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[Determination of total arsenic in sinters by hydride generation atomic fluorescence spectrometry].

A simple and sensitive method was proposed for the determination of total arsenic in sinters by hydride generation atomic fluorescence spectrometry (HGAFS). The method was based on the oxidation of arsenic compounds with strong acid mixtures in the pressure steel bomb. The linear range for AsV determination was 0-300 micrograms/L. The method was validated by analysis of standard reference material (coal fly ash) with satisfactory results and was successfully applied to the determination of total arsenic in sinters with RSD less than 4%.

Arsenic↗

Endonuclease III, formamidopyrimidine-DNA glycosylase, and proteinase K additively enhance arsenic-induced DNA strand breaks in human cells.

We report here that sequential digestion with endonuclease III, formamidopyrimidine-DNA glycosylase, and proteinase K in Tris buffer markedly increased the sensitivity for detecting DNA damage in arsenic-treated cells. These three enzymes increased DNA strand breaks in an additive manner. By using this sequential-enzyme-digestion comet assay, we demonstrated that trivalent inorganic arsenic induced more DNA damage than monomethylarsonous acid, monomethylarsonic acid, and dimethylarsinic acid in human blood cell lines. However, trivalent inorganic arsenic was far less potent than monomethylarsonous acid in inhibiting pyruvate dehydrogenase activity. Therefore, different mechanisms are involved in inhibiting pyruvate dehydrogenase activity and inducing DNA damage. Our results also indicate while trivalent inorganic arsenic induced more endonuclease III-digestible adducts, monomethylarsonous acid and monomethylarsonic acid induced more proteinase K-digestible adducts. These results suggest there is a difference in the mechanism for inducing DNA damage between inorganic and organic methylated arsenic compounds.

Arsenic↗

[Evaluation of the role of occupational and environmental exposure to inorganic arsenic in the urinary excretion of the metal: preliminary data].

INTRODUCTION: Urinary inorganic arsenic is an expression of occupational exposure to the metal, provided that there is no history of ingestion of foods containing high concentrations of inorganic and/or organic arsenic. The present study was conducted to assess the contribution of professional and environmental exposure to inorganic arsenic on urinary excretion of the metal. MATERIALS AND METHODS: We examined 195 workers at a steelfoundry in Taranto, exposed to very low concentrations of inorganic arsenic and two control groups consisting of 105 subjects resident near the factory and 144 subjects resident approximately 20 Km away. All participants were administered a questionnaire enquiring about general characteristics, lifestyle, occupational and extra occupational exposure to arsenic. Urinary arsenic was determined by atomic-absorption spectrophotometry. RESULTS: Exposed and non exposed subjects were similar as regards general characteristics and lifestyle. The environmental concentration of arsenic for the foundryworkers was invariably lower than 0.1 microg/m3. Urinary excretion of arsenic was higher in the subjects in all three groups, examined singly and together, if they had eaten crustaceans and/or shellfish in the three days before urine collection. There was a significant positive correlation with the consumption of shellfish and a significant negative correlation with the number of days since the last crustacean/shellfish meal. Multiple regression analysis showed a dependence of urinary elimination of arsenic on the days since the last crustacean/shellfish meal. DISCUSSION: The absence of occupational exposure to arsenic allowed us to attribute the higher urinary elimination of arsenic to ingestion of crustaceans and/or shellfish in the three days before collection of the urine, both in subjects exposed to inorganic arsenic and in the two groups belonging to the general population. Our results support the hypothesis that inorganic arsenic, determined by atomic-absorption spectrophotometry, may derive from the catabolism of organic arsenic compounds contained in crustaceans and/or shellfish included in the diet.

Arsenic↗

Arsenic and antimony: comparative approach on mechanistic toxicology.

