direction for further research.

Arsenobetaine and thio-arsenic species in marine macroalgae and herbivorous animals: Accumulated through trophic transfer or produced in situ?

Arsenobetaine (AB) and thio-arsenoribosides were measured in common macroalgae species (8 phaeophyta, 4 rhodophyta and 2 chlorphyta), along the Australian south east coast line. As well, arsenic species profiles were measured for two common marine herbivores, the sea urchin Centrostephanus rodgersii and the fish Odax cyanomelas that graze on these macroalgae to understand if trophic transfer of these species would account for their presence in marine herbivores. AB was found in seven of the fourteen macroalgae species investigated but does not contributed significantly to any of the macroalgae arsenic content (0.01-1.2μg/g). AB was found in only two of the brown macroalgae and all the red and green macroalgae (with the exception of Corallina officinalis). Thio-arsenic species were found sporadically, but not in high concentrations in any of the macroalgae investigated. AB present in macroalgae is likely to be associated with epiphytic organisms while thio-arsenoribosides are likely to be produced by decaying parts of damaged macroalgae. A laboratory feeding experiment in which the herbivorous gastropod, Austrocochlea constricta, was fed macroalgae containing thio-arsenoribosides for a 24hr period every three days showed that these are readily accumulated over a short period. Thio-arsenoribosides in herbivores are therefore probably obtained through trophic transfer. Some AB is also obtained through trophic transfer; however, the presence of trimethylated arsonioribosides, a hypothesized precursor of AB formation in herbivores, suggests that some AB is produced within herbivores from the transformation of arsenoribosides accumulated from their diet.

Uptake and transformation of arsenic during the vegetative life stage of terrestrial fungi

Many species of terrestrial fungi produce fruiting bodies that contain high proportions of arsenobetaine (AB), an arsenic compound of no known toxicity. It is unknown whether fungi produce or accumulate AB from the surrounding environment. The present study targets the vegetative life stage (mycelium) of fungi, to examine the role of this stage in arsenic transformations and potential formation of AB. The mycelia of three different fungi species were cultured axenically and exposed to AB, arsenate (As(V)) and dimethylarsinoyl acetic acid for 60 days. Agaricus bisporus was additionally exposed to hypothesized precursors for AB and the exposure time to As(V) and dimethlyarsinic acid was also extended to 120 days. The mycelia of all fungi species accumulated all arsenic compounds with two species accumulating significantly more AB than other compounds. Few biotransformations were observed in these experiments indicating that it is unlikely that the mycelium of the fungus is responsible for biosynthesizing AB.

Arsenic speciation in edible mushrooms.

The fruiting bodies, or mushrooms, of terrestrial fungi have been found to contain a high proportion of the nontoxic arsenic compound arsenobetaine (AB), but data gaps include a limited phylogenetic diversity of the fungi for which arsenic speciation is available, a focus on mushrooms with higher total arsenic concentrations, and the unknown formation and role of AB in mushrooms. To address these, the mushrooms of 46 different fungus species (73 samples) over a diverse range of phylogenetic groups were collected from Canadian grocery stores and background and arsenic-contaminated areas. Total arsenic was determined using ICP-MS, and arsenic speciation was determined using HPLC-ICP-MS and complementary X-ray absorption spectroscopy (XAS). The major arsenic compounds in mushrooms were found to be similar among phylogenetic groups, and AB was found to be the major compound in the Lycoperdaceae and Agaricaceae families but generally absent in log-growing mushrooms, suggesting the microbial community may influence arsenic speciation in mushrooms. The high proportion of AB in mushrooms with puffball or gilled morphologies may suggest that AB acts as an osmolyte in certain mushrooms to help maintain fruiting body structure. The presence of an As(III)-sulfur compound, for the first time in mushrooms, was identified in the XAS analysis. Except for Agaricus sp. (with predominantly AB), inorganic arsenic predominated in most of the store-bought mushrooms (albeit with low total arsenic concentrations). Should inorganic arsenic predominate in these mushrooms from contaminated areas, the risk to consumers under these circumstances should be considered.

