Analytik von Umwandlungsprodukten des Schwefellosts (S-LOST)

The results of investigations of the aquatic ecotoxicity of sternutators and their metabolites (phenyl arsenic compounds) are presented. The standardized luminescence inhibition test (LumisTox, Dr. Lange) with the marine bacteriaVibrio fischeri was applied according to the German norm DIN 38412, part 34. All investigated organic AS(III) compounds exhibit EC₅₀-values (50 % inhibition of the luminescence) of less than 1 mg/l, whereas all investigated organic As(V) compounds and inorganic arsenic show EC₅₀-values exceeding 100 mg/l     

Cellular metabolism of arsenic studied in mammalian cellsin vitro

The cytotoxicity of trivalent and pentavalent inorganic arsenic was studied in cultured mouse fibroblasts. Concentrations of As(III) in the M range and approximately 10-fold higher concentrations of As(V) led to a reduction of cellular proliferation and viability with a concomitant increase of LDH release and stimulation of lactate production. Cells pretreated with a low As(III) concentration were less sensitive to toxic doses of As(III) or As(V).Uptake of As(III) by the cells was greater than that of As(V). Both forms of inorganic arsenic were converted intracellularly to monomethylarsonic (MMA) and dimethylarsinic (DMA) acids, which were subsequently released into the culture medium. In As-pretreated cells, which proved more resistant to As toxicity, biotransformation of inorganic to MMA and DMA was increased.     

Fractionation and speciation of arsenic in fresh and combusted coal wastes from Yangquan, northern China

In this study, the content and speciation of arsenic in coal waste and gas condensates from coal waste fires were investigated, respectively, using the digestion and sequential extraction methods. The fresh and fired-coal waste samples were collected from Yangquan, which is one of the major coal production regions in northern China. High-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) was used to determine the concentrations of four major arsenic species [As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA)] in the extracts, while ICP-MS was used to measure total As content. Arsenic content in the investigated coal wastes and the condensate ranges between 23.3 and 69.3 mg/kg, which are higher than its reported average content in soils. Arsenic in coal waste exists primarily in the residual fraction; this is followed in decreasing order by the organic matter-bound, Fe–Mn oxides-bound, exchangeable, carbonates-bound, and water-soluble fractions. The high content of arsenic in the condensates indicates that combustion or spontaneous combustion is one of the major ways for arsenic release into the environment from coal waste. About 15% of the arsenic in the condensate sample is labile and can release into the environment under leaching processes. The water extractable arsenic (WEA) in the fresh coal waste, fired coal wastes, and the condensate varied between 14.6 and 341 μg/kg, with As(V) as the major species. Furthermore, both MMA and DMA were found in fresh coal wastes, fired coal wastes, and the condensate.     

Effect of arsenic species on the growth and arsenic accumulation in <Emphasis Type="Italic">Cucumis sativus</Emphasis>

The effects of arsenic (As) species, such as As(III), As(V) and dimethylarsinic acid (DMA), on the accumulation of As in cucumber (Cucumis sativus), as well as on its growth in a soil mesocosm were evaluated. When Cucumis sativus was cultivated in soils contaminated with 20 and 50 mg/kg of As(III), As(V) or DMA for 40 days, the growth was markedly inhibited by the inorganic As (As(III) and As(V)) rather than the organic As (DMA). Irrespective of the As species, the As concentrations accumulated in Cucumis sativus increased with increasing As concentration in the soil. The As bioaccumulation factors from soil into the tissue of Cucumis sativus were 17.5–35.4, 29.3–42.7 and 17.6–25.7 for As(III), As(V) and DMA, respectively. In addition, the As translocation factors from the roots to shoots were 0.025–0.031, 0.018–0.032 and 0.014–0.026 for As(III), As(V) and DMA, respectively. In conclusion, Cucumis sativus mainly accumulated As in its roots rather than its shoots and easily accumulated inorganic rather than organic As from the soil into its tissue.     

