Integrating Transcriptome and Metabolome Analyses Revealed Salinity Induces Arsenobetaine Biosynthesis in Marine Medaka (Oryzias melastigma).

Marine fish exhibit elevated levels of arsenobetaine (AsB), while the impact and underlying mechanism of salinity on AsB biosynthesis remain inadequately explored. In this study, marine medaka (Oryzias melastigma), typically inhabiting 30‰ high salinity, were gradually acclimated to low salinities of 20, 10, and 0‰. Following acclimation, the fish were exposed to arsenate (As(V)) in their diet for 30 days. Results showed a significant accumulation of total arsenic (As) and AsB concentrations in the muscle and head tissues of the exposed fish, with these accumulations exhibiting a positive correlation with water salinity. Transcriptome analyses revealed that exposure to As(V) at low salinity may disrupt membrane components and induce cytoskeletal injuries, while at high salinity, it triggered oxidoreductase activity and transmembrane transport. Metabolome analyses indicated that low salinity induced osmotic stress, resulting in an increased requirement for amino acids to upload intracellular osmotic equilibrium in O. melastigma. Furthermore, the key organic osmolytes and amino acids, including taurine, l-methionine, guanidinoethyl sulfonate, and N-acetyl-l-aspartic acid, exhibited a negative correlation with the AsB concentration. These findings indicated that salinity can regulate osmotic balance by influencing amino acid synthesis under low salinity and stimulating AsB synthesis under high salinity conditions in O. melastigma. This study provides insights into the impact of high salinity on AsB biosynthesis, the underlying regulatory mechanisms, and implications for managing As(V) risk.

Metabolome analysis revealed the critical role of betaine for arsenobetaine biosynthesis in the marine medaka (Oryzias melastigma).

Arsenobetaine (AsB), a non-toxic arsenic (As) compound found in marine fish, structurally resembles betaine (GB), a common methyl donor in organisms. This study investigates the potential role of GB in AsB synthesis in marine medaka (Oryzias melastigma) using metabolomic analysis. Dietary exposure to arsenate (As(V)) and varying GB concentrations (0.05% and 0.1% in diets) increased total As and AsB bioaccumulation, particularly in marine medaka muscle. Metabolomic analysis revealed that GB played a crucial role in promoting up-regulation in methylthioadenosine (MTA) by modulating the methionine cycle and down-regulation in glutathione (GSH) by modulating the glutathione cycle. Methionine metabolism and GSH, potentially binding again to exogenous GB, could synchronously produce more non-toxic AsB. Combining verification experiments of differential metabolites of Escherichia coli in vitro, GB, GSH, S-adenosylmethionine (SAM), and arsenocholine (AsC) entered methionine and glutathione metabolism pathways to generate more AsB. These findings underscore the GB's crucial regulatory role in modulating the synthesis of AsB. This study provides vital insights into the interplay between the structural analogs GB and AsB, offering specific strategies to enhance the detoxification mechanisms of marine fish in As-contaminated environments.

Speciation of arsenic in milk from cows fed seaweed.

BACKGROUND: Including seaweed in cattle feed has gained increased interest, but it is important to take into account that the concentration of toxic metals, especially arsenic, is high in seaweed. This study investigated the arsenic species in milk from seaweed-fed cows. RESULTS: Total arsenic in milk of control diets (9.3 ± 1.0 µg As kg-1, n = 4, dry mass) was significantly higher than seaweed-based diet (high-seaweed diet: 7.8 ± 0.4 µg As kg-1, P < 0.05, n = 4, dry mass; low-seaweed diet: 6.2 ± 1.0 µg As kg-1, P < 0.01, n = 4, dry mass). Arsenic speciation showed that the main species present were arsenobetaine (AB) and arsenate (As(V)) (37% and 24% of the total arsenic, respectively). Trace amounts of dimethylarsinic acid (DMA) and arsenocholine (AC) have also been detected in milk. Apart from arsenate being significantly lower (P < 0.001) in milk from seaweed-fed cows than in milk from the control group, other arsenic species showed no significant differences between groups. CONCLUSION: The lower total arsenic and arsenate in seaweed diet groups indicates a possible competition of uptake between arsenate and phosphate, and the presence of AC indicates that a reduction of AB occurred in the digestive tract. Feeding a seaweed blend (91% Ascophyllum nodosum and 9% Laminaria digitata) does not raise As-related safety concerns for milk. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Biodilution of Organic Species of Arsenic in Freshwater Food Webs.