Major and minor arsenic compounds accounting for the total urinary excretion of arsenic following intake of blue mussels (Mytilus edulis): A controlled human study

Blue mussels (Mytilus edulis) accumulate and biotransform arsenic (As) to a larger variety of arsenicals than most seafood. Eight volunteers ingested a test meal consisting of 150g blue mussel (680μg As), followed by 72h with an identical, low As controlled diet and full urine sampling. We provide a complete speciation, with individual patterns, of urinary As excretion. Total As (tAs) urinary excretion was 328±47μg, whereof arsenobetaine (AB) and dimethylarsinate (DMA) accounted for 66% and 21%, respectively. Fifteen minor urinary arsenicals were quantified with inductively coupled plasma mass spectrometry (ICPMS) coupled to reverse-phase, anion and cation-exchange high performance liquid chromatography (HPLC). Thio-arsenicals and non-thio minor arsenicals (including inorganic As (iAs) and methylarsonate (MA)) contributed 10% and 7% of the total sum of species excretion, respectively, but there were large individual differences in the excretion patterns. Apparently, formation of thio-arsenicals was negatively correlated to AB formation and excretion, possibly indicating a metabolic interrelationship. The results may be of toxicological relevance since DMA and MA have been classified as possibly carcinogenic, and six of the excreted As species were thio-arsenicals which recently have been recognized as toxic, while iAs toxicity is well known.

Arsenobetaine formation in plankton: a review of studies at the base of the aquatic food chain

Arsenobetaine is one of the major organoarsenic compounds found in aquatic organisms, including seafood and fish meant for human consumption. It has been widely studied over the last 50 years because of its non-toxic properties, and its origin is postulated to be at bottom of the aquatic food chains. The present review focuses on arsenobetaine formation in marine and freshwater plankton, comparing the arsenic compounds found in the different plankton organisms, and the methods used to assess arsenic speciation. The main findings indicate that in the marine environment, phytoplankton and micro-algae contain arsenosugars, with the first traces of arsenobetaine appearing in herbivorous zooplankton, and becoming a major arsenic compound in carnivorous zooplankton. Freshwater plankton contains less arsenobetaine than their marine relatives, with arsenosugars dominating. The possible role and formation pathways of arsenobetaine in plankton organisms are reviewed and the literature suggests that arsenobetaine in zooplankton comes from the degradation of ingested arsenosugars, and is selectively accumulated by the organism to serve as osmolyte. Several arsenic compounds such as arsenocholine, dimethylarsinoylacetate or dimethylarsinoylethanol that are intermediates of this pathway have been detected in plankton. The gaps in research on arsenobetaine in aquatic environments are also addressed: primarily most of the conclusions are drawn on culture-based experiments, and few data are present from the natural environment, especially for freshwater ecosystems. Moreover, more data on arsenic in different zooplankton species would be helpful to confirm the trends observed between herbivorous and carnivorous organisms.

Humans seem to produce arsenobetaine and dimethylarsinate after a bolus dose of seafood