Effect of arsenic species on the growth and arsenic accumulation in Cucumis sativus

The effects of arsenic (As) species, such as As(III), As(V) and dimethylarsinic acid (DMA), on the accumulation of As in cucumber (Cucumis sativus), as well as on its growth in a soil mesocosm were evaluated. When Cucumis sativus was cultivated in soils contaminated with 20 and 50 mg/kg of As(III), As(V) or DMA for 40 days, the growth was markedly inhibited by the inorganic As (As(III) and As(V)) rather than the organic As (DMA). Irrespective of the As species, the As concentrations accumulated in Cucumis sativus increased with increasing As concentration in the soil. The As bioaccumulation factors from soil into the tissue of Cucumis sativus were 17.5-35.4, 29.3-42.7 and 17.6-25.7 for As(III), As(V) and DMA, respectively. In addition, the As translocation factors from the roots to shoots were 0.025-0.031, 0.018-0.032 and 0.014-0.026 for As(III), As(V) and DMA, respectively. In conclusion, Cucumis sativus mainly accumulated As in its roots rather than its shoots and easily accumulated inorganic rather than organic As from the soil into its tissue.     

离子色谱-电感耦合等离子体质谱联用(IC-ICP-MS)测定水体中的砷形态

使用离子色谱(IC)-电感耦合等离子体质谱(ICP-MS)联用技术对水中砷的形态进行分离检测,对流动相、进样量和流速等条件进行了研究。使用IonpacAS18阴离子色谱柱,NH4HCO3作为淋洗液,1.0mL·min-1流速,成功的进行砷形态分离,该方法在100μL进样量下,4种砷形态(三价砷(As(III))、五价砷(As(V))、一甲基砷(MMA)和二甲基砷(DMA))的方法检出限在10～30ng·L-1之间,方法回收率为82.6%～110%,相对标准偏差(n=6)为2.2%～10.9%。     

碳纳米管影响无机砷(As(III)和As(V))对大型蚤毒性的研究：特定砷形态的作用

作为一种新兴的纳米材料,羟基多壁碳纳米管(OH-MWCNTs)可能与其他污染物在水环境中共存,并进一步影响它们的毒性、输移和归趋。因此,评价碳纳米管存在下砷的毒性变化需要得到更多的关注。该试验探索了在不同pH值条件下,OH-MWCNTs诱导砷(As(III)和As(V))对水生生物大型蚤的毒性变化的潜在机制。发现了H₂AsO₃^-和H₂AsO₄^-是对大型蚤毒性最大的As(III)和As(V)。比较As(III)和As(V)的结果,发现pH值是影响砷毒性最重要的因素。此外,OH-MWCNTs影响砷对大型蚤毒性的结果表明,OH-MWCNTs的存在可以提高砷的毒性。通过吸附实验进一步研究了砷与OH-MWCNTs的相互作用。OH-MWCNTs 对As(V)吸附容量高于As(III)。总而言之, OH-MWCNTs对某些形态砷的吸附是解释砷毒性增强的可靠证据。
精选自Xinghao Wang, Ruijuan Qu, Ahmed A. Allam, Jamaan Ajarem, Zhongbo Wei, Zuoyao Wang. Impact of carbon nanotubes on the toxicity of inorganic arsenic [As(III) and As(V)] to Daphnia magna: the role of the certain arsenic species. Environmental Toxicology and Chemistry: Volume 35, Issue 7, pages 1852–1859, July 2016. DOI: 10.1002/etc.3340
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3340/full
     

Differentiation in low molecular weight organic acids exudation into rhizosphere and their creation in Ulmus laevis Pall organs treated by As – pot experiment

Two-year old Ulmus laevis Pall (U. laevis) seedlings were cultivated in a three-month hydroponic experiment with inorganic (aresenite – As(III) and arsenate – As(V)) and organic (dimethylarsenic acid – DMA(V)) arsenic forms, at 0.06 and/or 0.6?mM concentrations. Further, the profile and content of total low molecular weight organic acids (LMWOAs) were investigated in the rhizosphere, roots and leaves of U. laevis. Obtained results showed that the addition of As(III) or As(V) individually or in a mixture led to increased LMWOAs concentration in the rhizosphere, especially of oxalic and malonic acids, in comparison to the control, while in roots the overall content of the profiled LMWOAs decreased. In both rhizosphere and roots, addition of the DMA(V) form resulted in the inhibition of LMWOAs exudation into the rhizosphere and their creation in plant roots. Leaves were characterised by a higher content of LMWOAs than in the rhizosphere and roots for all experimental systems, where the profile and content of LMWOAs was strictly correlated with the analysed As forms. Our study indicated that creation of LMWOAs in U. laevis organs and their exudation to the rhizosphere could be responsible for the As toxicity tolerance of the plants.     

