中国东部主要入海河流As元素分布、来源及影响因素分析

为查明中国河流中As等重金属元素的分布规律,于2007—2008年分丰水期和枯水期对中国东部30余条入海河流水体、悬浮物统一进行采样分析。结果表明:东部河流中As元素溶解态含量均值为3.1μg/L,同世界河流相比,明显偏高;且频率分布直方图具有多个峰值,反映出明显的人为污染。利用富集系数的研究表明,悬浮物同样受到较明显的人为污染。As在河水中的迁移形式以溶解态为主,pH值和温度对As的迁移形式有明显影响。流域内岩石类型对河流中As含量影响显著,火山岩、火山碎屑岩类广泛分布的流域河水中As含量明显偏高,花岗岩及中、深变质岩广泛分布的流域河流中As含量则偏小。利用生活、工业污水作为As元素人为来源端元,对海河、黄河、长江、珠江等河流人为源进行了估算,分别为46.7%、18.7%、13.5%、8.3%。     

微波消解电感耦合等离子体质谱法测定地球化学样品中钒铬镍锗砷

地质样品中多种元素的分析,通常采用高压密封消解电感耦合等离子体质谱法(ICP-MS),而应用于测定地球化学样品中的V、Cr、Ni、Ge、As等元素,影响分析准确度的主要原因有:样品前处理方面,高压密封罐会释放Cr和Ni污染样品,同时Ge和As属于易挥发元素容易造成损失;质谱测定方面,多原子分子离子会产生干扰。本文针对两方面的干扰因素,对比了微波消解硝酸提取、微波消解王水提取、高压密封硝酸复溶、高压密封王水复溶四种前处理方法中待测元素的溶出效果以及污染或损失情况。结果表明,采用微波消解替代高压密封罐消解可消除引入的Cr、Ni污染,避免了Ge、As挥发损失,同时微波消解的时间短。而采用硝酸提取,由于避免了氯的引入,分析效果优于王水提取。且使用八极杆ICP-MS氦气碰撞模式消除了样品基体中的氯多原子分子离子干扰(如37Cl14N对51V干扰,35Cl16OH对52Cr干扰,35Cl37Cl对72Ge干扰以及40Ar35Cl对75As干扰等)。应用微波消解硝酸提取、ICP-MS测定岩石、水系沉积物和土壤国家标准物质,V、Cr、Ni、Ge、As的检出限分别为1.09、0.19、0.55、0.02、0.50μg/g,精密度(RSD)4%,而采用高压密封消解、ICPMS测定V、Cr、Ni的检出限为3.48、13.09、21.67μg/g(Ge和As由于挥发无法用此法检测)。运用微波消解硝酸提取-ICP-MS氦气碰撞模式测定地球化学样品中V、Cr、Ni、Ge、As,简化了分析流程,样品消解时间仅2 h,相比于高压密封方法(消解时间48 h)具有消解快速、多元素同时测定、检出限低的特点。     

Distribution of arsenic in sediment of Hangjinhou Banner- Linhe transect in Hetao Basin,North China

In this research, we laid a Hangjinhou Banner-Linhe District drilling transect along western piedmont of Hetao Basin to the modern Yellow River, which passes through the Langshan Mountain piedmont alluvial-proluvial fan, the Yellow River paleochannel, alluvial-fluvial plain of the Yellow River and the modern Yellow River flood plain successively and based on which we collected sedimentary samples of different geomorphic units. Based on hydrogeology and sedimentology and by means of stratum tracing and transects comparison, the analysis result comes out that the arsenic (As) sediments in Hetao Basin is distributed in obvious zoning form and is closely related to the sedimentary environment. The paleochannel zone in northern Basin has the highest content of As sediments, average content reaching 12.24 μg/g. In the horizontal direction of the profile, the distribution regularity of As is consistent to that of elements like Mn, Fe, Al and TOC, since they have experienced the same geochemical process in sediments. In the vertical direction, the high-arsenic sediments are mainly formed of grey black silty-fine sand layers or interbedding layers of silty-fine sand and muddy clay, rich in organic matter. The sedimentary environments are mainly shallow lakes and depressions, where the content of As is related to that of elements like Sb, Mn, B, V, etc., and particularly has significant relation with Fe.     

镁铁—超镁铁质岩浆中铂族元素的富集机理：综述与实例

目前陆地上可利用的铂族元素(PGE)资源主要来自与镁铁—超镁铁质岩浆密切相关的岩浆硫化物矿床。岩浆硫化物矿床成矿理论关注的一个重要问题就是镁铁—超镁铁质岩浆中PGE的富集机理。经典成矿理论认为,由于PGE在平衡的硫化物熔体与硅酸盐熔体之间具有极高的分配系数(105～106),PGE富集成矿主要与成矿体系中硅酸盐熔体与硫化物熔体的质量比有关(R-factor)。但是近些年来,许多新的实验岩石学结果和天然矿石样品纳米尺度PGE赋存状态的观测结果对这一经典理论提出了挑战。本文列举了一些相关的研究实例,显示硅酸盐熔体中的PGE纳米颗粒可以被硫化物或铬铁矿机械捕获、并通过定向附着生长、聚集、粗化和融合,最终形成纳米颗粒集合体和纳米合金。另外,岩浆中半金属元素(TABS,即Te、As、Bi、Sb、Sn)和Se可以与PGE优先形成各种互化物,从而富集于砷化物、铋化物、碲化物或硒化物中,而非硫化物中。因此,镁铁—超镁铁质岩浆体系中PGE的富集可能不仅受其在硫化物熔体中极高的分配系数控制,一些物理过程导致的PGE分配以及半金属元素对PGE的富集作用也不容忽视。由于矿石中的铂族矿物一般为纳—微米级,采用聚...     