Seafood is the predominant food source of several organoarsenic compounds. Some seafood species, like crustaceans and seaweed, also contain inorganic arsenic (iAs), a well-known toxicant. It is unclear whether human biotransformation of ingested organoarsenicals from seafood result in formation of arsenicals of health concern. The present controlled dietary study examined the urinary excretion of arsenic compounds (total arsenic (tAs), iAs, AB (arsenobetaine), dimethylarsinate (DMA) and methylarsonate (MA)) following ingestion of a single test meal of seafood (cod, 780μg tAs, farmed salmon, 290μg tAs or blue mussel, 690μg tAs or potato (control, 110μg tAs)) in 38 volunteers. The amount of ingested tAs excreted via the urine within 0–72h varied significantly among the groups: Cod, 74% (52–92%), salmon 56% (46–82%), blue mussel 49% (37–78%), control 45% (30–60%). The estimated total urinary excretion of AB was higher than the amount of ingested AB in the blue mussel group (112%) and also ingestion of cod seemed to result in more AB, indicating possible endogenous formation of AB from other organoarsenicals. Excretion of iAs was lower than ingested (13–22% of the ingested iAs was excreted in the different groups). Although the ingested amount of iAs+DMA+MA was low for all seafood groups (1.2–4.5% of tAs ingested), the urinary DMA excretion was high in the blue mussel and salmon groups, counting for 25% and 11% of the excreted tAs respectively. In conclusion our data indicate a possible formation of AB as a result of biotransformation of other organic arsenicals. The considerable amount of DMA excreted is probably not only due to methylation of ingested iAs, but due to biotransformation of organoarsenicals making it an inappropriate biomarker of iAs exposure in populations with a high seafood intake.

ChemInform Abstract: Formation of Arsenobetaine from Arsenocholine by Microorganisms Occurring in Sediments.

ChemInform Abstract: Formation of Arsenobetaine from Arsenocholine by Microorganisms Occurring in Sediments.

Uptake and metabolism of arsenate, methylarsonate and arsenobetaine by axenic cultures of the phytoplankton Dunaliella tertiolecta

Abstract Axenic cultures of the phytoplankton Dunaliella tertiolecta were dosed with either arsenate [As(V)], methylarsonate (MA) or arsenobetaine (AB) at environmentally realistic concentrations (2 μg l-1) to investigate incorporation and transformation of arsenic species. Total arsenic concentrations in cultures dosed with As(V) were significantly higher than those dosed with MA and AB (6–10 μg g-1 compared to 1–3 μg g-1). Arsenic concentrations in As(V)-dosed cultures increased over time, whereas arsenic concentrations in MA- and AB-dosed cultures remained constant, indicating that As(V) is rapidly and continuously incorporated into the cell in comparison to MA and AB. Arsenic was found predominantly in the residue fractions (29–55%) of all cultures, irrespective of culture age. This was attributed to the ability of inorganic arsenic as arsenite [As(III)] to bind to proteins and/or phytochelatins. 2-Dimethylarsinoylethanol (DMAE) was the main arsenic species found in lipid cell fractions. Within the water-soluble and residue cell fractions, arsenic was isolated primarily as As(V), although it is likely the extraction procedure may have converted some As(III) to As(V). Small amounts of As(III), MA, dimethylarsinate (DMA) and arsenoribosides were also found in the lipid and water soluble As fractions. All cultures showed an increase in DMA and arsenoriboside species over time. The significance of these results is that while AB, the major arsenical in marine animals, is not produced or accumulated by this phytoplankton species, the possible precursors to AB formation are produced.

Arsenic species in Australian temperate marine food chains

Although over 50 arsenic species have been identified in marine organisms, the biochemical pathways by which these species are formed are not known. In this paper, we present an overview of bioconversions of arsenic species that occur in marine food chains based on studies conducted by our laboratory as well as the work of others. Phytoplankton and macroalgae only contain dimethylarsenoribosides or simple methylated arsenic compounds such as dimethylarsenate and dimethylarsenoethanol. Marine animals contain mostly arsenobetaine and a range of other arsenic species that may be precursors of arsenobetaine formation. The formation of arsenobetaine in marine animals from dimethylarsenoribosides may occur through a two-stage conversion pathway: arsenoriboside or trimethylarsonioriboside degradation to arsenocholine followed by quantitative oxidation to arsenobetaine. The minor arsenic species found in marine organisms are sulfur analogues of compounds found in the S-adenosylmethionine-methionine salvage and the dimethylsulfoniopropionate metabolic pathway of animals. A key intermediate in these pathways would be arsenomethionine, which could possibly be formed from dimethylarsinite, dimethylarsenoribosides or an arsenic-containing analogue of S-adenosylmethionine. Examining arsenic species in whole ecosystems has the advantage of using the pattern of arsenic species found to postulate the biochemical pathways of their formation.