砷浓度、形态及碳酸氢盐对蜈蚣草吸收砷的影响

为了探讨超富集植物蜈蚣草在处理高砷地下水方面的可行性,研究了水培条件下砷的浓度、形态和碳酸氢盐(HCO-3)对超富集植物蜈蚣草吸收砷的影响。实验中使用了浓度为0.1～100mg·L-1的As(III)和As(V)溶液。HCO-3处理中,HCO-3浓度范围为0.5～20mmol·L-1,As(III)或As(V)的浓度为5mg·L-1。结果表明,在水培条件下,蜈蚣草具有明显的耐高砷特征。当介质砷含量高达100mg·L-1时,砷的去除率可达到80%,且对As(III)的吸收效率高于As(V)。植物体内砷形态研究表明,蜈蚣草体内2种形态砷的含量与外源砷形态有一定的关系,As(V)处理条件下,植物体中的As(V)比例较As(III)处理高。高浓度的HCO-3(20mmol·L-1)处理对蜈蚣草地上部分生物量没有明显影响,但是抑制了地下部分的生长,并且对砷的吸收表现出明显的抑制作用。     

砷浓度、形态及碳酸氢盐对蜈蚣草吸收砷的影响

大同盆地是典型的高砷地下水分布区。利用从地方性砷中毒严重病区山阴县采集的高砷地下水样品,用稀释培养法实验研究了外加砷源对地下水中微生物数量的影响;同时基于生物学可培养法和16S rDNA序列比对法,选取代表性高砷水样,研究了耐砷菌的种群特征。结果表明,外加砷源对地下水中微生物数量影响显著,高浓度砷会抑制大部分微生物生长,使微生物数量减少;低浓度砷对微生物生长具有一定促进作用。通过多次分离、纯化从3个不同砷含量地下水样中分离到多株砷抗性菌,经鉴定属于主要为Bacillus、Pseudomonas、Paenibacillus、Aeromonas、Enterobacter5个属。从RDP(Ribosomal Database Project)分析显示3个水样可培养微生物组成不同,都有生存能力强能够耐低浓度NaAsO₂的Bacillales,优势耐砷菌是γ-proteobacteria,其中Enterbacter具有耐高浓度NaAsO₂的能力。     

Arsenite oxidation by <Emphasis Type="Italic">Alcaligenes</Emphasis> sp. strain RS-19 isolated from arsenic-contaminated mines in the Republic of Korea

Arsenite [As(III)]-oxidizing bacteria play important roles in reducing arsenic [As] toxicity and mobility in As-contaminated areas. As-resistant bacteria were isolated from the soils of two abandoned mines in the Republic of Korea. The isolated bacteria showed relatively high resistances to As(III) up to 26 mM. The PCR-based 16S rRNA analysis revealed that the isolated As-resistant bacteria were close relatives to Serratia marcescensa, Pseudomonas putida, Pantoea agglomerans, and Alcaligenes sp. Among the five As-resistant bacterial isolates, Alcaligenes sp. strain RS-19 showed the highest As(III)-oxidizing activity in batch tests, completely oxidizing 1 mM of As(III) to As(V) within 40 h during heterotrophic growth. This study suggests that the indigenous bacteria have evolved to retain the ability to resist toxic As in the As-contaminated environments and moreover to convert the species to a less toxic form [e.g., from As(III) to As(V)] and also contribute the biogeochemical cycling of As by being involved in speciation of As.     

As(V)-reduction to As(III) by arsenic-resistant Bacillus spp. bacterial strains isolated from low-contaminated sediments of the Oliveri-Tindari Lagoon,Italy

Five arsenic-resistant bacterial strains designated MT1, MT2, MT3, V1 and V2 were isolated from sediments of the Oliveri-Tindari Lagoon (Italy), which comprises six small lakes whose sediments contain low arsenic concentrations. Phylogenetic analysis of the 16S rRNA gene sequences assigned them to the genus Bacillus. Bacillus sp. strain MT3 showed higher tolerance to As(III) and As(V), as indicated by minimum inhibitory concentrations of 14 and 135 mmol^?1, respectively. Bacillus sp. strain V1 showed growth inhibition at 14 mmol^?1 in the presence of As(III) and at 68 mmol^?1 in the presence of As(V), whereas the arsenic resistance of Bacillus sp. strain MT1 was 10 and 27 mmol^?1 for As(III) and As(V), respectively. The strains Bacillus spp. MT2 and V2 showed low levels of As(III) and As(V) resistance, as it was unable to grow at concentrations>7 and 14 mmol^?1, respectively. The isolated arsenic-resistant Bacillus spp. strains were able to reduce As(V) to As(III), especially Bacillus spp. strain MT3. This study suggests that the isolated bacterial strains play a role in the arsenic biogeochemical cycle of arsenic-poor sediments in the Oliveri-Tindari Lagoon.     