Arsenic can accumulate in freshwater biota, sometimes reaching potentially harmful levels. However, the toxicity of arsenic strongly depends on which arsenic species are present. Although organic species are considered less harmful than inorganic ones, they have not been extensively studied in freshwater environments, and drivers of variation in arsenic speciation among sites and taxa remain unclear. We assessed concentrations of two organic arsenic species, arsenobetaine (AsB) and dimethylarsinic acid (DMA), in fish and invertebrates from three lakes near Sudbury, Ontario, Canada-a region with widespread mining impacts. Both AsB and DMA were detected in most samples (n = 212), varying across a wide range of concentrations (<0.001-30.144 and <0.006-5.262 mg/kg dry wt, respectively). The lake with the most severe mining impacts typically had the highest concentrations (designated by square brackets []) of AsB and DMA. In contrast, the percentage of total arsenic made up by AsB (%AsB) and DMA (%DMA) did not vary significantly between lakes. Arsenic speciation in fish muscle varied with fish size, selenium concentrations, and trophic elevation (inferred from nitrogen stable isotope ratios δ15N), but relationships with dietary carbon source (inferred from carbon stable isotope ratios δ13C) were more varied. Within all three lake food webs, [AsB] and [DMA] typically underwent biodilution, decreasing with trophic elevation (i.e., δ15N). Although the aforementioned factors explained some variation in arsenic speciation, there remains considerable unexplained variation. Further studies on arsenic speciation in freshwater biota should target a wider diversity of taxa to better understand drivers of variation in arsenic speciation. In addition, research emphasizing the percentage of inorganic arsenic and other organic arsenic species is needed to improve environmental and human health risk assessments. Environ Toxicol Chem 2024;43:833-846. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Significant Biotransformation of Arsenobetaine into Inorganic Arsenic in Mice.

Arsenic (As) is extremely toxic to living organisms at high concentrations. Arsenobetaine (AsB), confirmed to be a non-toxic form, is the main contributor to As in the muscle tissue of marine fish. However, few studies have investigated the biotransformation and biodegradation of AsB in mammals. In the current study, C57BL/6J mice were fed four different diets, namely, Yangjiang and Zhanjiang fish diets spiked with marine fish muscle containing AsB, and arsenite (As(III)) and arsenate (As(V)) diets spiked with As(III) and As(V), respectively, to investigate the biotransformation and bioaccumulation of AsB in mouse tissues for 42 d. Different diets exhibited different As species distributions, which contributed to varying levels of As bioaccumulation in different tissues. The intestines accumulated the highest level of As, regardless of form, which played a major part in As absorption and distribution in mice. We observed a significant biotransformation of AsB to As(V) following its diet exposure, and the liver, lungs, and spleen of AsB-treated mice showed higher As accumulation levels than those of As(III)- or As(V)-treated mice. Inorganic As showed relatively high accumulation levels in the lungs and spleen after long-term exposure to AsB. Overall, these findings provided strong evidence that AsB undergoes biotransformation to As(V) in mammals, indicating the potential health risk associated with long-term AsB intake in mammals.

Chronic dietary exposure to total arsenic, inorganic arsenic and water-soluble organic arsenic species based on results of the first German total diet study.