A chemico-toxicological similarity between arsenic and antimony exists and their toxicology is often seen. Indeed, both elements possess several common properties, e.g. they are clastogenic but not mutagenic in the trivalent state and they have a carcinogenic potential: trivalent arsenicals are known to be human carcinogens and antimony(III) oxide (by inhalation) has been shown to cause lung cancer in female rats. For years, arsenic has been known to be environmentally toxic. Elevated human exposure to this element, mostly caused by the intake of contaminated tap water, is associated with increased incidences of cancer at various sites. It is still not clear how arsenic compounds exert their genotoxic effect. It may be connected with an inhibition of DNA repair or the induction of oxidative stress. Little work has been done on the toxicology of antimony as it is less widely present in the environment. There is evidence that in mammals antimony, unlike arsenic, is not detoxified via methylation but it still remains unclear what mechanism is responsible for antimony's genotoxicity. In general, there is little information known about this element to accurately determine its impact on human health. Thus, the aim of this paper is to review current knowledge for future risk assessment and further scientific work.

Animals↗

Identification and quantification of arsenocholine and acetylarsenocholine in trace amounts in biological material by use of pyrolysis gas chromatography/mass spectrometry.

An analytical method, based on a selective extraction and pyrolysis gas chromatography/mass spectrometry assay of arsenocholine and acetylarsenocholine in aquatic organisms, is described. Characteristic fragmentation patterns were obtained from pyrolytically demethylated compounds. The molecules were rearranged in unique pathways which differed from those of corresponding nitrogen analogues. Qualitative determination of arsenocholine and acetylarsenocholine was achieved by gas chromatographic as well as mass spectrometric analysis of the thermal degradation products (trimethylarsine, dimethylvinylarsine and the demethylated arsenocholine or acetylarsenocholine). Arsenocholine and acetylarsenocholine in fish from industrially polluted water were isolated and identified. Massfragmentographic quantification of the arsenic compounds in fish was carried out by use of deuterium labelled analogues of arsenocholine and acetylarsenocholine as internal standards. The method showed a high sensitivity.

Animals↗

Arsenic speciation and distribution in an arsenic hyperaccumulating plant.

Arsenic-contaminated soil is one of the major arsenic sources for drinking water. Phytoremediation, an emerging, plant-based technology for the removal of toxic contaminants from soil and water, has been receiving renewed attention. Although a number of plants have been identified as hyperaccumulators for the phytoextraction of a variety of metals, and some have been used in field applications, no hyperaccumulator for arsenic had been previously reported until the recent discovery of Brake fern (Pteris vittata), which can hyperaccumulate arsenic from soils. This finding may open a door for phytoremediation of arsenic-contaminated soils. Speciation and distribution of arsenic in the plant can provide important information helpful to understanding the mechanisms for arsenic accumulation, translocation, and transformation. In this study, plant samples after 20 weeks of growth in an arsenic-contaminated soil were used for arsenic speciation and distribution study. A mixture of methanol/water (1:1) was used to extract arsenic compounds from the plant tissue. Recoveries of 85 to 100% were obtained for most parts of the plant (rhizomes, fiddle heads, young fronds and old fronds) except for roots, for which extraction efficiency was approximately 60%. The results of this study demonstrate the ability of Brake fern as an arsenic hyperaccumulator. It transfers arsenic rapidly from soil to aboveground biomass with only minimal arsenic concentration in the roots. The arsenic is found to be predominantly as inorganic species; and it was hypothesized that the plant uptakes arsenic as arsenate [As(V)I and arsenate was converted to arsenite [As(III)] within the plant. The mechanisms of arsenic uptake, translocation, and transformation by this plant are not known and are the objectives of our on-going research.

Arsenic↗

Embryotoxic effects of sodium arsenite and sodium arsenate on mouse embryos in culture.

Embryotoxic effects of two inorganic arsenic compounds, sodium arsenite (Asi) and sodium arsenate (Asa), on the development of mouse embryos during early organogenesis were studied using the whole embryo culture technique. Embryos with three to five somites exposed to 1-40 microM Asi or to 10-400 microM Asa were cultured for 48 hours and their development was compared with that of control embryos. Asi proved to be teratogenic between 3 and 4 microM and embryolethal at higher concentrations; Asa had similar activity but at concentrations ten times higher than for Asi. Both compounds produced a growth retardation and a similar pattern of defects. Growth retardation was indicated by a statistically significant reduction in crown-rump length, head length, and yolk sac diameter. Abnormal embryos were characterized by hypoplasia of the prosencephalon with open neural tube, hydropericardium, somite abnormalities, and failure of development of limb buds and sensory placodes. These results confirm that both Asa and Asi are embryotoxic compounds and that the Asi activity occurs at concentrations ten times lower than for Asa. Our results suggest that in humans both of these compounds may be involved in part of "unaccountable" early abortions and malformations claimed to be due to the toxicity of heavy metals.

