Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Congener-specific detection of dioxins using jet-REMPI

Although 210 chemically different polychlorinated dibenzo-p-dioxin and dibenzofuran congeners can be produced during combustion, it is currently believed that fewer than 20 are toxic enough to warrant monitoring. SRI is developing a continuous emissions monitor to study the emission levels of these most toxic dioxins, leading eventually to an improved understanding of the formation of these molecules and to improved means of monitoring and control. We report here the first results of performing congener-specific detection for two dichloro dibenzo-p-dioxins present in low ppt concentrations in a mixture using the supersonic jet/resonantly enhanced multiphoton ionization time-of-flight mass spectrometer technique. In addition, we present preliminary data on the detection of chlorinated aromatic compounds using a two-color REMPI scheme with the same instrument.     

Analysis of accumulation, extractability, and metabolization of five different phenylarsenic compounds in plants by ion chromatography with mass spectrometric detection and by atomic emission spectroscopy

Phenylated arsenic compounds occur as highly toxic contaminants in former military areas where they were formed as degradation products of chemical warfare agents. Some phenylarsenic compounds such as roxarsone and aminophenylarsonic acids were applied as food additive and veterinary drugs in stock-breeding and therefore pose an environmental risk in agricultural used sites. Very few data exist in the literature concerning uptake and effects of phenylarsenic compounds in plants growing on contaminated soils. In this study, the accumulation, extractability, and metabolization of five different phenylarsenic compounds, phenylarsonic acid, p- and o-aminophenylarsonic acid, phenylarsine oxide, and 3-nitro-4-hydroxyphenylarsonic acid called roxarsone, by the terrestrial plant Tropaeolum majus were investigated. Ion chromatography coupled to inductively coupled plasma mass spectrometry was used to differentiate these arsenic compounds, and inductively coupled plasma atomic emission spectroscopy was used for total arsenic quantification. All compounds considered were taken up by the roots and transferred to stalks, leaves, and flowers. The strongest accumulation was observed for unsubstituted phenylarsonic acid followed by its trivalent analogue phenylarsine oxide that was mostly oxidized in soil whereas the amino- or nitro- and hydroxy-substituted phenylarsonic acids were accumulated to a smaller degree.The highest extraction yield of 90% for ground leaf material was achieved by 0.1 M phosphate buffer, pH 7.7, in a two-step extraction with a total extraction time of 24 h. The extraction of higher amounts of arsenic (50–70% of total arsenic present in leaves depending on arsenic species application) from non-ground intact leaves with deionized water in comparison with the buffer (20–40% of total arsenic) is ascribed to osmotic effects. The arsenic species analysis revealed a cleavage of the amino groups from the phenyl ring for plants treated with aminophenylarsonic acids. A further important metabolic effect consisted in the production of inorganic arsenate and arsenite from the phenylated arsonic acid groups.     

Analysis of accumulation,extractability, and metabolization of five different phenylarsenic compounds in plants by ion chromatography with mass spectrometric detection and by atomic emission spectroscopy

Phenylated arsenic compounds occur as highly toxic contaminants in former military areas where they were formed as degradation products of chemical warfare agents. Some phenylarsenic compounds such as roxarsone and aminophenylarsonic acids were applied as food additive and veterinary drugs in stock-breeding and therefore pose an environmental risk in agricultural used sites. Very few data exist in the literature concerning uptake and effects of phenylarsenic compounds in plants growing on contaminated soils. In this study, the accumulation, extractability, and metabolization of five different phenylarsenic compounds, phenylarsonic acid, p- and o-aminophenylarsonic acid, phenylarsine oxide, and 3-nitro-4-hydroxyphenylarsonic acid called roxarsone, by the terrestrial plant Tropaeolum majus were investigated. Ion chromatography coupled to inductively coupled plasma mass spectrometry was used to differentiate these arsenic compounds, and inductively coupled plasma atomic emission spectroscopy was used for total arsenic quantification. All compounds considered were taken up by the roots and transferred to stalks, leaves, and flowers. The strongest accumulation was observed for unsubstituted phenylarsonic acid followed by its trivalent analogue phenylarsine oxide that was mostly oxidized in soil whereas the amino- or nitro- and hydroxy-substituted phenylarsonic acids were accumulated to a smaller degree.The highest extraction yield of 90% for ground leaf material was achieved by 0.1 M phosphate buffer, pH 7.7, in a two-step extraction with a total extraction time of 24 h. The extraction of higher amounts of arsenic (50–70% of total arsenic present in leaves depending on arsenic species application) from non-ground intact leaves with deionized water in comparison with the buffer (20–40% of total arsenic) is ascribed to osmotic effects. The arsenic species analysis revealed a cleavage of the amino groups from the phenyl ring for plants treated with aminophenylarsonic acids. A further important metabolic effect consisted in the production of inorganic arsenate and arsenite from the phenylated arsonic acid groups.     