For risk assessment purposes, the dietary exposure to total arsenic and inorganic arsenic was estimated within the first German total diet study (BfR MEAL Study) for the whole population in Germany. Therefore, occurrence data of 356 different foods from the BfR MEAL Study were combined with consumption data from German nutrition surveys. Due to the different toxicological potentials of other water-soluble organic arsenic species present in rice-based foods, fish and seafood, dietary exposure to dimethylarsinic acid, monomethylarsonic acid and arsenobetaine was assessed in consumers in Germany through such foods for the first time. Related to the bodyweight, dietary exposure to total arsenic and inorganic arsenic in infants and young children (0.5-<5 years) were higher than in adolescents/adults (≥14 years). The highest median exposure estimates to inorganic arsenic resulted for the age group of infants from 0.5 to <1 year under modified lower bound conditions and for young children from 1 to <2 years under upper bound conditions (0.17 µg kg-1 bodyweight day-1-0.24 µg kg-1 bodyweight day-1 and 0.26 µg kg-1 bodyweight day-1-0.34 µg kg-1 bodyweight day-1, respectively). 'Grains and grain-based products' (especially rice) were identified as the main contributors for dietary exposure to total arsenic and inorganic arsenic for all age classes. Especially, for infants and young children, high consumption of rice-based foods and fish fingers is driving the dietary exposure to dimethylarsinic acid. The dietary exposure calculations indicate that a further reduction of dietary exposure to inorganic arsenic and further investigations to water-soluble organic arsenic species are necessary.

Biotransformation and detoxification mechanism of inorganic arsenic in a freshwater benthic fish Tachysurus fulvidraco with dietborne exposure.

Inorganic arsenic (iAs) is a pervasive environmental toxin, its metabolism and detoxification mechanism in freshwater benthic fish under dietary exposure remain unknown. In this study, dietborne exposure of two iAs (arsenate (AsV) and arsenite (AsIII)) was conducted for yellow catfish (Tachysurus fulvidraco) to investigate the bioaccumulation, biotransformation, and detoxification of iAs in the fish liver. The results showed that As significantly accumulated in both the AsIII and AsV treatments compared to the control, and the final As concentration was comparable for both treatments. The detoxification of iAs in freshwater fish depends on the degree of arsenic methylation and the level of antioxidants. Both reduction processes of AsV to AsIII and oxidation processes of AsIII to AsV were found in AsV and AsIII treatments. The major-low toxicity intermediates, which also are detoxification products in the AsIII treatment, were pentavalent dimethylarsinic acid and arsenobetaine (AsB), and AsB was major-low toxicity intermediate in the AsV treatment. Both antioxidants glutathione and glutathione S-transferase contribute to the detoxification of iAs by scavenging excessive reactive oxygen species and promoting iAs methylation in yellow catfish under iAs exposure.

Seasonal variations in mercury, cadmium, lead and arsenic species in Norwegian blue mussels (Mytilus edulis L.) - Assessing the influence of biological and environmental factors.

BACKGROUND: Blue mussels (Mytilus edulis L.) can accumulate undesirable substances, including the potentially toxic elements (PTEs) cadmium (Cd), mercury, (Hg), lead (Pb), arsenic (As) and As species. In this study, the levels of PTEs and As species were determined in samples of blue mussels to assess the influence of environmental and biological factors, and evaluate the potential risk associated with blue mussels in terms of food and feed safety. METHODOLOGY: Blue mussels were collected monthly from one location in Western Norway from February 2018 to December 2018, and from April 2019 to April 2020. Samples were analyzed for PTEs using inductively coupled plasma mass spectrometry (ICP-MS), and high-performance liquid chromatography (HPLC) coupled to ICP-MS. Temperature, salinity and fluorescence (chlorophyll a) were monitored in the seawater column by STD/CTD, to assess the potential influence of these environmental factors on the PTE levels in the mussels. RESULTS: The results showed seasonal variations in the PTEs, with somewhat higher concentrations in spring and winter months. Unusually high levels of total As (101.2 mg kg-1 dw) and inorganic As (53.6 mg kg-1 dw) were observed for some of the time points. The organic As species arsenobetaine was generally the major As species (17-82% of total As) in the mussels, but also simple methylated As species and arsenosugars were detected. Principal components analysis (PCA) did not show a consistent relationship between the environmental factors and the PTE concentrations, showing contrary results for some elements for the periods studied. The condition index (CI) could explain variations in element concentration with significant correlations for Cd (r = -0.67, p = 0.009) and Pb (r = -0.62, p = 0.02 in 2019/20 and r = -0.52, p = 0.02 in 2018), whereas the correlation between As and CI was not significant (r = 0.12 in 2018, and r = -0.06 in 2019/20). Higher concentrations of iAs and arsenosugars coincided with increased signals of chlorophyll a, suggesting that phytoplankton blooms could be a source of As in the blue mussels. CONCLUSION: To our knowledge, this is the first study of As species in blue mussels collected over a time period of two years, providing an insight into the natural variations of these chemical forms in mussels. In terms of mussel as food and future feed material, concentrations of Cd, Hg and Pb were below the maximum levels (MLs) established in the EU food and feed legislation. However, levels of As and iAs in mussels at some time points exceeded the MLs for As in the feed legislation, and the margin of exposure (MOE) was low if these mussels were for human consumption, highlighting the importance of determining the chemical forms of As in feed and food.