Arsenic biotransformation in earthworms from contaminated soils

Two species of arsenic (As) resistant earthworm, Lumbricus rubellus and Dendrodrillus rubidus, their host soils and soil excretions (casts) were collected from 23 locations at a former As mine in Devon, UK. Total As concentrations, measured by ICP-MS, ranged from 255 to 13,080 mg kg(-1) in soils, 11 to 877 mg kg(-1) in earthworms and 284 to 4221 mg kg(-1) in earthworm casts from a sub-sample of 10 of the 23 investigated sites. The samples were also measured for As speciation using HPLC-ICP-MS to investigate potential As biotransformation pathways. Inorganic arsenate (As(V)) and arsenite (As(III)) were the only species detected in the soil. As(V) and As(III) were also the dominant species found in the earthworms and cast material together with lower proportions of the organic species methylarsonate (MA(V)), dimethylarsinate (DMA(V)), arsenobetaine (AB) and three arsenosugars. Whilst the inorganic As content of the earthworms increased with increasing As body burden, the concentration of organic species remained relatively constant. These results suggest that the biotransformation of inorganic arsenic to organic species does not contribute to As resistance in the sampled earthworm populations. Quantification of As speciation in the soil, earthworms and cast material allows a more comprehensive pathway for the formation of AB in earthworms to be elucidated.

Arsenic Occurrence and Species in Near-Shore Macroalgae-Feeding Marine Animals

This study was undertaken to improve the understanding of arsenic species and their pathways of formation in marine animals: fish (Odax cyanomelas), abalone (Haliotis rubra), and sea urchins (Heliocidaris erythrogramma and Centrostephanus rodgersii) that are directly exposed through their diets to dimethyl arsenoriboses in macroalgae (Phyllospora comosa and Halopteris platycena). The identification of dimethyl arsenoriboses (phosphate, sulfonate, and glycerol) in both dominant macroalgae species, and especially digestive tissues of marine animals that consume them, suggests these arsenic species, are to some degree accumulated directly from their diets without degradation or conversion. An unknown arsenic species in H. rubra intestinal tissue was identified using tandem mass spectrometry as 2',3'-dihydroxypropyl 5-deoxy-5-trimethyl arsonioriboside (trimethyl glycerol arsenoribose). The concentration of trimethyl glycerol arsenoribose in H. rubra intestinal tissue was estimated to account for 28% (5.0 microg g(-1) dry mass) of the methanol-water-soluble arsenic fraction. The presence of a trimethyl glycerol arsenoribose in marine animal tissues may be due to microbial-mediated processes that promote the reduction and methylation of dimethyl arsenoriboses released during the breakdown of macroalgae in their diets. Arsenobetaine formation may then occur in the lumen of the digestive tract (i.e., mediated by microorganisms) or in the liver catalyzed by enzymes. The identification of a large amount of trimethyl glycerol arsenoribose in H. rubra intestinal tissue suggests this species is a main constituent in the pathway for arsenic in this marine animal.

