高效液相色谱-电感耦合等离子体质谱法分析食用菌中6种砷形态及其分布特征

建立同时测定食用菌中亚砷酸根、砷酸根、一甲基砷酸、二甲基砷酸、砷甜菜碱、砷胆碱6种砷形态化合物的高效液相色谱-电感耦合等离子体质谱分析方法。选择5 mmol/L和80 mmol/L(pH 8.0)碳酸铵溶液作为梯度洗脱的流动相，0.50 mol/L乙酸溶液作为提取剂，采用微波萃取的提取方式进行分析。6种砷形态化合物的质量浓度在0～100μg/L范围内与色谱峰面积线性关系良好，相关系数均大于0.999 0，亚砷酸根、砷酸根、一甲基砷酸、二甲基砷酸、砷甜菜碱、砷胆碱的检出限分别为0.04、0.05、0.08、0.07、0.05、0.09μg/L，定量限分别为0.13、0.15、0.20、0.20、0.16、0.28μg/L。样品加标回收率为88.3%～96.3%，测定结果的相对标准偏差为4.37%～8.98%(n=6)。采用该方法研究市售食用菌中砷形态分布特征，结果表明，不同类型食用菌中砷形态分布种类和含量不同，需综合无机砷和有机砷的含量评估食用菌中砷的危害性。     

基于HPLC-ICP-MS的海螵蛸中不同砷形态含量及其转移率研究

建立了高效液相色谱-电感耦合等离子体质谱（HPLC-ICP-MS）测定海螵蛸药材中多种砷形态的分析方法，并研究了海螵蛸药材煎煮后砷及砷形态的转移率。样品采用0.02 mol/L乙二胺四乙酸二钠（EDTA-2Na）溶液超声提取60 min，以Dionex IonPac As7阴离子交换柱为色谱柱，2 mmol/L和100 mmol/L碳酸铵溶液为流动相进行梯度洗脱。结果显示，27批海螵蛸药材中均检出砷甜菜碱（As B）和砷胆碱（As C），其中26批检出二甲基砷（DMA）,10批检出一甲基砷（MMA）,1批检出微量亚砷酸（AsⅢ），并发现3个未知砷形态；海螵蛸药材水煎煮后砷及砷形态的平均转移率均大于50%，且存在个体差异。该方法准确度高，专属性好，明确了海螵蛸药材中砷形态的分布规律，并揭示了海螵蛸药材在煎煮过程中砷及砷形态的转移规律，可为海螵蛸药材的安全性评价奠定基础。     

砷对植物生长的影响及植物耐砷机理研究进展

砷污染问题是全球面临的重大环境污染问题之一。综述了不同浓度砷及不同形态砷对植物生长的影响，耐砷植物及植物耐砷机理，指出了今后研究的主攻方向。     

湘西地层中的砷锑汞及其赋存特征

湘西是金，砷，锑，汞等有色金属的重要成矿带。区域地层微量元素地球化学研究表明，湘西所出露的地层均显著富集砷，是砷的高区域地球化学异常区，元素存在相态实验进一步表明，新元古界至寒武系中的砷以易迁移形式为主，新元古界至寒武系可能构成砷矿矿源层。其风化所成土壤中砷的含量也一定较高。     

环境砷与地方性砷中毒

综述了环境砷与地方性砷中毒的关系，主要内容包括：地方性砷中毒简史，环境中砷与地方性砷中毒，地方性砷中毒流行概况，砷摄入量与地方性砷中毒关系和外源性摄砷中止后效应。     

高效液相色谱-电感耦合等离子体质谱法分析尿中6种砷形态

采用高效液相色谱-电感耦合等离子体质谱法（HPLC-ICP-MS）分析人尿中砷甜菜碱（AsB）、二甲基砷（DMA）、砷胆碱（AsC）、亚砷酸盐（As（Ⅲ））、一甲基砷（MMA）、砷酸盐（As(V)）6种砷形态。样品经水稀释后，采用Dionex IonPac As7阴离子交换色谱柱为分析柱，20 mmol/L碳酸铵（2%甲醇）和100 mmol/L碳酸铵（含2%甲醇）为流动相，梯度洗脱，HPLC-ICP-MS分析砷形态。6种砷形态在0～100μg/L范围内线性关系良好，相关系数（r）均大于0.999，检出限为0.05～0.15μg/L，不同浓度水平砷形态的相对标准偏差（RSD）均小于5.0%。3种不同浓度水平的加标回收率为91.8%～108%，有证标准物质“冷冻人尿中砷形态”（NIST SRM 3669）中5种砷形态的测定结果在标准值范围内。实验结果表明，该方法准确可靠、灵敏度高、分析时间短，适用于人尿中砷形态的分析测定。同时研究了食用不同含砷食物后尿中砷形态的种类，结果显示不同的含砷食品，其砷在人体内的代谢转化不同。     

