Role of complex organic arsenicals in food in aggregate exposure to arsenic

For much of the world''s population, food is the major source of exposure to arsenic. Exposure to this non-essential metalloid at relatively low levels may be linked to a wide range of adverse health effects. Thus, evaluating foods as sources of exposure to arsenic is important in assessing risk and developing strategies that protect public health. Although most emphasis has been placed on inorganic arsenic as human carcinogen and toxicant, an array of arsenic-containing species are found in plants and animals used as foods. Here, we 2evaluate the contribution of complex organic arsenicals (arsenosugars, arsenolipids, and trimethylarsonium compounds) that are found in foods and consider their origins, metabolism, and potential toxicity. Commonalities in the metabolism of arsenosugars and arsenolipids lead to the production of di-methylated arsenicals which are known to exert many toxic effects. Evaluating foods as sources of exposure to these complex organic arsenicals and understanding the formation of reactive metabolites may be critical in assessing their contribution to aggregate exposure to arsenic.     

Arsenic speciation in fish from Greek coastal areas

Arsenic speciation analysis was conducted on fish samples(sardine and anchovy) collected from six areas along the Greek coastline, i.e. Artemisium Straits, Thermaikos Gulf, Amvrakikos Gulf,Strymonian Gulf, Thracian Sea, and Elefsina Gulf. Total arsenic levels ranging from 11.8 to62.6 mg As/kg dry weight were determined. Arsenobetaine, a non-toxic form of arsenic, was found to be the main arsenic species, present at 8.6 to 58.8 mg As/kg dry weight, accounting for67–95% of the total arsenic. Also detected in all fish samples was dimethylarsinic acid, although at considerably lower concentrations, ranging from 0.072–0.956 mg As/kg dry weight.Monomethylarsonic acid was detected at low levels in all anchovy samples, and only in sardines from one area. Finally, inorganic arsenic in the form of arsenate was detected only in fish at one area, indicating the possible effect of an environmental parameter on its presence at detectable amounts. Statistical analysis revealed the environmental variables, such as salinity,total organic carbon and nitrogen, ammonium, phosphate, total phosphorus, dissolved oxygen and pressure index, are potentially correlated to As species concentrations. Furthermore, based on factor analysis, the biological parameters, such as fish weight, lipids, protein and ash content,that are correlated to As species concentrations of fish were also identified. The interrelationship of arsenobetaine and dimethylarsinic acid concentrations within each fish species was evaluated.     

The dynamic changes of arsenic biotransformation and bioaccumulation in muscle of freshwater food fish crucian carp during chronic dietborne exposure

Dietary uptake is the major way that inorganic arsenic (iAs) enters into benthic fish; however, the metabolic process of dietborne iAs in fish muscle following chronic exposure remains unclear. This was a 40-day study on chronic dietborne iAs [arsenite (AsIII) and arsenate (AsV)] exposure in the benthic freshwater food fish, the crucian carp (Carassius auratus), which determined the temporal profiles of iAs metabolism and toxicokinetics during exposure. We found that an adaptive response occurred in the fish body after iAs dietary exposure, which was associated with decreased As accumulation and increased As transformation into a non-toxic As form (arsenobetaine). The bioavailability of dietary AsIII was lower than that of AsV, probably because AsIII has a lower ability to pass through fish tissues. Dietary AsV exhibited a high potential for transformation into AsIII species, which then accumulated in fish muscle. The largely produced AsIII considered more toxic at the earlier stage of AsV exposure should attract sufficient attention to human exposure assessment. Therefore, the pristine As species and exposure duration had significant effects on As bioaccumulation and biotransformation in fish. The behavior determined for dietborne arsenic in food fish is crucial for not only arsenic ecotoxicology but also food safety.     

水泥窑共处置过程中砷挥发特性及动力学研究

针对不同形态的含As化合物开展了热重实验、熟料煅烧以及熟料消解实验,研究了水泥窑共处置过程中砷在等温条件下随时间的挥发特性和可能的化学反应.结果表明,不同化学形态的砷挥发规律不尽相同,砷酸钠在水泥生产涉及的温度区间基本不挥发;硫化亚砷在水泥窑共处置的过程中,砷的挥发率随时间逐渐增大,25min以后基本不再挥发,低于1000℃时,砷的挥发率随温度的升高而增大,但高于1000℃时,挥发率随温度的增大而减小;亚砷酸钠在1000℃以上的挥发规律与硫化亚砷类似,挥发率随温度的升高而减小,25min以后基本不再挥发.硫化亚砷在1000℃以下煅烧时,挥发率随时间和温度变化的动力学方程为a =1-exp[-1.77exp(-3158/T)t],可以根据此方程计算不同温度和停留时间工况下砷挥发的理论值,进而控制含砷废物的投加量,避免对环境造成危害.     