The anaerobic degradation of endosulfan by indigenous microorganisms from low-oxygen soils and sediments

Indigenous mixed populations of anaerobic microorganisms from an irrigation tailwater drain and submerged agricultural chemical waste pit readily biodegraded the major isomer of endosulfan (endosulfan I). Endosulfan I was biodegraded to endosulfan diol, a low toxicity degradation product, in the presence of organic carbon sources under anaerobic, methanogenic conditions. While there was extensive degradation (>85%) over the 30 days, there was no significant enhancement of degradation from enriched inocula. This study demonstrates that endosulfan I has the potential to be biodegraded in sediments, in the absence of enriched microorganisms. This is of particular importance since such sediments are prevalent in cotton-growing areas and are typically contaminated with endosulfan residues. The importance of minimizing non-biological losses has also been highlighted as a critical issue in determining anaerobic biodegradation potential. Seals for such incubation vessels must be both oxygen and pollutant impermeable. Teflon-lined butyl rubber provides such a seal because of its resistance to the absorption of volatiles and in preventing volatilization. Moreover, including a 100 mM phosphate buffer in the anaerobic media has reduced non-biological losses from chemical hydrolysis, allowing biodegradation to be assessed.     

Effect of sulfide on the cytotoxicity of arsenite and arsenate in human hepatocytes (HepG2) and human urothelial cells (UROtsa)

Arsenic, a common poison, is known to react with sulfide in vivo, forming thioarsenates. The acute toxicity of the inorganic thioarsenates is currently unknown. Our experiments showed that a fourfold sulfide excess reduced acute arsenite cytotoxicity in human hepatocytes (HepG2) and urothelial cells (UROtsa) significantly, but had little effect on arsenate toxicity. Speciation analysis showed immediate formation of thioarsenates (up to 73 % of total arsenic) in case of arsenite, but no speciation changes for arsenate. Testing acute toxicity of mono- and trithioarsenate individually, both thioarsenates were found to be more toxic than their structural analogue arsenate, but less toxic than arsenite. Toxicity increased with the number of thio groups. The amount of cellular arsenic uptake after 24 h corresponded to the order of toxicity of the four compounds tested. The dominant to almost exclusive intracellular arsenic species was arsenite. The results imply that thiolation is a detoxification process for arsenite in sulfidic milieus. The mechanism could either be that thioarsenates regulate the amount of free arsenite available for cellular uptake without entering the cells themselves, or, based on their chemical similarity to arsenate, they could be taken up by similar transporters and reduced rapidly intracellularly to arsenite.     

Arsenic-transforming microbes and their role in biomining processes

It is well known that microorganisms can dissolve different minerals and use them as sources of nutrients and energy. The majority of rock minerals are rich in vital elements (e.g., P, Fe, S, Mg and Mo), but some may also contain toxic metals or metalloids, like arsenic. The toxicity of arsenic is disclosed after the dissolution of the mineral, which raises two important questions: (1) why do microorganisms dissolve arsenic-bearing minerals and release this metal into the environment in a toxic (also for themselves) form, and (2) How do these microorganisms cope with this toxic element? In this review, we summarize current knowledge about arsenic-transforming microbes and their role in biomining processes. Special consideration is given to studies that have increased our understanding of how microbial activities are linked to the biogeochemistry of arsenic, by examining (1) where and in which forms arsenic occurs in the mining environment, (2) microbial activity in the context of arsenic mineral dissolution and the mechanisms of arsenic resistance, (3) the minerals used and technologies applied in the biomining of arsenic, and (4) how microbes can be used to clean up post-mining environments.     

Arsenic speciation in marine fish and shellfish from American Samoa

We speciated arsenic compounds in marine fish and shellfish from two islands of the United States Territory of American Samoa in the South Pacific, and found that inorganic arsenic occurred as a minor fraction. The proportion of inorganic arsenic was generally far below the levels of prevailing assumptions typically used in human health risk assessments when only total arsenic is analysed. Fish and shellfish were collected from Tutuila and Ofu between May 2001 and March 2002 (n=383 individual specimens, with 117 composites); sites were selected based on habitat type and were representative of those frequented by local fishers. These islands have moderately developed reef fish fisheries among artisanal fishers, are far removed from any industrial or mining sources of arsenic, and presented an opportunity to study arsenic variations in marine biota from un-impacted environments. Target species were from various trophic levels and are among those frequently harvested for human consumption. We found evidence that arsenic concentrated in some marine species, but did not tend to follow classic trophic patterns for biomagnification or bioaccumulation. For the majority of samples, inorganic arsenic was less than 0.5% of total arsenic, with only a few samples in the range of 1-5%, the latter being mollusks which are recognized to have unusually high arsenic levels in general. This work supports the importance of speciation analysis for arsenic, because of the ubiquitous occurrence of arsenic in the environment, and its variable toxicity depending on chemical form.     