Key genes for arsenobetaine synthesis in marine medaka (Oryzias melastigma) by transcriptomics.

Marine fish undergo detoxification to overcome As stress, forming non-toxic metabolites arsenobetaine (AsB). Genes associated with AsB synthesis remain unknown. Therefore, in this study, we explored the key genes involved in the synthesis of AsB by transcriptomic analysis in marine medaka (Oryzias melastigma), and then screened candidate genes related to AsB synthesis. In the liver, 40 genes were up-regulated and 23 genes were down-regulated, whereas in muscle, 83 genes were up-regulated and 331 genes were down-regulated. We revealed that bhmt, mat2aa, and gstt1a can play a significant role in the glutathione and methionine metabolic pathway. These three genes can affect the conversion of arsenocholine (AsC) to AsB by the vitro gene transformation experiments of E. coli BL21(DE3). E. coli BL21-bhmt overexpressing bhmt resulted in more oxidation of precursor AsC to AsB. Furthermore, the AsB concentration was decreased after E. coli BL21 overexpressing mat2aa and gstt1a, which were down-regulated in marine medaka. Therefore, we concluded that bhmt, mat2aa, and gstt1a are involved in AsB synthesis. Overall, this is the first report on transcriptome screening and identification of key genes for AsB synthesis in marine medaka. We provided important insights to reveal the mystery of AsB synthesis in marine fish.

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.

The strategy of arsenic metabolism in an arsenic-resistant bacterium Stenotrophomonas maltophilia SCSIOOM isolated from fish gut.

Bacteria are candidates for the biotransformation of environmental arsenic (As), while As metabolism in bacteria is not yet fully understood. In this study, we sequenced the genome of an As-resistant bacterium strain Stenotrophomonas maltophilia SCSIOOM isolated from the fish gut. After arsenate (As(V)) exposure, S. maltophilia transformed As(V) to organoarsenicals, along with the significant change of the expression of 40 genes, including the upregulation of arsH, arsRBC and betIBA. The heterogeneous expression of arsH and arsRBC increased As resistance of E. coli AW3110 by increasing As efflux and transformation. E. coli AW3110 (pET-betIBA) could transform inorganic As into dimethylarsinate (DMA) and nontoxic arsenobetaine (AsB), which suggested that AsB could be synthesized through the synthetic pathway of its analog-glycine betaine. In addition, the existence of arsRBC, betIBA and arsH reduced the reactive oxygen species (ROS) induced by As exposure. In total, these results demonstrated that S. maltophilia adopted an As metabolism strategy by reducing As accumulation and synthesizing less toxic As species. We first reported the production and potential synthetic pathway of AsB in bacteria, which improved our knowledge of As toxicology in microorganisms.

The speciation of arsenic in the muscle tissue of inland and coastal freshwater fish from a remote boreal region.