CaO对含砷废渣烧结过程砷的形态及释放特性的影响

为揭示CaO对含As废渣烧结陶粒过程中As挥发和结构形态变化的影响规律,对添加CaO前、后含As废渣在不同温度下烧结体中的As残留量、形貌、结构形态和环境释放行为的变化进行了研究. 结果表明:①在400~1 000 ℃,CaO对As的挥发有很强的抑制作用,As的固化率均大于85%;当温度>1 000 ℃时,CaO对As的挥发抑制作用减弱. ②在400~1 000 ℃,CaO对烧结体As的浸出释放抑制作用显著;当温度>1 000 ℃时,CaO对As的浸出释放抑制作用随温度升高显著降低. ③在1 000 ℃时,CaO与As化合生成了稳定的砷酸钙,残留于烧结体中,大幅降低了As的挥发和浸出释放特性,As的固化率最高可达95.14%;As的浸出浓度(以ρ计)也达到最小值,其中水平振荡法、硫酸硝酸法和TCLP法处理后的浸出值分别为1.33、130和0.85 μg/L;温度升至1 300 ℃时,砷酸钙消失,As以溶解度高的As₂O₃形式存在,导致As的浸出浓度增大.      

垃圾焚烧炉飞灰的低温玻璃固化初步研究

在研究我国城市生活垃圾焚烧炉飞灰的毒性特征和高温灼烧特性的基础上，试验了几种常用玻璃熔制助溶剂、烟气净化产物中的成分对飞灰的溶融温度和熔融减量的影响，以实现低温玻璃固化。实验发现受热温度越高、时间越长，飞灰减量越大；B2O3、硼砂、CaF2对飞灰助溶效果明显，而废玻璃、CaO、CaCl2能使悄灰溶融后形成的玻璃态物质地均匀、少孔。按一定比例同时加入硼砂、CaF2、废玻璃、CaO、CaCl2于飞灰中，混合物的熔融温度降到1000℃以下，大大低于飞灰自身的熔融温度（1200℃）。对该熔融物在空气中淬火形成的玻璃态物质按标准方法浸沥，选择测量了浸出液中铅、汞、镉、砷的浓度，初步发现低温玻璃态物质对重金属铅和镉具有较好的固化效果，而对汞有砷的固化效果尚不确定。     

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.     

HPLC-DRC-ICP-MS检测四种尿砷化合物

拟建立检测尿液中As(Ⅲ)、DMA(Ⅴ)、MMA(Ⅴ)和As(Ⅴ)4种砷化合物形态的HPLC-DRC-ICP-MS的方法。采用DRCTM(反应气为O2)与HPLC联用作为检测器,Phenomenex ODS-3作为分离柱,5 mmol/L四丁基羟胺,3 mmol/L丙二酸,5%(体积分数)甲醇为流动相(pH=5.0~6.0),建立了同时分析尿液中As(Ⅲ)、DMA(Ⅴ)、MMA(Ⅴ)和As(Ⅴ)的方法。实验结果显示:该分析方法对上述4种砷化合物的检测限均在0.1μg/L以下,在1~20μg/L范围内线性关系良好,准确度和精密度良好,回收率为89%~106%,样品中的Cl-1对测定没有影响。所建立的HPLC-DRC-ICP-MS分析方法稳定、可靠,适用于快速、批量测定尿砷形态。     

Novel Fe/glass composite adsorbent for As(V) removal

An effective adsorbent for arsenic removal was synthesized by hydrothermal treatment of waste glass powder (GP), followed by loading Fe(Ⅲ) oxyhydroxide onto the surface of waste glass powder. The ≡Si-O-H group was formed on the surface of GP and the specific surface area of GP powder was slightly increased after hydrothermal treatment. FeOOH was loaded onto the surface of hydrothermally treated waste glass powder (HGP) by the hydrolysis of FeCl3. The formation conditions of FeOOH were also investigated. The...     