From classic methodologies to application of nanomaterials for soil remediation: an integrated view of methods for decontamination of toxic metal(oid)s

Soil pollution with toxic elements is a recurrent issue due to environmental disasters, fossil fuel burning, urbanization, and industrialization, which have contributed to soil contamination over the years. Therefore, the remediation of toxic metals in soil is always an important topic since contaminated soil can affect the environment, agricultural safety, and human health. Many remediation methods have been developed; however, it is essential to ensure that they are safe, and also take into account the limitation of each methodology (including high energy input and generation of residues). This scenario has motivated this review, where we explore soil contamination with arsenic, lead, mercury, and chromium and summarize information about the methods employed to remediate each of these toxic elements such as phytoremediation, soil washing, electrokinetic remediation, and nanoparticles besides elucidating some mechanisms involved in the remediation. Considering all the discussed techniques, nowadays, different techniques can be combined together in order to improve the efficiency of remediation besides the new approach of the techniques and the use of one technique for remediating more than one contaminant.     

Evaluating of arsenic(V) removal from water by weak-base anion exchange adsorbents

Arsenic contamination of groundwater has been called the largest mass poisoning calamity in human history and creates severe health problems. The effective adsorbents are imperative in response to the widespread removal of toxic arsenic exposure through drinking water. Evaluation of arsenic(V) removal from water by weak-base anion exchange adsorbents was studied in this paper, aiming at the determination of the effects of pH, competing anions, and feed flow rates to improvement on remediation. Two types of weak-base adsorbents were used to evaluate arsenic(V) removal efficiency both in batch and column approaches. Anion selectivity was determined by both adsorbents in batch method as equilibrium As(V) adsorption capacities. Column studies were performed in fixed-bed experiments using both adsorbent packed columns, and kinetic performance was dependent on the feed flow rate and competing anions. The weak-base adsorbents clarified that these are selective to arsenic(V) over competition of chloride, nitrate, and sulfate anions. The solution pH played an important role in arsenic(V) removal, and a higher pH can cause lower adsorption capacities. A low concentration level of arsenic(V) was also removed by these adsorbents even at a high flow rate of 250–350 h^?1. Adsorbed arsenic(V) was quantitatively eluted with 1 M HCl acid and regenerated into hydrochloride form simultaneously for the next adsorption operation after rinsing with water. The weak-base anion exchange adsorbents are to be an effective means to remove arsenic(V) from drinking water. The fast adsorption rate and the excellent adsorption capacity in the neutral pH range will render this removal technique attractive in practical use in chemical industry.     

Quantitative determination of arsenobetaine,the major water-soluble arsenical in three species of crab,using high pressure liquid chromatography and an inductively coupled argon plasma emission spectrometer as the arsenic-specific detector

The major water-soluble arsenic compound in the Alaskan king crab, the Alaskan snow crab, and the Dungeness crab was identified as arsenobetaine by HPLC/ICP analysis. This technique is suitable for the identification and quantitative determination of naturally occurring organic arsenic compounds in purified and partially purified extracts from biota.     

Toxicity assessment of the maize herbicides S-metolachlor,benoxacor, mesotrione and nicosulfuron,and their corresponding commercial formulations,alone and in mixtures,using the Microtox® test

The Microtox® test, using the prokaryote Vibrio fischeri, was employed to assess the toxicity of the maize herbicides S-metolachlor, benoxacor, mesotrione and nicosulfuron, and their formulated compounds: Dual Gold Safeneur®, Callisto® and Milagro®; alone and in mixtures. For each compound we obtained original IC₅₀ values, with consistent higher toxicities for formulated compounds compared to active ingredients alone. Mixtures of the four herbicides, prepared according to application doses encountered in agriculture, were found to be toxic at a lower concentration than single molecules. Mesotrione and nicosulfuron mixture appeared to be highly toxic to V. fischeri, however, this recommended post-emergence combination for maize crops got its toxicity decreased in formulated compound mixtures, suggesting that chemical interactions could potentially reduce the toxicity. Data comparisons to theoretical models showed a good prediction of mixture toxicity by Concentration Addition concept. Results seemed to exclude any synergistic effects on V. fischeri for the tested herbicide mixtures. Additional work coupling these bioassay data to ecosystemic level studies (aquatic and soil compartments) and data on additives and degradation products toxicity, will help to fill the gap in our knowledge of the environmental impact of these xenobiotics and in the choice of a more sustainable use of pesticides.     