Animals↗

Preliminary studies on arsenic species in some environmental samples.

Arsenic compounds have been determined in some environmental samples from the German Environmental Specimen Bank (ESB) (marine mussels, freshwater mussel and fish, sea-gull eggs) and certified reference materials (DORM-1, DOLT-1, NBS Oyster Tissue) after separation by open column cation and anion exchange chromatography by two different methods of total arsenic determination in separated fractions (instrumental neutron activation analysis or hydride generation atomic absorption spectrometry). Arsenobetaine has been identified as the major species in all the different materials.

Journal Article↗

Death by arsenic: a comparative evaluation of exhumed body tissues in the presence of external contamination.

External contamination of hair or nails by inorganic arsenic compounds cannot effectively be removed with H2O or dilute HCl. The use of a modified Gutzeit apparatus allowed to establish or rule out external contamination. It was found that contaminated samples will generate large amounts of arsine gas when treated with Zn, Kl, SnCl2, and dilute HCl in a Gutzeit arsine generator. Arsenic present in the sample due to metabolic deposition resulted in significant arsine formation only after digestion. In one chronic arsenic death, digestion increased the liberated amount of arsine from nail by a factor of twenty. Direct examination of hair and nail from a female resulted in values near 100 micrograms As/g tissue even after washing with HCl and H2O. Deep thigh muscle and spinal cord released arsine only after digestion. Control hair soaked in a NaAsO2 solution, washed and dried, bound 775 micrograms of As/g.

Adult↗

Arsenic biotransformation by the brown macroalga, Fucus serratus.

The brown alga Fucus serratus was maintained in aquaria with added arsenate (0, 20, 50, and 100 microg As/L, four individuals per treatment) for up to 19 weeks. Biotransformation of arsenic by Fucus was monitored by high-performance liquid chromatography/inductively coupled plasma mass spectrometry and liquid chromatography/electrospray mass spectrometry analysis of aqueous extracts of algal frond tips removed periodically throughout the experiment. Major arsenic species monitored were arsenate, arsenite, methylarsonate, dimethylarsinate, and the four arsenosugars 1 to 4 found naturally in Fucus. Algae accumulated arsenate readily and transformed it into several arsenic compounds depending on the exposure concentration. At 100 microg As/L, the major metabolite was arsenite with smaller quantities of methylarsonate and dimethylarsinate, but only traces of arsenosugars were formed. In contrast, the 20-microg-As/L group accumulated only small quantities of arsenite and methylarsonate, while dimethylarsinate and arsenosugars were major arsenic metabolites. At 50 microg As/L exposure, algae had significant quantities of all arsenic metabolites monitored. Arsenate was toxic to the algae at 100 microg As/L but had no obvious detrimental effect at 20 microg As/L. The data are consistent with a process of arsenate detoxification by reduction and alkylation; at higher exposures, however, the alkylation processes become saturated, leading to an accumulation of arsenite and subsequent toxicity.

Alkylation↗

Determination of arsenic in seafood by focused microwave digestion and hydride generation-atomic fluorescence detection.

A new method was developed for total arsenic determination in seafood products such as oysters, mussels, tuna fish, and algae. Matrix decomposition and oxidation to arsenate of all the arsenic compounds in the product were completed in 25 min by using a 3-step program of focused microwaves (40-120 W) with nitric and sulfuric acids. Quantitation was performed by hydride generation-atomic fluorescence detection (HG-AFS). Results of method optimization are presented and discussed. A detection limit <125 microg/kg arsenic was obtained; the quantitation limit was close to 400 microg/kg, with repeatability and reproducibility <5% relative standard deviation. Validation was performed by analyzing 4Reference Materials (arsenic concentration expressed as mg/kg): The National Institute of Standards and Technology SRM 1566a Oyster tissue (14.0 +/- 1.2); the Bureau Community of Reference (now Standard Measurements & Testing Program) CRM 278 Mussel tissue (5.9 +/- 0.2) and CRM 627 Tuna fish (4.8 +/- 0.3); and the International Atomic Energy Agency RM 140 Fucus sample (44.3 +/- 2.1).