Impact of roxarsone on the UASB reactor performance and its degradation

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid, ROX) has been widely used for decades as an organoarsenic feed additive to control intestinal parasites and improve feed efficiency in animal production. However, most of the ROX is excreted into the manure, causing arsenic contamination in wastewater. The arsenic compounds are toxic to microorganisms, but the influence of continuous ROX loading on upflow anaerobic sludge blanket (UASB) reactor is still unknown. In this study, the impact of ROX and its degradation products on the performance of the UASB reactor and the degradation and speciation of ROX in the reactor were investigated. The UASB reactor (hydraulic retention time: 1.75 d) was operated using synthetic wastewater supplemented with ROX for a period of 260 days. With continuous ROX addition at 25.0 mg·L^–1, severe inhibition to methanogenic activity occurred after 87 days operation accompanied with an accumulation of volatile fatty acids (VFAs) and a decline in pH. The decrease of added ROX concentration to 13.2 mg·L^–1 did not mediate the inhibition. As(III), As (V), MMA(V), DMA(V), HAPA and an unknown arsenic compound were detected in the reactor, and a possible biotransformation pathway of ROX was proposed. Mass balance analysis of arsenic indicated that 60%–70% of the arsenic was discharged into the effluent, and 30%–40% was precipitated in the reactor. The results from this study suggest that we need to pay attention to the stability in the UASB reactors treating organoarsenic-contaminated manure and wastewater, and the effluent and sludge from the reactor to avoid diffusion of arsenic contamination.

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Toxicity of tri- and penta-valent arsenic, alone and in combination, to the cladoceran Daphnia carinata: the influence of microbial transformation in natural waters

The acute toxicity of arsenic(III) and arsenic(V) alone and in combination to a cladoceran, Daphnia carinata, was studied in both cladoceran culture medium and natural water collected from a local suburban stream. As(III) was found to be more toxic than As(V) to Daphnia survival. The LC₅₀ values for As(III), As(V), and As(III) + As(V) were 0.554, 1.499, and 0.692 mg l⁻¹, respectively. Although various species of As, particularly As(III) and As(V) co-exist together in natural waters, the existing guidelines for water quality are based on individual As species. The results of this investigation suggest that As(III) and As(V) can interact either synergistically or additively resulting in an increase in the overall toxicity of the mixture compared to individual As species. Also, indigenous microorganisms in natural water may play a significant role in the transformation of As, thereby influencing the toxicity of As in receiving waters. This study clearly suggests that the joint action of As species should be considered in the development of water quality guidelines. To our knowledge this is the first study on the interactive effect of As(III) and As(V) to a cladoceran. Thus, this study suggests that these two species of As, when present together above 0.1 mg l⁻¹ concentration, are toxic to fresh water invertebrates; therefore, pollution with these compounds may adversely affect natural ecosystems.     

磺胺与金属氧化物纳米颗粒对发光菌的急性联合毒性及其机制初探

磺胺与金属氧化物纳米颗粒同作为抗菌剂对环境与人体健康皆有危害。为探究其对细菌的毒性作用,测定了4种磺胺,包括磺胺氯哒嗪(SCP)、磺胺吡啶(SPY)、磺胺甲基异恶唑(SMZ)、磺胺嘧啶(SD),与3种金属氧化物纳米颗粒,纳米ZnO(n-ZnO)、纳米CuO(n-CuO)、纳米Cr_2O_3(n-Cr_2O_3)对发光菌(Vibriofischeri)的单一毒性及二元急性联合毒性。结果表明,SCP对V.fischeri的单一毒性明显大于其他3种磺胺;n-ZnO的单一毒性远大于n-CuO和n-Cr_2O_3;磺胺与金属氧化物纳米颗粒的二元急性联合毒性效应表现为拮抗、相加和协同,协同居多,说明金属氧化物纳米颗粒增加了磺胺的生物毒性,两者在环境中的共存带来了更大的环境生态风险。     

集胞藻(Synechocystis sp. PCC6803)对砷吸收转化特性的初步研究

砷是一种广泛存在于环境中的有毒物质.集胞藻属于单细胞藻类,广泛分布在淡水生态环境中.采用营养液培养的方法探讨了集胞藻(Synechocystis sp.PCC6803)对砷的累积和转化特性.当集胞藻分别暴露于2和100 μM的无机As(Ⅲ)和As(Ⅴ)14 d后,体内的砷形态均以As(Ⅴ)为主,并且在100 μM浓度处...     