Leaching of cyanogenic glucosides and cyanide from white clover green manure

Use of crops for green manure as a substitute for chemical fertilizers and pesticides is an important approach towards more sustainable agricultural practices. Green manure from white clover is rich in nitrogen but white clover also produces the cyanogenic glucosides (CGs) linamarin and lotaustralin; CGs release toxic hydrogen cyanide (HCN) upon hydrolysis which may be utilized for pest control. We demonstrate that applying CGs in the form of a liquid extract of white clover to large columns of intact agricultural soils can result in leaching of toxic cyanide species to a depth of at least 1m. Although degradation of the CGs during leaching proceeded with half lives in the interval 1.5-35 h depending on soil characteristics, a fraction of the applied CGs (0.9-3.2%) was recovered in the leachate as either CGs or toxic cyanide species. Detoxification of the HCN formed was rapid in soil and leachate from both sandy and loamy soil. However, 30% of the leachate samples exceeded the EU threshold value of 50 micrgl(-1) total cyanide for drinking water and 85% exceeded the US threshold of 5 micrgl(-1) for cyanide chronic ecotoxicity in fresh water. This study demonstrates that even easily degradable natural products present in crop plants as defense compounds pose a threat to the quality of groundwater and surface waters. This aspect needs consideration in assessment of the risk associated with use of crops as green manure to replace chemical fertilizers and pesticides as well as in genetic engineering approaches to design crops with improved pest resistance.     

Current and emerging strategies for organophosphate decontamination: special focus on hyperstable enzymes

Organophosphorus chemicals are highly toxic molecules mainly used as pesticides. Some of them are banned warfare nerve agents. These compounds are covalent inhibitors of acetylcholinesterase, a key enzyme in central and peripheral nervous systems. Numerous approaches, including chemical, physical, and biological decontamination, have been considered for developing decontamination methods against organophosphates (OPs). This work is an overview of both validated and emerging strategies for the protection against OP pollution with special attention to the use of decontaminating enzymes. Considerable efforts have been dedicated during the past decades to the development of efficient OP degrading biocatalysts. Among these, the promising biocatalyst SsoPox isolated from the archaeon Sulfolobus solfataricus is emphasized in the light of recently published results. This hyperthermostable enzyme appears to be particularly attractive for external decontamination purposes with regard to both its catalytic and stability properties.     

Heavy metals detection in river water with cantilever nanobiosensor

Abstract

Heavy metals can be highly toxic depending on the dose and the chemical form. In this context, sensing devices such as nanobiosensors have been presented as a promising tool to monitor contaminants at micro and nanoscale. In this work, cantilever nanobiosensors with phosphatase alkaline were developed and applied to detect heavy metals (Pb, Ni, Cd, Zn, Co, and Al) in river water. The nanobiosensor surface was functionalized by the self-assembled monolayers (SAM) technique using 16-mercaptohexadecanoic acid, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (EDC) and N- hydroxysuccinimide (NHS), and phosphatase alkaline enzyme. The sensing layer deposited on the cantilever surface presented a uniform morphology, at nanoscale, with 80?nm of thickness. The nanobiosensor showed a detection limit in the ppb range and high sensitivity, with a stability of fifteen days. The developed cantilever nanobiosensor is a simple tool, suitable for the direct detection of contaminants in river water.     

Grundwasserbelastung durch Rüstungsaltlast-Emissionen Nachweis von Arsenkampfstoffen und weiteren kampfmittelspezifischen Rückst?nden

Die Ergebnisse der Untersuchung von Wasserproben aus dem Einflu?ereich der Rüstungsaltlast „Dethlinger Teich“ bei Munster/Niedersachsen werden dargestellt und bewertet. Von mehr als 50 untersuchten spezifischen Substanzen wurden Arsenkampfstoffe als Hauptkontaminanten erkannt. Im Rahmen der Gef?hrdungsabsch?tzung wird hier erstmals eine Analysenmethode zur Unterscheidung zwischen anorganisch und organisch gebundenem Arsen vorgestellt. Groundwater analyses in the area of the former munitions depository (World War II) „Dethlinger Teich“ near Munster/Niedersachsen were evaluated. Results from 50 different chemical substances showed that arsenic compounds are the main contaminating chemicals. A new method has been developed to distinguish between morganically- and organically bound compounds. This differentiation is required for risk assessment and evaluation. Also, the relationship of chemical structure and physiological effects in organo arsenic compounds is described.     