Animals↗

Therapeutic field trial of a macro- and microfilaricidal agent in canine filariasis.

The discovery in 1973 of a synergistic effect of the arsenical compound F 151, a macrofilaricide, and the benzimidazole compound HOE 33258, a microfilaricide, led to the preparation of the reaction product of F 151 and HOE 33258 (in the proportion 1 mol to 2 mol, respectively), which was designated by the letter E. This compound E proved to be an effective macro- and microfilaricidal agent when administered subcutaneously in a single well-tolerated dose to dogs that were naturally infected with Dirofilaria immitis.

Animals↗

Comparative and environmental genotoxicity of antimony and arsenic.

Antimony and arsenic compounds are known to have a genotoxic potential. Soil contamination with these elements can be due to the presence of natural ore sources of fahlore (gray copper). As a result, human and animal populations may be highly exposed. The sister chromatid exchange (SCE) test is an adequate tool for the sensitive detection of antimony and arsenic genotoxicity. We used this assay to investigate the coergism of the two elements in vitro to gain data for the assessment of a putative risk from coexposure. The combinative effect of antimony and arsenic in the SCE test appeared subadditive. Additionally, the SCE served to determine the genotoxic potential in extracts of contaminated fahlore soil samples gained under mildly acidic conditions. The genotoxicity observed was very low because antimony and arsenic predominated in the pentavalent, non-genotoxic state, but, the partial antagonism observed in the in vitro experiments could be an additional explanation for the low genotoxicity.

Adult↗

Trypanosoma brucei: lack of cross-resistance to melarsoprol in vitro by cymelarsan-resistant parasites.

We have examined cross-resistance between trypanocidal drugs using a well-characterised drug-sensitive line, 247, and its cymelarsan-resistant derivative, 247melCyR. The cymelarsan-resistant line was cross-resistant to trimelarsen and melarsen oxide, and partially cross-resistant to two diamidines, pentamidine and berenil (diminazene aceturate). It was cross-resistant to lipid-soluble melarsoprol in vivo but to only a trivial degree in two in vitro assays. The potential role of adenosine transport in arsenical-induced killing of parasites was investigated. Adenosine, adenine, and the diamidines, but not inosine, were able to inhibit killing of drug-sensitive STIB 247 trypanosomes by cymelarsan and melarsen oxide in a concentration-dependent manner. These results are consistent with the view that these arsenical compounds enter trypanosomes via an adenosine-specific transporter. Melarsoprol-induced killing of trypanosomes was unaffected, however, by either purine and to only a slight degree by the diamidines. These data suggest that melarsoprol can enter trypanosomes by a route other than through an adenosine transporter and that there may be two mechanisms contributing to arsenical resistance in this drug-resistant line of trypanosomes.

Adenine↗

Arsenic accumulation in livers of pinnipeds, seabirds and sea turtles: subcellular distribution and interaction between arsenobetaine and glycine betaine.

Concentrations of total arsenic and individual arsenic compounds were determined in liver samples of pinnipeds (northern fur seal Callorhinus ursinus and ringed seal Pusa hispida), seabirds (black-footed albatross Diomedea nigripes and black-tailed gull Larus crassirostris) and sea turtles (hawksbill turtle Eretmochelys imbricata and green turtle Chelonia mydas). Among these species, the black-footed albatross contained the highest hepatic arsenic concentration (5.8+/-3.7 microg/g wet mass). Arsenobetaine was the major arsenic species found in the liver of all these higher tropic marine animals. To investigate the cause of high accumulation of arsenobetaine, subcellular distribution of arsenic and relationship between arsenobetaine and glycine betaine concentrations were examined in the livers of these animals. There was no relationship between total arsenic concentration and its subcellular distribution in liver tissues. However, a significant negative correlation was found between arsenobetaine and glycine betaine concentrations in the liver of six species examined. This result may indicate that arsenobetaine is accumulated in these marine animals as an osmolyte along with glycine betaine, which is a predominant osmolyte in marine animals because the chemical structure and properties of arsenobetaine are similar to those of glycine betaine.