土壤－水稻系统中砷污染表征与相关性校验

研究了青紫泥田、黄筋泥田和红砂田中水溶性砷、酸溶性砷和总砷与水稻生物产量和砷积累的关系，探讨了它们之间的相关性，为表征和校验土壤水稻系统中砷污染提供依据。     

土壤—水稻系统中砷污染表征与相关性校验

研究了青紫泥田、黄筋泥田和红砂田中水溶性砷、酸溶性砷和总砷与水稻生物产量和砷积累的关系，探讨了它们之间的相关性，为表征和校验土壤水稻系统中砷污染提供依据。     

煤中砷与硫洗选过程迁移和燃烧过程释放特性

以宁武煤田两个洗煤厂原煤及洗选产物为研究对象，采用微波消解与氢化物发生-原子荧光光谱相结合方法考察了洗煤过程硫和砷迁移规律，采用砷质量平衡验证的逐级化学提取法探讨了原煤、精煤、矸石、洗中煤和煤泥燃烧后硫和砷形态转化与释放特性及其依赖性。原煤中20%-28%硫和砷迁移至精煤中，46%-61%迁移至矸石中，Pearson相关系数结果表明，样品中无机矿物质是硫和砷迁移的控制因素。精煤中有机硫和砷提高至30%-50%，而矸石中无机硫和砷占比达90%以上，说明原煤及洗选产物中砷与硫赋存形态具有一定相关性。精煤中较多的有机硫和砷在500℃以下伴随水分和挥发分析出呈现明显释放特征，矸石中以无机态为主的砷则主要在500-1000℃伴随黄铁矿和硫酸盐等矿物质分解与硫一起释放，体现了原煤及洗选产物燃烧时硫与砷释放的同步性。精煤中硫和砷释放速率最快，300和200 s分别达到最大释放率80%-95%和60%-75%；矸石中最慢，300 s时砷达到最大释放率40%-45%，而硫600 s时仍未达最大释放率；洗中煤和原煤介于精煤和矸石之间，样品燃烧时硫和砷赋释放速率差异是由其固有赋存形态差异所致。     

氢化物发生-原子吸收光谱法测定大米中微量砷

砷是一种毒性很大的元素，对人的心肺、呼吸、神经、生殖、造血、免疫系统都有不同程度的损伤作用]。由于大气、地下水、土壤、肥料和农药等污染，砷会在粮食的可食部分积累，因此砷的测定已成为食品和环境监测的必测项目。测砷的常规方法有砷斑法、银盐法。目前，氢化物原子吸收光谱法，氢化物原子荧光法已有报道。本文采用氢化物发生—原子吸收光谱法测定大米中砷，本法具有灵敏度高，干扰少，操作简便等特点，结果满意。     

砷迁移释放过程中吸附-脱附作用机制的研究进展

高砷地下水污染是一个全球性的环境问题。在特定地质、地貌、气候和水文及水化学条件下,含砷矿物发生吸附-脱附反应,砷元素迁移和释放进入水体,导致高砷地下水生成并危害周围人群健康。本文在系统总结前人研究工作基础上,从吸附质和吸附剂两方面讨论了竞争吸附、氧化还原、pH和有机质等因素对砷吸附-脱附行为的影响,总结得到三种砷吸附-脱附控制机制,即静电吸附机制、离子交换机制和络合形态机制。本文可以为揭示高砷地下水发生机制以及开展砷污染控制和治理提供有益帮助。     

黑苦荞保健茶中重金属的分析评价

采用原子吸收光谱法和原子荧光光度法测定了四川省凉山州某几个品牌黑苦荞保健茶中的重金属铅、镉、铬、无机砷和汞的含量,并以NY/T 1510-2007标准绿色食品麦类制品为依据,对黑苦荞保健茶重金属污染状况进行了分析评价。结果表明,黑苦荞保健茶受重金属元素污染的程度由高到低表现为铅、铬、镉、无机砷和汞,但含量均未超过国家标准规定;黑苦荞叶芽茶和全株茶的重金属污染较为严重,全胚茶未受重金属污染。     