The potential for kelp manufacture to lead to arsenic pollution of remote Scottish islands

Burning seaweed to produce kelp, valued for its high potash and soda content, was formerly a significant industry in remote coastal areas of Scotland and elsewhere. Given the high concentrations of arsenic in seaweeds, up to 100 mg kg(-1), this study investigates the possibility that the kelp industry caused arsenic contamination of these pristine environments. A series of laboratory-scale seaweed burning experiments was conducted, and analysis of the products using HPLC ICP-MS shows that at least 40% of the arsenic originally in the seaweed could have been released into the fumes. The hypothesis that the burning process transforms arsenic from low toxicity arsenosugars in the original seaweeds (Fucus vesiculosus and Laminaria digitata) to highly toxic inorganic forms, predominantly arsenate, is consistent with As speciation analysis results. A field study conducted on Westray, Orkney, once a major centre for kelp production, shows that elevated arsenic levels (10.7+/-3.0 mg kg(-1), compared to background levels of 1.7+/-0.2 mg kg(-1)) persist in soils in the immediate vicinity of the kelp burning pits. A model combining results from the burning experiments with data from historical records demonstrates the potential for arsenic deposition of 47 g ha(-1) year(-1) on land adjacent to the main kelp burning location on Westray, and for arsenic concentrations exceeding current UK soil guideline values during the 50 year period of peak kelp production.     

Arsenic speciation in arsenic-rich Brazilian soils from gold mining sites under anaerobic incubation

BACKGROUND: Arsenic speciation in environmental samples is essential for studying toxicity, mobility and bio-transformation of As in aquatic and terrestrial environments. Although the inorganic species As(III) and As(V) have been considered dominant in soils and sediments, organisms are able to metabolize inorganic forms of arsenic into organo-arsenic compounds. Arsenosugars and methylated As compounds can be found in terrestrial organisms, but they generally occur only as minor constituents. We investigated the dynamics of arsenic species under anaerobic conditions in soils surrounding gold mining areas from Minas Gerais State, Brazil to elucidate the arsenic biogeochemical cycle and water contamination mechanisms. METHODS: Surface soil samples were collected at those sites, namely Paracatu Formation, Banded Iron Formation and Riacho dos Machados Sequence, and incubated in CaCl2 2.5 mmol L(-1) suspensions under anaerobic conditions for 1, 28, 56 and 112 days. After that, suspensions were centrifuged and supernatants analyzed for soluble As species by IC-ICPMS and HPLC-ICPMS. RESULTS: Easily exchangeable As was mainly arsenite, except when reducible manganese was present. Arsenate was mainly responsible for the increase in soluble arsenic due to the reductive dissolution of either iron or manganese in samples from the Paracatu Formation and Riacho dos Machados Sequence. On the other hand, organic species of As dominated in samples from the Banded Iron Formation during anaerobic incubation. DISCUSSION: Results are contrary to the expectation that, in anaerobic environments, As release due to the reductive dissolution of Fe is followed by As(V) reduction to As(III). The occurrence of organo-arsenic species was also found to be significant to the dynamics of soluble arsenic, mainly in soils from the Banded Iron Formation (BIF), under our experimental conditions. CONCLUSIONS: In general, As(V) and organic As were the dominant species in solution, which is surprising under anaerobic conditions in terrestrial environments. The unexpected occurrence of organic species of As was attributed to enrollment of ternary organic complexes or living organisms such as algae or cyanobacteria. PERSPECTIVES: These findings are believed to be useful for remediation strategies in mine-affected regions, as the organic As species are in general considered to be less toxic than inorganic ones and even As(V) is considered less mobile and toxic than As(III).     

Evaluation of reverse phase liquid chromatography/mass spectrometry for estimation of n-octanol/water partition coefficients for organic chemicals

A reverse-phase high pressure liquid chromatography/mass spectrometry (HPLC/MS method was developed for estimating n-octanol/water partition coefficients (K_ow) of anthropogenic molecules in complex chemical mixtures (e.g., complex effluents and solid waste leachates). The average error for an estimated log K_ow was ca. 0.5 and this error was similar for both aliphatic and aromatic compounds. The minimum level of detection using the total ion current profile generally decreased with increasing molecular weight between 100 and 600 daltons. Results obtained demonstrate that the HPLC/MS method is a viable technique for estimating log K_ow's of anthropogenic chemicals in complex environmental samples.