Elevated concentrations of total arsenic (As) have been reported in boreal freshwater fish in both human-impacted and relatively pristine areas. We assessed the arsenic speciation profiles in muscle tissue of six fish species (n = 300) sampled from nine locations across a remote freshwater watershed in northern Ontario, Canada, extending from inland headwater lakes to the coastal marine confluence. Of the five arsenic species measured, only arsenobetaine (AsB) and dimethylarsinic acid (DMA) were detected in these fish. Riverine fish had up to 10-fold higher total [As] when compared to lacustrine fish. On average, these riverine fish also had higher percentages of AsB (%AsB, 60 ± 26%) and lower percentages of unmeasured arsenic (%UNM, 20 ± 21%), compared to lacustrine fish (28 ± 18% and 52 ± 21% %AsB and %UNM, respectively). DMA percentages (%DMA) were relatively consistent across the watershed, averaging 20 ± 21% across all fish. We examined ecological drivers of As speciation and found that %AsB increased slightly with fish weight in large-body predatory fish, but not in forage fish or insectivores. Furthermore, %AsB was positively related to trophic elevation (inferred from δ15N) in lacustrine fish across 3 out of 4 communities and within some populations. Lastly, riverine fish with a more marine-based diet had markedly higher %AsB when compared to fish with more freshwater-based diets, indicating an effect of anadromy on arsenic speciation. Overall, knowledge on arsenic speciation in freshwater fish has been limited and these results indicate potential drivers that can be considered in future studies. Furthermore, the absence of toxic inorganic As species in these boreal fish is an important consideration for future environmental monitoring practices and risk assessments, some of which assume 10-20% of total [As] in fish is present as toxic inorganic As. Additional studies on As bioaccumulation and biotransformation are needed in freshwater systems, particularly at the base of aquatic food webs.

Biodegradation of arsenobetaine to inorganic arsenic regulated by specific microorganisms and metabolites in mice.

Arsenobetaine (AsB) is a primary arsenic (As) compound found in marine organisms. However, in mammals, the metabolic mechanism of AsB remains indistinct. Therefore, in this study, we investigated the biotransformation and regulatory mechanism of AsB, particularly the biodegradation process, in a mouse model to assess the underlying health hazards of AsB. We studied the biotransformation process of AsB in mice through the food chain [AsB feed-marine fish (Epinephelus fuscoguttatus)-mice (Mus musculus)]. Our results showed the significant bioaccumulation of total As, AsB, and, in particular, arsenate [As(V)] through biodegradation in mice tissues. As the abundance of Staphylococcus and Blautia (phylum, Firmicutes) increased, the expression of aqp7 (absorption) and methyltransferase (as3mt) (methylation) was upregulated. In contrast, the expression of S-adenosyl methionine (sam) (methylation) was downregulated. These findings suggest that demethylation and methylation occurred simultaneously in the intestines, with demethylation capacity being greater than that of methylation. Furthermore, Firmicutes such as Staphylococcus and Blautia showed a significant inverse relationship with arachidonic acid, choline, and sphingosine. Gene, microbiome, and metabolomics analyses indicated that Staphylococcus and Blautia and arachidonic acid, choline, and sphingosine participated in the degradation of AsB to As(V) in mouse intestines. Therefore, long-term AsB ingestion through marine fish consumption could cause potential health hazards in humans.

Arsenic species in mesopelagic organisms and their fate during aquafeed processing.

A responsible harvest of mesopelagic species as aquafeed ingredients has the potential to address the United Nations Sustainable Development Goal 14, which calls for sustainable use of marine resources. Prior to utilization, the levels of undesirable substances need to be examined, and earlier studies on mesopelagic species have reported on total arsenic (As) content. However, the total As content does not give a complete basis for risk assessment since As can occur in different chemical species with varying toxicity. In this work, As speciation was conducted in single-species samples of the five most abundant mesopelagic organisms in Norwegian fjords. In addition, As species were studied in mesopelagic mixed biomass and in the resulting oil and meal feed ingredients after lab-scale feed processing. Water-soluble As species were determined based on ion-exchange high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). This was supplemented by extracting arsenolipids (AsLipids) and determining total As in this fraction. The non-toxic arsenobetaine (AB) was the dominant form in mesopelagic crustaceans and fish species, accounting for approximately 70% and 50% of total As, respectively. Other water-soluble species were present in minor fractions, including carcinogenic inorganic As, which, in most samples, was below limit of quantification. The fish species had a higher proportion of AsLipids, approximately 35% of total As, compared to crustaceans which contained 20% on average. The feed processing simulation revealed generally low levels of water-soluble As species besides AB, but considerable fractions of potentially toxic AsLipids were found in the biomass, and transferred to the mesopelagic meal and oil. This study is the first to report occurrence data of at least 12 As species in mesopelagic organisms, thereby providing valuable information for future risk assessments on the feasibility of harnessing mesopelagic biomass as feed ingredients.