金属有机框架材料吸附去除水中有机砷的研究进展

有机砷作为饲料添加剂在家禽养殖中被广泛使用,并伴随着家禽粪便大量进入环境中. 进入环境后有机砷容易被生物降解或(光)化学氧化转化为剧毒的无机砷,危害环境和人体健康. 因此,高效处理有机砷污染受到广泛关注. 金属有机框架(metal organic frameworks, MOFs)材料因其具有孔隙率和比表面积大、孔道尺寸可调、易功能化改性和材料性能可定制等特点,在水体污染物的去除中展现了良好的应用前景. 本文综述了目前MOFs材料作为吸附剂去除水环境中有机砷的最新研究进展,介绍了吸附有机砷MOFs材料的种类、制备方法和吸附性能,总结了MOFs材料吸附有机砷的关键影响因素,并归纳了不同类型MOFs材料吸附的再生方法和稳定性. 最后,指出了当前MOFs存在的技术缺陷及限制工程应用的关键因素,并提出相对应的建议及解决措施.      

Determination of total arsenic by photo-decomposition of organoarsenic compounds and hydride generation electrothermal atomic absorption spectrometry

A method was developed for the determination of total arsenic concentration in less than ng/ml level by decomposition of organoarsenicals using photo -oxidation combined with in situ trapping of arsenic hydride on a palladium coated graphite tube with subsequent atomization and detection by AAS. The organoarsenicals include monomethylarsenic, dimethylarsenic, arsenobetaine, arsenocholine, o -aminobenzenarsenate and p -aminobenzenarsenate. The method is simple and sensitive. Detection limit was obtained from different arsenic compounds over the range from 0. 058 to 0.063 ng/ml as As (based on three times of the standard deviation of 10 blank measurements) and the relative standard deviations for ten replicate measurements were from 2.0 to 3.8%. The calibration curves of arsenic compounds including inorganic and organic arsenicals were linear over the range from 0.1 to 3.0 ng/ml as As. The recommended method has been applied to the determination of total arsenic in tap and lake water samples at ng/ml leve     

岩溶地下河水中多环芳烃、脂肪酸分布特征及来源分析

为探究重庆青木关岩溶地下河水中多环芳烃(PAHs)和脂肪酸的含量组成、分布特征、来源及污染水平,2013年雨季和旱季分别于地下河中进行水样采集,并利用气相色谱-质谱联用仪(GC-MS)对水样中PAHs和脂肪酸的组分进行定量分析.结果表明,青木关地下河水中PAHs和脂肪酸的含量范围分别为77.3~702 ng·L~(-1)和3 302~45 254 ng·L~(-1).组成上,PAHs以2~3环为主,其比例高于90%,脂肪酸碳数范围为C10~C28,以饱和直链脂肪酸为主,其次为单不饱和脂肪酸.分布特征上,雨季:地下河水中各采样点PAHs的含量差异较小,脂肪酸的含量在入口、出露处和出口呈现依次降低的趋势,其中出露处和出口脂肪酸的含量较为接近;旱季:地下河水中PAHs含量在入口、出露处和出口呈现先降后升的趋势,脂肪酸含量在各采样点较为接近.总体上,地下河水中PAHs和脂肪酸的含量都表现为雨季显著高于旱季.来源分析表明,青木关地下河水中PAHs主要来源于该河流域煤和木材、农作物秸秆等生物质的燃烧;脂肪酸主要来自该河流域内硅藻、绿藻等水生藻类和细菌,其中以水生藻类的贡献占主导.地下河水受到PAHs中轻度污染,相对于旱季,雨季污染更严重.     

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.     

磁性吸附材料CuFe2O4吸附砷的性能

根据Cu(Ⅱ)和Fe(Ⅲ)都对砷有较强的亲和性,制备了同时含有Cu(Ⅱ)和Fe(Ⅲ)的、可用磁分离方法进行分离回收的磁性吸附材料CuFe₂O₄,并对其进行了表征及吸附砷的性能研究.结果表明,该吸附剂对砷的吸附能力与溶液pH有关,在弱酸性及中性条件下,吸附砷的能力最强,而对As(V)的吸附能力比对As(Ⅲ)更强些,在平衡浓度为10μg/L时,其吸附容量可达10mg/g左右,可以很容易地将水中浓度为1～20mg/L的As(V)降到10μg/L以下.实验考察了几种无机阴离子对吸附砷的影响,表明较高浓度(砷浓度的20倍)的硫酸盐对As(Ⅲ)和As(V)的吸附均有一定影响,盐酸盐及磷酸盐则影响不明显;负载的As(V)可较容易地用0.1mol/L NaOH洗脱下来,使吸附剂再生,而As(Ⅲ)则难以洗脱,这与2种价态砷的吸附机理不同有关.     

