Enhanced adsorption of arsenate on titanium dioxide using Ca and Mg ions

In this study, we report the effects of pH and divalent cations on the adsorption of arsenate (As(V)) by titanium dioxide (TiO₂) nanoparticles. The extent of As(V) adsorption on TiO₂ decreased with increasing pH due to the decrease of positively charged binding sites on the TiO₂ surface. The Langmuir maximum uptake capacity at pH 4 is about three times higher than that at pH 7. Here we show that the relatively low As(V) uptake at circumneutral pH could be substantially enhanced by the addition of common divalent cations such as magnesium and calcium. At a concentration of approximately 7 mM, magnesium and calcium increased the extent of As(V) adsorption from 2.1 to 6.5 and 7.7 mg As(V)/g TiO₂, respectively.     

Characterization of arsenic content in marine organisms from temperate, tropical, and polar environments

Arsenic is a widely distributed element which occurs in several chemical forms in the marine environment. Inorganic arsenic mediates the most toxic effects and predominates in sea water and sediments, while organisms generally accumulate non-toxic organic forms to concentrations probably reflecting species-specific characteristics in arsenic metabolism. This work represents an additional contribution to our knowledge on natural levels and chemical speciation of arsenic in marine organisms; basal concentrations were characterized in several species (bivalves, crustaceans, and fishes) from different environments (polar, temperate, and tropical latitudes), and results revealed an elevated variability with values ranging from less than 5 to about 200 μg g^-1. No significant effects were observed as a function of the geographical area, with the only exception of crustaceans always showing more elevated arsenic concentrations in Mediterranean species (about 45-110 μg g^-1) compared with tropical species (lower than 30 μg g^-1). Chemical speciation of arsenic was investigated in representative species from the three studied taxa; the predominance of organic forms confirmed the general tendency of marine organisms to bioaccumulate non-toxic arsenic compounds, probably resulting from a detoxification pathway.     

碳酸盐岩矿区河流沉积物中重金属的形态特征及潜在生态风险

黔西北土法炼锌及铅锌选矿厂对河流造成严重的重金属污染。河流沉积物中重金属的化学形态研究表明,同一采样点中不同重金属的形态分布和同一重金属在不同采样点中的形态分布均有较大差异。这可能与沉积物组分的不同亲和力,不同河段沉积物中粘土矿物、有机质、Fe Mn氧化物含量的不同以及人为活动(生活污水、选矿剂、矿渣等)的加入等有关,而碳酸盐岩地质背景的河床本身可能也有较大影响。潜在生态危害指数法研究表明,沉积物中重金属表现出强生态风险性,产生生态危害的主要重金属污染物是Pb,其后依次是Cd、Cu和Zn。     

新疆奎屯垦区地下水砷-氟复合污染及成因初探

通过对新疆奎屯垦区3个团场现有自流井水的采样测定,研究了该地区地下水中砷、氟的污染现状、砷和氟的相关性,并对该地区砷氟复合污染的成因进行了分析,同时与中国北方其他砷、氟污染较为严重的地区进行了对比。结果表明:新疆奎屯3个团场自流井水中砷浓度在0.079~0.381 mg/L、氟浓度在2.30~8.02 mg/L,均高于国家饮用水标准,属于重度污染,砷最高值为饮用水标准的38倍,氟最高值为饮用水标准的8倍;自流井水中砷与氟呈显著正相关,砷与海拔高度呈显著负相关,氟与海拔高度呈极显著负相关;新疆奎屯垦区地下水属于原生高砷高氟地下水,该地区为第四纪洪积平原,气候干燥、蒸发量远大于降水量,蒸发浓缩作用强烈,该地区地下水中砷和氟浓度高于我国北方其它高砷高氟地区。     

Arsenic retention and transport behavior in the presence of typical anionic and nonionic surfactants

The massive production and wide use of surfactants have resulted in a large amount of surfactant residuals being discharged into the environment,which could have an impact on arsenic behavior.In the present study,the influence of the anionic surfactant sodium dodecyl benzene sulfonate(SDBS) and nonionic surfactant polyethylene glycol octylphenyl ether(Triton X-100) on arsenic behavior was investigated in batch and column tests.The presence of SDBS and Triton X-100 reduced arsenic retention onto ferrihydrite(FH),enhanced arsenic transport through FH coated sand(FH-sand) columns and promoted arsenic release from the FH surface.With coexisting surfactants in solution,the equilibrium adsorbed amount of arsenic on FH decreased by up to 29.7% and the adsorption rate decreased by up to 52.3%.Pre-coating with surfactants caused a decrease in the adsorbed amount and adsorption rate of arsenic by up to 15.1% and 58.3%,respectively.Because of the adsorption attenuation caused by surfactants,breakthrough of As(Ⅴ) and As(Ⅲ) with SDBS in columns packed with FH-sand was 23.8% and 14.3%faster than that in those without SDBS,respectively.In columns packed with SDBS-coated FH-sand,transport of arsenic was enhanced to a greater extent.Breakthrough of As(Ⅴ) and As(Ⅲ) was 52.4% and 43.8% faster and the cumulative retention amount was 44.5% and 57.3% less than that in pure FH-sand column systems,respectively.Mobilization of arsenic by surfactants increased with the increase of the initial adsorbed amount of arsenic.The cumulative release amount of As(Ⅴ) and As(Ⅲ) from the packed column reached 10.8% and 36.0%,respectively.     