Phototransformation and ecotoxicity of the drug Naproxen-Na

The phototransformation of naproxen Na in aqueous medium has been investigated. Irradiation of the drug in drinking water affords seven photoproducts. Three of them are dimeric photoproducts isolated for the first time. The compounds, isolated by chromatographic processes, have been identified by spectroscopic means. The toxicity of the photoproducts and the parent drug has been assayed on Daphnia magna and Vibrio fischeri. The results indicate that some photoproducts are more toxic than naproxen.     

Distribution of arsenic compounds in Plantaginaceae and Cyperaceae plants growing in contaminated soil

The ability of plant species to accumulate arsenic (As) species in the biomass from As-contaminated soils is variable. Among the plants widely grown at the As-contaminated locations, Plantaginaceae and Cyperaceae families belong to the frequent ones. In this study, the ability of Plantago lanceolata (Plantaginaceae) and three wetland plant species representing the family Cyperaceae (Carex praecox, Carex vesicaria, and Scirpus sylvaticus) naturally occurring in the soils with an elevated As in the Czech Republic were investigated. The plants were cultivated under controlled conditions in an As-contaminated soil reaching 735?mg?kg^?1 of the total As. The total As in plants reached up to 8.3?mg?kg^?1 in leaves, and up to 155?mg?kg^?1 in roots of C. praecox. Dominant As compounds were arsenite and arsenate with a small abundance of dimethylarsinic acid (DMA) in all the plant species. In Cyperaceae, small percentages of arsenobetaine (AB) and arsenocholine (AC) were detected, suggesting the ability of these plants to transform As into less toxic compounds. Moreover, the important role of As(V) sequestration on iron plaque on the root surface of Cyperaceae was confirmed. In this context, root washing with oxalic acid partially disrupted the iron plaque for the better release of arsenate.     

内蒙古自治区河套平原砷中毒高发区作物中砷的检测及健康风险评价

为了研究地方性砷中毒高发区作物中砷含量及其对人体健康的威胁,在内蒙古自治区河套平原4个自然村采集了72个谷物蔬菜水果、81份人体尿样和8个自来水样品。用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)分析测定采集的样品中各形态砷及其含量;用ICP-MS分析测定消解后的作物样品中砷总量。结果表明,自来水中总砷含量均小于1.0μg·L-1。尿液样品中总砷含量为4.50～319μg·L-1(平均值为56.9μg·L-1),二甲基砷(DMA)是尿砷的主要形态(>70%)。作物中砷的主要形态有无机三价砷As(III)、无机五价砷As(V)和DMA。谷物和蔬菜水果中总砷含量的最大值分别为102和335μg·kg-1。成人和儿童最大日摄入砷量分别为232和205μg。通过分析采样地人体尿砷、作物砷和地方性砷中毒发病率的相关性得出,作物中砷的含量虽未明显超过国家标准,但对人体健康有明显的潜在威胁。政府改水后(饮用水由井水变为达标的自来水),人体的健康风险主要来自作物中的砷,而不是饮用水中的砷。     

Counterillumination in the Hawaiian bobtail squid,<Emphasis Type="Italic"> Euprymna scolopes</Emphasis> Berry (Mollusca: Cephalopoda)

The mutualism between the Hawaiian bobtail squid Euprymna scolopes and the luminescent symbiont Vibrio fischeri has been used extensively as a model system for studies ranging from co-speciation and biogeography to gene regulation and the evolution of pathogenesis. In this association, the luminescent bacterium V. fischeri is housed in a complex light organ within the mantle cavity of E. scolopes. Prior hypotheses have assumed that sepiolid squids in general utilize the bioluminescence produced by their V. fischeri symbionts for counterillumination, a behavior that helps squid camouflage themselves by matching down-welling moonlight via silhouette reduction. This assumption, based solely on the morphology of the squid light organ, has never been empirically tested for Euprymna in the laboratory. Here, we present data demonstrating that E. scolopes can modify the intensity of light produced by V. fischeri in the light organ as down-welling light intensity changes. Bacterial bioluminescence from the light organ is directly correlated with down-welling light intensity, suggesting that E. scolopes individuals utilize and control V. fischeri luminescence for counterillumination.Communicated by P.W. Sammarco, Chauvin