Arsenic and its speciation analysis using high-performance liquid chromatography and inductively coupled plasma mass spectrometry

It is known that arsenic has different toxicological properties dependent upon both its oxidation state for inorganic compounds, as well as the different toxicity levels exhibited for organic arsenic compounds. The field of arsenic speciation analysis has grown rapidly in recent years, especially with the utilization of high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICP-MS), a highly sensitive and robust detector system. Complete characterization of arsenic compounds is necessary to understand intake, accumulation, transport, storage, detoxification and activation of this element in the natural environment and living systems. This review describes the essential background and toxicity of arsenic in the environment, and more importantly, some currently used chromatographic applications and sample handling procedures necessary to accurately detect and quantify arsenic in its various chemical forms. Applications and work using only HPLC-ICP-MS for arsenic speciation of environmental and biological samples are presented in this review.     

Accumulation of arsenic(III) by chlorella vulgaris

Arsenic occurs naturally in the environment and also through agricultural and industrial pollution. Since arsenic species show different toxicities, it is important to be able to separate them. Methods using microorganisms are being applied increasingly to remove metal ions and different metal species from aqueous solutions. Accumulation of As(III) by Chlorella vulgaris algae was studied, including various factors that influence on accumulation capacity, e.g. pretreatment of the algae (live, dry and lyophilized algae), temperature (4, 22, 37 and 100 °C), pH and exposure time of the algae to arsenic solutions. The pH appears to be the most critical factor, probably due to the species presenting different charges with pH variation. For arsenic species determination, hydride generation atomic absorption spectrometry (HG–AAS) was employed. Copyright © 1999 John Wiley & Sons, Ltd.     

Overview of analysis of carcinogenic and/or mutagenic metals in biological and environmental samples. I. Arsenic, beryllium, cadmium, chromium and selenium

One of the most dangerous and pernicious forms of pollution arises from the potential mobilization of a spectrum of toxic trace metals and metalloids in our environment. Among the most important elements in this regard are arsenic, beryllium, cadmium, chromium and selenium whose adverse toxic effects are now well recognized including their carcinogenicity and/or mutagenicity. These agents (and their derivatives) can be widely dispersed throughout the environment as a result of fossil fuel combustion, industrial and agricultural processes and natural processes. The trend for the immediate future appears to be of greater exposure to these metals not only as a result of generally increased usage patterns but also because of prospective enhanced use of fossil fuels for space heating and electricity generation. In order to more readily evaluate trends of human exposure as well as the toxicity, bioavailability, bioaccumulation and transport of these elements, sensitive analytical procedures are required for the determination of their various oxidation states (as well as their organic derivatives) in complex matrices such as those found in both environmental and biological samples. Hence, the principal objective of this overview is to highlight the more recent trends and state-of-the-art methodologies for the determination of arsenic, beryllium, cadmium, chromium and selenium (in their various forms) in environmental compartments such as air, water, soil and in human tissues (primarily blood, urine, and milk). Techniques to be discussed primarily include atomic absorption spectrometry, neutron activation analysis, gas chromatography, differential pulse polarography and electrochemical analysis. The importance of quality control and differentiation according to speciation will also be stressed.     

燃煤电厂砷、硒、铅的排放与控制技术研究进展

煤炭是中国重要的能源资源，而中国煤中重金属砷、硒、铅含量较高，燃煤电厂已经成为重要的砷、硒、铅排放源之一。针对电厂燃煤带来严峻的砷、硒、铅污染问题， 本文首先介绍了燃煤释放的砷、硒、铅排放量大且危害性强，概述了世界各国关于重金属排放控制的相关政策法规，指出中国对燃煤重金属砷、硒、铅的排放控制势在必行；其次从煤中赋存形态、燃烧过程中的形态转化和质量分布三个方面阐释了燃煤过程中砷、硒、铅的迁移转化规律，重点描述了砷、硒、铅在颗粒物上的形态特征和尺度分布；最后综述了燃烧前、燃烧中和燃烧后对砷、硒、铅的排放控制技术，详述了吸附剂捕集和烟气净化装置协同脱除的研究进展，并论述了低低温除尘器和团聚技术对砷、硒、铅的强化脱除潜力。以期为燃煤电厂重金属砷、硒、铅超低排放的实现提供参考和指导。     

Arsenic compounds in marine and terrestrial organisms: Analytical,chemical and biochemical aspects

