Human exposure to organic arsenic species from seafood.

Human exposure to dietary inorganic arsenic and other arsenic species: State of knowledge, gaps and uncertainties.

High arsenic (As) levels in food and drinking water, or under some occupational conditions, can precipitate chronic toxicity and in some cases cancer. Millions of people are exposed to unacceptable amounts of As through drinking water and food. Highly exposed individuals may develop acute, subacute, or chronic signs of poisoning, characterized by skin lesions, cardiovascular symptoms, and in some cases, multi-organ failure. Inorganic arsenite(III) and organic arsenicals with the general formula R-As2+ are bound tightly to thiol groups, particularly to vicinal dithiols such as dihydrolipoic acid (DHLA), which together with some seleno-enzymes constitute vulnerable targets for the toxic action of As. In addition, R-As2+-compounds have even higher affinity to selenol groups, e.g., in thioredoxin reductase that also possesses a thiol group vicinal to the selenol. Inhibition of this and other ROS scavenging seleno-enzymes explain the oxidative stress associated with arsenic poisoning. The development of chelating agents, such as the dithiols BAL (dimercaptopropanol), DMPS (dimercapto-propanesulfonate) and DMSA (dimercaptosuccinic acid), took advantage of the fact that As had high affinity towards vicinal dithiols. Primary prevention by reducing exposure of the millions of people exposed to unacceptable As levels should be the prioritized strategy. However, in acute and subacute and even some cases with chronic As poisonings chelation treatment with therapeutic dithiols, in particular DMPS appears promising as regards alleviation of symptoms. In acute cases, initial treatment with BAL combined with DMPS should be considered.

https://www.mdpi.com/2218-273X/10/2/235/pdf

Arsenic toxicity: Molecular targets and therapeutic agents

This is the 30th annual review of the application of atomic spectrometry to the chemical analysis of environmental samples. This Update refers to papers published approximately between August 2013 and July 2014 and continues the series of Atomic Spectrometry Updates (ASUs) in environmental analysis that should be read in conjunction with other related ASUs in the series, namely: clinical and biological materials, foods and beverages, advances in atomic spectrometry and related techniques, elemental speciation,X-ray fluorescence spectrometry, and the analysis of metals, chemicals and functional materials. In the field of air analysis, highlights within this review period included: the use of 3D printing technology for the rapid prototyping of new air sampler components; single particle ICP-MS studies; use of a new triple-quadrupole ICP-MS for the analysis of radioactive species and the use of FEG-SEM and IBA for the analysis of gun-shot residues. In the field of water analysis, methods continue to be developed: for the extraction and preconcentration of elements; speciation of As, Cr, Hg and Sb forms and determination of elemental constituents in colloidal and NP fractions. Instrumental developments reported include the use of MC-ICP-MS for isotopic tracer studies and a review of XRF techniques and associated preconcentration procedures for trace element analysis. Many articles featuring the analysis of plants and soils appeared but, as usual, most focused on environmental applications rather than the advancement of atomic spectrometry. There have, however, been interesting developments, such as the almost bewildering increase in types of micro-extraction for analyte preconcentration and the resurgence of CS-AAS. Clearly LIBS is maturing rapidly, with soil analysis becoming more routine in nature. Also notable was the way the accident at the Fukishima-Daiichi nuclear power plant triggered development of analytical methods for the assessment of contamination in the surrounding area. Recent research indicates that geological applications still drives many of the instrumental and methodological advances in LA-ICP-MS. Fundamental studies continue to shed light on the processes involved and hence ways of improving the analysis of laser-produced aerosols. The preparation of NP powders for the production of matrix-matched RMs for microanalytical techniques such as LA-ICP-MS and SIMS showed great promise for addressing one of the major issues when analysing geological materials by these techniques. Steady advances in MC-ICP-MS methodology is feeding through to applications in isotope geochemistry, while new SIMS instrumentation is being directed towards probing fine growth structures in biogenic carbonates and inferring past climate conditions from their geochemistry. Feedback on this review is most welcome and the review coordinator can be contacted using the email address provided.

/pdf/atomic-spectrometry-update-a-review-of-advances-in-2r8uzbiose.pdf

Atomic spectrometry update – a review of advances in environmental analysis

More than 100 different arsenic species of diverse characteristics are present in the environment and biological systems. The identification and quantification of individual arsenic species are critical to understanding the distribution, environmental fate and behaviour, metabolism, and toxicity of arsenic. This review summarizes sample preparation, separation, detection, and method validation for arsenic speciation analysis. An emphasis is placed on chromatographic separation techniques, relating the physicochemical properties of arsenic species to their efficient separation. Anion exchange, cation exchange, reversed-phase, ion pair, and size exclusion chromatography are useful to separate various arsenic species. Recent research has explored hydrophilic interaction liquid chromatography (HILIC), multiple separation mechanisms, and testing of fluorophenyl and graphene oxide stationary phases for the separation of arsenic species. Sample preparation, extraction of arsenic species, recovery of arsenic species from separation columns, and method validation are discussed in light of their importance to the integrity and accuracy of speciation analysis.