Distribution and Speciation of Arsenic in Temperate Marine Saltmarsh Ecosystems

Environmental Context. The pathways by which arsenic is accumulated and transferred in aquatic ecosystems are relatively unknown. Examination of whole marine ecosystems rather than individual organisms provides greater insights into the biogeochemical cycling of arsenic. Saltmarshes with low ecological diversity are an important terrestrial–marine interface about which little is known regarding arsenic concentrations and species distribution. This study examines the cycling of arsenic within Australian saltmarsh ecosystems to further understand its distribution and trophic transfer. Abstract. This paper reports the distribution of total arsenic and arsenic species in saltmarsh ecosystems located in south-east Australia. We also investigated the relationship between arsenic, iron, and phosphorus concentrations in saltmarsh halophytes and associated sediment. Total mean arsenic concentrations in saltmarsh plants, S. quinqueflora and S. australis, for leaves ranged from 0.03 ± 0.05 to 0.67 ± 0.48 μg g−1 and 0.03 ± 0.02 to 0.08 ± 0.06 μg g−1, respectively, and for roots ranged from 2 ± 2 to 6 ± 12 μg g−1 and 0.39 ± 0.20 to 0.57 ± 1.06 μg g−1 respectively. Removal of iron plaque from the roots reduced the arsenic concentration variability to 0.40–0.79 µg g−1 and 0.95–1.05 µg g−1 for S. quinqueflora and S. australis roots respectively. Significant differences were found between locations for total arsenic concentrations in plant tissues and these differences could be partially attributed to differences in sediment arsenic concentrations between locations. For S. quinqueflora but not S. australis there was a strong correlation between arsenic and iron concentrations in the leaf and root tissues. A significant negative relationship between arsenic and phosphorus concentrations was found for S. quinqueflora leaves but not roots. Total mean arsenic concentrations in salt marsh animal tissues (7 ± 2–21 ± 13 µg g−1) were consistent with those found for other marine animals. The concentration of total arsenic in gastropods and amphipods could be partially explained by the concentration of total arsenic in the dominant saltmarsh plant S. quinqueflora. Of the extractable arsenic, saltmarsh plants were dominated by arsenic(iii), arsenic(v) (66–99%), and glycerol arsenoribose (17–35%). Arsenobetaine was the dominant extractable arsenic species in the gastropods Salinator soilda (84%) and Ophicardelus ornatus (89%) and the crab Neosarmatium meinerti (89%). Amphipods contained mainly arsenobetaine (44%) with some phosphate arsenoribose (23%). Glycerol trimethyl arsonioribose was found in both gastropods (0.7–0.8%) and the visceral mass of N. meinerti (0.1%). These results show that arsenic uptake into plants from uncontaminated saltmarsh environments maybe dependent on plant iron uptake and inhibited by high phosphorus concentrations. Arsenic in saltmarsh plants is mainly present as inorganic arsenic, but arsenic in animals that eat plant detritus is present as organo arsenic species, primarily arsenobetaine and arsenosugars. The presence of glycerol trimethyl arsonioribose poses the question of whether trimethylated arsonioriboses are transitory intermediates in the formation of arsenobetaine.

Formation of arsenobetaine from arsenocholine by micro‐organisms occurring in sediments

AbstractAs one of the experiments to pursue marine circulation of arsenic, we studied microbiological conversion of arsenocholine to arsenobetaine, because arsenocholine may be a precursor of arsenobetaine in these ecosystems. Two culture media, 1/5 ZoBell 2216E and an aqueous solution of inorganic salts, were used in this in vitro study. To each medium (25 cm3) were added synthetic arsenocholine (0.2%) and about 1 g of the sediment, and they were aerobically incubated at 25°C in the dark. These conversion experiments were performed in May and July 1990. In both seasons, two or three metabolites were derived in each mixture. These metabolites were purified using cation‐exchange chromatography. Their structures were confirmed as arsenobetaine, trimethylarsine oxide and dimethylarsinic acid by high‐performance liquid chromatography, thin‐layer chromatography, FAB mass spectrometry and a combination of gas‐chromatographic separation with hydride generation followed by a cold‐trap technique and selected‐ion monitoring mass spectrometric analysis. From this and other evidence it is concluded that, in the arsenic cycle in these marine ecosystems, as recently postulated by us, the pathway arsenocholine → arsenobetaine → trimethylarsine oxide → dimethylarsinic acid → methanearsonic acid → inorganic arsenic can be carried out by micro‐organisms alone.