Physiologically based pharmacokinetic model revealed the distinct bio-transportation and turnover of arsenobetaine and arsenate in marine fish.

Arsenobetaine (AsB) is the major form of arsenic in marine fish; however, its biodynamics within the fish tissues is not well understood. This study simulated the biodynamics and biotransportation (absorption, distribution, and elimination) of dietary AsB and arsenate [As(V)] in the marine grouper Epinephelus fuscoguttatus, by constructing a physiologically based pharmacokinetic (PBPK) model. The transfer rates between different compartments (gill, intestine, liver, heart, kidney, and muscle) and blood were modeled during exposure (14 d) and depuration (20 d). The model showed that AsB had a weak ability to cross the intestinal membranes and circulated slowly in the blood. The newly AsB absorbed from the blood did not enter the hepatointestinal circulation for elimination, but was effectively distributed in liver. Thereafter, it was slowly absorbed and finally stored in the muscle, the most important organ for AsB deposition, at a constant rate of 63.5 d-1. In contrast, As(V) displayed a dynamic behavior, including rapid crossing through the intestinal membranes, quick circulation in the blood and transportation to other tissues, and elimination. Biodynamics coupled with biotransformation illustrated, for the first time, the unique strategies of dietary AsB that passed slowly through the fish intestine with the highest deposition rate in the muscle, thereby contributing to the high AsB bioaccumulation in the muscle tissue of marine fish. CAPSULE: AsB displayed a weaker ability to cross the intestine membranes, slowly absorbed and finally stored in muscle, whereas As(V) displayed rapid crossing the intestine membranes, quick transportation, and elimination.

Contribution of diet and other factors for urinary concentrations of total arsenic and arsenic species: data for US children, adolescents, and adults.

A comprehensive analysis of the associations between the consumptions of 17 food products with urinary concentrations of arsenobetaine, total arsenic, arsenous acid, dimethylarsinic acid (UDMA), monomethylarsonic acid (UMMA), and total inorganic arsenic for US children aged 3-5 years (N = 439), children aged 6-11 years (N = 2139), adolescents aged 12-19 years (N = 2434), and adults aged >= 20 years (N = 10902) was conducted. Data from National Health and Nutrition Examination Survey for 2005-2016 were used for this study. Concentrations of arsenobetaine were as much as > 15 times higher among consumers of fish/shellfish than non-consumers for children aged 6-11 years, > 12 times higher for children aged 3-5 years, > 13 times higher for adolescents, and > 7 times higher for adults. Consumption of rice as opposed to non-consumption of rice was associated with as much as 36.5% higher concentrations of total arsenic, 12.7% higher concentrations of arsenous acid, 43.9% higher concentrations of UDMA, 18.2% higher concentrations of UMMA, and 14.1% higher concentrations of total inorganic arsenic. Thus, consumption of fish/shell fish and rice was associated with higher concentrations of organic/inorganic arsenic. In addition, consumption of alcohol was also found to be associated with higher concentrations of organic/inorganic arsenic. However, consumption of milk and milk products, vegetables, organ and other meats, and nutritional drinks was found to be associated with lower concentrations of organic/inorganic arsenic. Thus, while consumption of several foods is associated with higher concentrations of arsenic, there are also foods whose consumption is associated with decreased concentrations of arsenic. Further studies are needed to identify foods that may lead to decreased concentrations of arsenic and as such arsenic toxicity.

Dietary intake and urinary excretion of methylated arsenicals of Japanese adults consuming marine foods and rice.

Dietary intake and urinary excretion of monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine (AsB) were measured in 150 adult Japanese subjects. Duplicate diet (DD) samples and first void of urine on the next morning of DD sampling day were collected and analysed for arsenic species with liquid chromatography-ICP mass spectrometry. Median (min-max) intakes of MMA, DMA and AsB were <2.3 (<2.3-<2.3), 4.57 (<2.3-24.3), and 13.6 (<2.4-231) µg As/day, respectively, and median urinary concentrations were 1.90 (<0.37-26.), 21.9 (<0.27-141) and 19.6 (<0.37-1063) ng As/mg creatinine, respectively. Interrelationships between intake levels and urinary concentrations were mostly significant with positive coefficients indicating mutual association due to co-exposure, metabolism and/or dietary habit. Urinary concentrations and intake levels of AsB were also positively correlated confirming the applicability of urine analysis as biomarker of exposure. The present descriptive results provide with essential piece of information in assessing health risk of methylated arsenicals for population who consume marine products and rice.