Cellular arsenic transport pathways in mammals

Natural contamination of drinking water with arsenic results in the exposure of millions of people world-wide to unacceptable levels of this metalloid. This is a serious global health problem because arsenic is a Group 1 (proven) human carcinogen and chronic exposure is known to cause skin, lung, and bladder tumors. Furthermore, arsenic exposure can result in a myriad of other adverse health effects including diseases of the cardiovascular, respiratory, neurological, reproductive, and endocrine systems. In addition to chronic environmental exposure to arsenic, arsenic trioxide is approved for the clinical treatment of acute promyelocytic leukemia, and is in clinical trials for other hematological malignancies as well as solid tumors. Considerable inter-individual variability in susceptibility to arsenic-induced disease and toxicity exists, and the reasons for such differences are incompletely understood. Transport pathways that influence the cellular uptake and export of arsenic contribute to regulating its cellular, tissue, and ultimately body levels. In the current review, membrane proteins (including phosphate transporters, aquaglyceroporin channels, solute carrier proteins, and ATP-binding cassette transporters) shown experimentally to contribute to the passage of inorganic, methylated, and/or glutathionylated arsenic species across cellular membranes are discussed. Furthermore, what is known about arsenic transporters in organs involved in absorption, istribution, and metabolism and how transport pathways contribute to arsenic elimination are described.     

Comparative cytotoxicity of fourteen trivalent and pentavalent arsenic species determined using real-time cell sensing

The occurrence of a large number of diverse arsenic species in the environment and in biological systems makes it important to compare their relative toxicity. The toxicity of arsenic species has been examined in various cell lines using different assays, making comparison difficult. We report real-time cell sensing of two human cell lines to examine the cytotoxicity of fourteen arsenic species: arsenite(As~Ⅲ), monomethylarsonous acid(MMA~Ⅲ) originating from the oxide and iodide forms, dimethylarsinous acid(DMA~Ⅲ), dimethylarsinic glutathione(DMAG~Ⅲ), phenylarsine oxide(PAO~Ⅲ), arsenate(AsV), monomethylarsonic acid(MMA~Ⅴ), dimethylarsinic acid(DMA~Ⅴ),monomethyltrithioarsonate(MMTTA~Ⅴ), dimethylmonothioarsinate(DMMTA~Ⅴ),dimethyldithioarsinate(DMDTA~Ⅴ), 3-nitro-4-hydroxyphenylarsonic acid(Roxarsone, Rox),and 4-aminobenzenearsenic acid(p-arsanilic acid, p-ASA). Cellular responses were measured in real time for 72 hr in human lung(A549) and bladder(T24) cells. IC50 values for the arsenicals were determined continuously over the exposure time, giving rise to IC50 histograms and unique cell response profiles. Arsenic accumulation and speciation were analyzed using inductively coupled plasma-mass spectrometry(ICP-MS). On the basis of the 24-hr IC50 values, the relative cytotoxicity of the tested arsenicals was in the following decreasing order: PAO~Ⅲ? MMA~Ⅲ≥ DMA~Ⅲ≥ DMAG~Ⅲ≈ DMMTA~Ⅴ≥ As~Ⅲ? MMTTA~Ⅴ AsV DMDTA~ⅤDMA~Ⅴ MMA~Ⅴ≥ Rox ≥ p-ASA. Stepwise shapes of cell response profiles for DMA~Ⅲ, DMAG~Ⅲ,and DMMTA~Ⅴcoincided with the conversion of these arsenicals to the less toxic pentavalent DMA~Ⅴ. Dynamic monitoring of real-time cellular responses to fourteen arsenicals provided useful information for comparison of their relative cytotoxicity.     

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

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

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

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

Arsenic methylation by an arsenite S-adenosylmethionine methyltransferase from Spirulina platensis

Arsenic-contaminated water is a serious hazard for human health. Plankton plays a critical role in the fate and toxicity of arsenic in water by accumulation and biotransformation.Spirulina platensis(S. platensis), a typical plankton, is often used as a supplement or feed for pharmacy and aquiculture, and may introduce arsenic into the food chain, resulting in a risk to human health. However, there are few studies about how S. platensis biotransforms arsenic. In this study, we investigated arsenic biotransformation by S. platensis. When exposed to arsenite(As(Ⅲ)), S. platensis accumulated arsenic up to 4.1 mg/kg dry weight.After exposure to As(Ⅲ), arsenate(As(Ⅴ)) was the predominant species making up 64% to86% of the total arsenic. Monomethylarsenate(MMA(Ⅴ)) and dimethylarsenate(DMA(Ⅴ))were also detected. An arsenite S-adenosylmethionine methyltransferase from S. platensis(Sp Ars M) was identified and characterized. Sp Ars M showed low identity with other reported Ars M enzymes. The Escherichia coli AW3110 bearing Spars M gene resulted in As(Ⅲ) methylation and conferring resistance to As(Ⅲ). The in vitro assay showed that Sp Ars M exhibited As(Ⅲ) methylation activity. DMA(Ⅴ) and a small amount of MMA(Ⅴ) were detected in the reaction system within 0.5 hr. A truncated Sp Ars M derivative lacking the last 34 residues still had the ability to methylate As(Ⅲ). The three single mutants of Sp Ars M(C59S, C186 S, and C238S) abolished the capability of As(Ⅲ) methylation, suggesting the three cysteine residues are involved in catalysis. We propose that Sp Ars M is responsible for As methylation and detoxification of As(Ⅲ) and may contribute to As biogeochemistry.