电子废弃物显像管玻璃中Pb渗出的研究

文章对显像管玻璃中Pb渗出机理分析并通过实验证明,用水、盐、酸和碱溶液处理显像管玻璃后,都会有铅渗出。因此如果将显像管玻璃随意丢弃,会有大量的铅渗出并进入环境,对环境产生极大危害。所以必须加大宣传力度,使人们都认识到丢弃显像管的危害性。并尽快的回收、处理废旧显像管。     

高浓度含砷污泥的药剂稳定化和水泥固化研究

以某铜冶炼厂高浓度含砷污泥为研究对象,分别开展了药剂稳定化和水泥固化小试研究,并对比分析了不同剂量的两种稳定化药剂和矿渣硅酸盐水泥（PSA）单独投加后污泥中砷的浸出毒性。研究发现：该铜冶炼厂污泥中砷含量极高,达到危废级别。对含砷污染土壤具有较好稳定化效果的两种药剂对高浓度含砷污泥的处理效果并不理想,在高剂量投加（15％）条件下仍不能使污泥中砷的浸出浓度低于5mg／L的危废鉴别标准值。相比而言,传统的水泥固化处置方式能有效降低污泥中砷的浸出浓度,使其低于5mg／L,但该处置方式污泥增容显著,会增加后续相关处理费用和难度。本研究对开展含重金属污泥和污染土壤的固化／稳定化修复提供了有重要价值的参考和借鉴。     

Novel Fe/glass composite adsorbent and its property for arsenic(V) removal

An effective adsorbent for arsenic removal was synthesized by hydrothermal treatment of waste glass powder (HGP), followed by loading iron(III) oxyhydorxide on the surface of waste glass powder (GP). The ?Si-O-H group was formed on the surface of GP and the specific surface area of GP powder was slightly increased after hydrothermal treatment. FeOOH was loaded on the surface of HGP by the hydrolysis of FeCl3. The formation conditions of FeOOH were also investigated. The ability of this new adsorbent for arsenic removal was tested. The results indicate that the highest arsenic removal efficiency is about 97% for 1 mg/L As(V) solution at pH 6 and keeping time 2h.     

含砷烟尘作玻璃澄清剂的应用研究

通过理论分析和试验证明,可采用有色冶炼厂的含砷烟尘代替白砒作玻璃澄清剂。砷烟尘加入量1．2％时,其澄清效果最好,它还兼有助熔和脱色功能,采用此法基本消除了有色冶炼厂的砷害,也使玻璃厂排出的废气中砷含量降低到原来的17．3％,大大减轻了玻璃厂对环境的污染。      

一种强富集砷的欧洲蕨——能从被污染土壤中萃取砷的耐寒、适应性强的速生植物

我们的研究首次发现一种耐寒的、适应性强的、速生的欧洲蕨，能在短时间内将土壤中有大量砷吸收并积累到其复叶之中，它不仅能祛除土壤中不同浓度的砷，还能祛除土壤中不同形态的砷，且欧洲蕨体内高达93％的砷被富集到复叶，从而使欧洲蕨成为修复土壤砷污染的救星。     

石油类过滤及脱水方法的改进研究

选取实验室常用的过滤介质,通过空白试验、标准样品试验,对过滤材质进行测试,确定经550℃烘干的玻璃纤维滤膜作为红外测油仪测定石油类过滤介质,将其用于实际样品测定,并与标准方法进行比对实验,结果证明,用550℃烘干的玻璃纤维滤膜替代玻璃砂芯滤器,实验结果无明显差异.检出限低于国家标准要求,该方法简便易行,耗材便宜,减少了四氯化碳使用量,简化了无水硫酸钠脱水的操作步骤,可用于环境监测中石油类的测定中.