The effect of Ulva lactuca and Sargassum hemiphyllum var. chinense on arsenic metabolites and enzymes in broilers.

This study investigated the effect of seaweed supplementation (Ulva lactuca (UL) or Sargassum hemiphyllum var. chinense (SHC)) on the distribution and metabolites of As in broiler breasts. Broilers fed 5% UL or 5% SHC ingested 1.4- or 78- fold greater total As than birds fed the control diet. The majority of As species were arsenate in the SHC feed and dimethylarsinic acid in breasts from chicks fed the SHC-containing diet. Arsenate and arsenobetaine were the dominant metabolites in the UL-containing feed, and arsenobetaine was the major metabolite in breasts from chicks fed the UL-containing diet. Feeding SHC enhanced hepatic S-adenosyl-methionine and arsenic methyltransferase, whereas feeding UL elevated renal arsenic methyltransferase. Taken together, considerable variation in the profiles of As species and As metabolites existed in broilers fed seaweed. The use of SHC-containing feeds in poultry production should be approached cautiously because of the potential accumulation of inorganic As species in chicken breasts.

Speciation analysis of arsenic in edible mushrooms by high-performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry.

Some varieties of edible mushrooms can accumulate high contents of arsenic, which is a public health concern. In this study, we developed a high-performance liquid chromatography method linked to inductively coupled plasma triple quadrupole mass spectrometry (HPLC-ICP-MS/MS) for sensitive and accurate determination of arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenocholine and arsenobetaine in edible mushrooms. The six arsenic species were extracted ultrasonically from mushrooms using ultrapure water at 60 °C as the solvent, separated on a PRP-X100 anion exchange column (4.1 × 250 mm, 10 µm), with 20 mmol/L NH4HCO3 and 50 mmol/L (NH4)2CO3 as the mobile phase, and quantified using ICP-MS/MS in the oxygen reaction mode. The linear range of the method was 0.5 µg/L-100 µg/L with detection and quantification limits of 2.5 µg/kg-10 µg/kg (S/N = 3), and 8 µg/kg-33 µg/kg (S/N = 10), respectively. This method was applied successfully to the detection and speciation of arsenic in eight varieties (266 samples) of mushrooms. Our results indicated that most wild edible mushrooms contained organic arsenic, mainly arsenobetaine and arsenocholine. However, the inorganic arsenic content of Armillariella tabescens (3.63 mg/kg) and parts of the cultivated Agaricus blazei murrill (up to 4.50 mg/kg) were relatively high, which is potential risk to the health of consumers.

Influence of different arsenic species on uptake, speciation and efflux of arsenic in hydroponic rice plants.

Uptake, translocation and speciation of As in rice plants have been investigated through hydroponic cultivations under stress from different As species. After germination, rice seedlings were treated with arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMA) or dimethylarsinic acid (DMA) at concentrations of 50, 100, 150, 200 and 250 µg/L for 24 days. Only inorganic As species were detected in the rice plants treated with As(III) or As(V), indicating that rice seedlings could not methylate inorganic As in hydroponic culture. As(V) in the rice roots was readily reduced to As(III) after uptake; thus, As(III) was the dominant species in the rice roots (>60%) and shoots (>80%) regardless of As(III) or As(V) treatment. The increased As(III) proportion in the nutrient solutions was due to the efflux of As(III) from the rice roots. MMA with relatively low stability in the blank nutrient solution was demethylated to As(III). Moreover, demethylation and methylation of MMA might occur simultaneously in rice plants. Specific proportions of MMA and AsB were observed in the rice roots treated with DMA, implying that MMA and AsB were the DMA metabolites in rice roots after detoxification.