Arsenic has a reputation as a poison, because arsenic trioxide was used during medieval times as an agent for murder. Lingering memories of these events make any arsenic-containing material suspect. Toxicity is a property of a specific compound and varies with the composition and structure of compounds. Developments in analytical methodology made it possible not only to determine total arsenic in a variety of matrices but also arsenic compounds. Knowledge about the arsenic cycle in marine systems has expanded considerably during the past decade. The marine arsenic cycle appears to be more complex than the cycle in the terrestrial environment. More attention must be given to the minor arsenic-containing compounds detected in organisms and experiments should be undertaken that provide information about the biochemical pathways used for the transformation of arsenic compounds.     

Poly(ethylene terephthalate) waste recycling and uses for enhancement of bioremediation of arsenic in groundwater

Various studies on arsenic pollution reveal that high concentrations of arsenic were found in many districts of western Uttar Pradesh, India. There arsenic concentrations were higher than the permissible limit given by the World Health Organization (WHO) and Bureau of Indian Standards (BIS). There is a requirement to bioremediate arsenic due to its harmful effect. On the other hand, Poly(ethylene terephthalate) was being repeatedly used as packaging materials, due to which various environmental issues regarding PET waste disposal have generated. In the present study, PET waste was recycled into various aromatic amides by aminolysis and ammonolysis. These aromatic amides were used as surfactants. Various studies have been carried out for biosorption of heavy metal through Bacillus cereus. The efforts were made to enhance bioremediation of arsenic in different water samples spiked with Bacillus cereus in the presence of synthesized aromatic amides. This study explored the possibility to increase bioremediation of arsenic by bacteria using recycled PET waste. The results of this study indicated that in the presence of aromatic amides the percent biosorption could be enhanced by bacteria up to 20–60%.The other significant approach of this study is recycling of PET waste.     

Blank values, adsorption, pre-concentration, and sample preservation for arsenic speciation of environmental water samples

Arsenic is the focus of public attention because of its toxicity. Arsenic analysis, its toxicity, and its fate in the environment have been broadly studied, still its blank values, adsorption to sampling materials and pre-concentration of water samples as well as stabilization of arsenic compounds in water samples under field conditions have been very little investigated. In this study, we investigate the blank values and adsorption of arsenic compounds for different laboratory materials. We focused our work onto pre-concentration of water samples and how to stabilize arsenic compounds under field conditions. When using glassware for arsenic analysis, we suggest testing arsenic blank values due to the potential release of arsenic from the glass. Adsorption of arsenic compounds on different laboratory materials (<10%) showed little influence on the arsenic speciation. Pre-concentration of methanol-water solutions could result in potential overestimation of arsenic compounds concentrations. Successful pre-concentration of water samples by nitrogen-purge provides an analytical possibility for arsenic compounds with high recoveries (>80%) and low transformation of arsenic compounds. Thus, concentrations as low as 1 ng As l⁻¹ can be determined. Addition of ethylenediaminetetraacetic acid (EDTA) and storage in the dark can decrease the transformation among arsenic compounds in rainwater and soil-pore water for at least a week under field conditions.     

高效液相色谱-原子荧光光谱法分析底泥孔隙水中形态砷

砷是我国实施排放总量控制的指标之一,不同形态砷的毒性差别较大,因此研究砷的形态具有重要的意义. 当前形态砷的研究主要集中在水产品方面,而对底泥孔隙水中形态砷研究较少. 底泥孔隙水中砷的形态及污染情况是重要的环境指标,可影响生活于其中的生物并间接影响人类健康. 采用高效液相色谱-原子荧光光谱法,以磷酸氢二铵为流动相,盐酸为载流,硼氢化钾为还原剂,对流动相的pH、光电倍增管负高压、空心阴极灯电流、盐酸体积分数、硼氢化钾浓度等参数进行了优化. 在优化的测试条件下,亚砷酸盐[As(Ⅲ)]、二甲基砷(DMA)、一甲基砷(MMA)和砷酸盐[As(Ⅴ)] 4种砷的形态在5~100 μg/L范围内线性关系良好,标准曲线线性相关系数均大于0.999 1,4种形态砷的检出限在0.22~0.43 μg/L之间,相对标准偏差(RSD)均小于4.0%,各组分的加标回收率在89.0%~103.0%之间. 测试结果表明方法准确可靠、操作简单,可用于底泥孔隙水中形态砷的测定.