Arsenic speciation analysis: A review with an emphasis on chromatographic separations

The importance of measuring arsenic (As) species has been appreciated for a long time mainly because of the wide spread knowledge of arsenic's toxicity and its use as a poison. Increasingly health, environmental and food regulations have been written around As species rather than total concentrations. Knowledge of As speciation is important as the chemical form of As controls its bioavailability, toxicity, mobility and therapeutic benefits. Arsenic is present as inorganic (arsenate, arsenite, thioarsenates), complexed (arsenic glutathionines and phytochelatins), low molecular weight (monomethylarsonate, dimethylarsenate, arsenobetaine, arsenocholine etc.) and high molecular weight (arsenic hydrocarbons and arsenic phospholipids) species. In this review we cover the intergrity of As species during collection, storage, sample preparation and measurement by HPLC-ICPMS and HPLC-HG-AFS. It is essential to ensure that As species, especially in waters and sediments, are not artefacts of the preservation or extraction procedure. Most samples can be stored frozen (−20 °C), but the stability of water and sediment samples is matrix dependent and depends on preservation technique applied. Arsenic cannot be extracted from samples using a single set of conditions but must be optimised for each sample type. Methanol–water mixtures with microwave heating are commonly used to extract polar As species from tissues while As-lipids required a non-polar solvent. Dilute acid can be used to increase the efficiencies of extraction of hard to extract tissue As species. Freeze drying is suitable for the drying of biotic material while sediments should not be dried before analysis. Extraction efficiencies are critically dependent on particle size. Polar As species have a wide variety of ionic characteristics thus complimentary chromatographic approaches utilising ion-exchange or reverse phase columns with modifiers are needed to separate all the As species. Arsenic-lipids require the use of a reverse phase column and gradient elution with high concentrations of organic solvents and require compensation for carbon enhancement effects in the ICPMS. Care must be taken that chromatographic peaks are not misidentified and matrix interferences accounted for that may influence quantification. Finally, to ensure accurate results, mass balances and extraction and column recoveries need to be determined at all steps. Methods need to be evaluated using As spikes and certified reference materials to provide a means of assessing the quality of results.

Measurement of arsenic species in environmental, biological fluids and food samples by HPLC-ICPMS and HPLC-HG-AFS

Overview of hyphenated techniques using an ICP-MS detector with an emphasis on extraction techniques for measurement of metalloids by HPLC–ICPMS

Arsenic-containing hydrocarbons (AsHCs), a subgroup of arsenolipids (AsLs) occurring in fish and edible algae, possess a substantial neurotoxic potential in fully differentiated human brain cells. Previous in vivo studies indicating that AsHCs cross the blood–brain barrier of the fruit fly Drosophila melanogaster raised the question whether AsLs could also cross the vertebrate blood–brain barrier (BBB). In the present study, we investigated the impact of several representatives of AsLs (AsHC 332, AsHC 360, AsHC 444, and two arsenic-containing fatty acids, AsFA 362 and AsFA 388) as well as of their metabolites (thio/oxo-dimethylpropionic acid, dimethylarsinic acid) on porcine brain capillary endothelial cells (PBCECs, in vitro model for the blood–brain barrier). AsHCs exerted the strongest cytotoxic effects of all investigated arsenicals as they were up to fivefold more potent than the toxic reference species arsenite (iAsIII). In our in vitro BBB-model, we observed a slight transfer of AsHC 332 across the BBB after 6 h at concentrations that do not affect the barrier integrity. Furthermore, incubation with AsHCs for 72 h led to a disruption of the barrier at sub-cytotoxic concentrations. The subsequent immunocytochemical staining of three tight junction proteins revealed a significant impact on the cell membrane. Because AsHCs enhance the permeability of the in vitro blood–brain barrier, a similar behavior in an in vivo system cannot be excluded. Consequently, AsHCs might facilitate the transfer of accompanying foodborne toxicants into the brain.

Effects of arsenolipids on in vitro blood-brain barrier model.

Arsenic-containing hydrocarbons (AsHCs), a subgroup of arsenolipids found in fish and algae, elicit substantial toxic effects in various human cell lines and have a considerable impact on cellular energy levels. The underlying mode of action, however, is still unknown. The present study analyzes the effects of two AsHCs (AsHC 332 and AsHC 360) on the expression of 44 genes covering DNA repair, stress response, cell death, autophagy, and epigenetics via RT-qPCR in human liver (HepG2) cells. Both AsHCs affected the gene expression, but to different extents. After treatment with AsHC 360, flap structure-specific endonuclease 1 (FEN1) as well as xeroderma pigmentosum group A complementing protein (XPA) and (cytosine-5)-methyltransferase 3A (DNMT3A) showed time- and concentration-dependent alterations in gene expression, thereby indicating an impact on genomic stability. In the subsequent analysis of epigenetic markers, within 72 h, neither AsHC 332 nor AsHC 360 showed an impact on the global DNA methylation level, whereas incubation with AsHC 360 increased the global DNA hydroxymethylation level. Analysis of cell extracts and cell media by HPLC–mass spectrometry revealed that both AsHCs were considerably biotransformed. The identified metabolites include not only the respective thioxo-analogs of the two AsHCs, but also several arsenic-containing fatty acids and fatty alcohols, contributing to our knowledge of biotransformation mechanisms of arsenolipids.

Arsenic-containing hydrocarbons: effects on gene expression, epigenetics, and biotransformation in HepG2 cells.

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Measurement of arsenic species in environmental, biological fluids and food samples by HPLC-ICPMS and HPLC-HG-AFS

Overview of hyphenated techniques using an ICP-MS detector with an emphasis on extraction techniques for measurement of metalloids by HPLC–ICPMS

Effects of arsenolipids on in vitro blood-brain barrier model.

Arsenic-containing hydrocarbons: effects on gene expression, epigenetics, and biotransformation in HepG2 cells.