Animals↗

Determination of arsenic in blood and stomach contents by inductively coupled plasma/mass spectrometry (ICP/MS).

Inductively coupled plasma/mass spectrometry (ICP/MS) was used and evaluated for the practical analysis of the arsenic content of body fluid samples without ashing. The calibration curve for arsenic in blood solution was shown to have good sensitivity, linearity and reproducibility. Blood obtained from normal volunteers was determined by ICP/MS, and compared with that determined by atomic absorption spectrometry (AAS). The arsenic contents determined by ICP/MS showed a linear correlation with that determined by AAS. Furthermore, arsenic was determined in the blood and supernatant of stomach contents obtained from a suicide autopsy case resulting from ingestion of an arsenic compound. It was therefore concluded that ICP/MS could be used rapidly and conveniently in the field of forensic toxicology in acute metal poisoning cases.

Arsenic↗

Arsenic accumulation in three species of sea turtles.

Arsenic in the liver, kidney and muscle of three species of sea turtles, e.g., green turtles (Chelonia mydas), loggerhead turtles (Caretta caretta) and hawksbill turtles (Eretmochelys imbricata), were determined using HG-AAS, followed by arsenic speciation analysis using HPLC-ICP-MS. The order of arsenic concentration in tissues was muscle > kidney > liver. Unexpectedly, the arsenic concentrations in the hawksbill turtles feeding mainly on sponges were higher than the two other turtles primarily eating algae and mollusk which accumulate a large amount of arsenic. Especially, the muscles of the hawksbill turtles contained remarkably high arsenic concentrations averaging 153 mg kg(-1) dry weight with the range of 23.1-205 mg kg(-1) (n = 4), even in comparison with the data from other organisms. The arsenic concentrations in the tissues of the green turtles were significantly decreased with standard carapace length as an indicator of growth. In arsenic compounds, arsenobetaine was mostly detected in the tissues of all the turtles. Besides arsenobetaine, a small amount of dimethylarsinic acid was also observed in the hawksbill turtles.

Animals↗

Biogeochemical transformations of arsenic in circumneutral freshwater sediments.

Arsenic is a wide-spread contaminant of soils and sediments, and many watersheds worldwide regularly experience severe arsenic loading. While the toxicity of arsenic to plants and animals is well recognized, the geochemical and biological transformations that alter its bioavailability in the environment are multifaceted and remain poorly understood. This communication provides a brief overview of our current understanding of the biogeochemistry of arsenic in circumneutral freshwater sediments, placing special emphasis on microbial transformations. Arsenic can reside in a number of oxidation states and complex ions. The common inorganic aqueous species at circumneutral pH are the negatively charged arsenates (H2As(V)O4(-) and Has(V)O4(2-)) and zero-charged arsenite (H3As(III)O3(0)). Arsenic undergoes diagenesis in response to both physical and biogeochemical processes. It accumulates in oxic sediments by adsorption on and/or co-precipitation with hydrous iron and manganese oxides. Burial of such sediments in anoxic/suboxic environments favors their reduction, releasing Fe(II), Mn(II) and associated adsorbed/coprecipitated As. Upward advection can translocate these cations and As into the overlying oxic zone where they may reprecipitate. Alternatively, As may be repartitioned to the sulfidic phase, forming precipitates such as arsenopyrite and orpiment. Soluble and adsorbed As species undergo biotic transformations. As(V) can serve as the terminal electron acceptor in the biological oxidation of organic matter, and the limited number of microbes capable of this transformations are diverse in their phylogeny and physiology. Fe(III)-respiring bacteria can mobilize both As(V) and As(III) bound to ferric oxides by the reductive dissolution of iron-arsenate minerals. SO4(2-)-reducing bacteria can promote deposition of As(III) as sulfide minerals via their production of sulfide. A limited number of As(III)-oxidizing bacteria have been identified, some of which couple this reaction to growth. Lastly, prokaryotic and eukaryotic microbes can alter arsenic toxicity either by coupling cellular export to its reduction or by converting inorganic As to organo-arsenical compounds. The degree to which each of these metabolic transformations influences As mobilization or sequestration in different sedimentary matrices remains to be established.

Arsenic↗