Removal Arsenic(V) Efficiency and Characteristics Using Modified Basic Oxygen Furnace Slag in Aqueous Solution

Basic oxygen furnace (BOF) slag, the solid waste produced in the steelmaking process, is reused in industry, agriculture and environmental treatment. However, as an adsorbent for wastewater, the removal effect of BOF slag on anionic pollutants needs to be improved. In this study, acid and alkali were used to modify BOF slag, and the removal efficiency and mechanism of arsenic(V) with modified BOF slag in solution were studied. The effects of the As(V) initial concentration, solution pH and reaction time on the removal efficiency were determined by batch experiments, and the removal mechanism of As(V) using modified BOF slag was studied by an adsorption kinetic model and isothermal adsorption model and the Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) spectral analysis. The results showed that the slag modified by 15% sulfuric acid had the best removal effect on As(V), while the removal effect of As(V) by alkali-modified slag was not ideal. The removal rate of As(V) by acid-modified slag increased with the increase in the initial concentration, decreased slowly with the increase in pH and reached equilibrium in 180 min. The adsorption kinetic model and isothermal adsorption model of As(V) by acid-modified BOF slag showed that the chemical adsorption was the limiting step. The FTIR and XPS analysis results showed that the silicate and ferrite in the acid-modified slag could remove As(V) in the solution by ion exchange to form an arsenate precipitate. Therefore, modified BOF slag can be used as a potential adsorbent for large scale arsenic polluted waterbody to realize the ecological utilization of industrial solid waste.     

Arsenic and trace metal contents in sediment profiles from the Admiralty Bay, King George Island, Antarctica

Admiralty Bay (Antarctica) hosts three scientific stations (Ferraz, Arctowski and Macchu Picchu), which require the use of fossil fuel as an energy source. Fossil fuels are also considered the main source of pollution in the area, representing important inputs of major pollutants (organic compounds) and trace metals and metalloids of environmental interest. Accordingly, this work presents the results of As, Cd, Cr, Cu, Ni, Pb and Zn in sediment profiles from Admiralty Bay. The sediment results from Ferraz station were slightly higher than the other sampling sites. The highest contents were observed for Cu and Zn (from 44 to 89 mg kg⁻¹). Otherwise, by using enrichment factors and geochronology analysis, the most relevant enrichment was observed for As in the samples collected close to the Ferraz station, indicating that increasing As content may be associated with the activities associated with this site.     

氢化物发生-电感耦合等离子体发射光谱法同时测定土壤中痕量砷锑铋汞

土壤样品用水浴加热王水溶解1 h,在10%的盐酸介质下,用0.5 L/min的载气流量,10 g/L的硼氢化钠-氢氧化钠作为还原剂,将自行设计的一种新型氢化物发生器与电感耦合等离子体发射光谱法(ICP-AES)联用测定痕量砷、锑、铋、汞,一次溶样即可实现多元素在同母液同条件下同时测定。方法检出限为0.01～0.06 ng/g,加标回收率为92.0%～102.0%,精密度(RSD)低于5%。此方法通过加入抗坏血酸-硫脲溶液预先将砷和锑还原,汞的测定不受还原剂的影响,同时解决了目前多元素分次测量带来的不便和试剂消耗多等问题,样品前处理及测量过程快速、简单,无记忆效应的影响,适合环境样品中痕量砷、锑、铋、汞的同时测定。     

Uptake and Accumulation of Arsenic in Different Organs of Carrot Irrigated with As‐Rich Water

Irrigation with arsenic (As)‐rich water in agricultural soil may increase high levels of As in crops and cause food chain contamination. In this study, a greenhouse experiment was established using Spanish agricultural soil (Valladolid and Segovia provinces), that are extensively cultivated for carrot plant, to investigate the process of As uptake, bioaccumulation, and translocation of As from root to shoot and leaves in carrot plant. Arsenic concentrations in different organs of carrot plant, rhizosphere soil, and soil solutions were determined by hydride generation atomic absorption spectrometry (AAS). High concentrations of As in irrigation water, and the alkaline and sandy character of this soil enhanced As uptake in carrot plants indicating the potential health risk from consumption of carrots cultivated in these areas. Bioaccumulation of As into the leaves and roots increased with increase of As concentration in irrigation water. Both roots and leaves demonstrated a higher accumulation rate of As at an As concentration of 41 than 131 µg L^?1 in the soil solution. The ratios of As_root/As_leaves showed no statistically significant differences for the different irrigation treatments, and had an average value of 0.36 indicating the high magnitude of As translocation from roots to leaves in carrot plants. The leaves of carrots had a higher affinity for As than roots did. The correlation between As uptake by leaves or roots of carrots and the soluble As in rhizosphere soil did not demonstrate a linear or a plateau curve, indicating a slow but continuous constant As absorption which could be prolonged over time with high potential environmental risks.     

Arsenic and other water‐quality issues affecting groundwater,Indus alluvial plain,Pakistan

Groundwater beneath the alluvial plain of the Indus River, Pakistan, is reported to be widely polluted by arsenic (As) and to adversely affect human health. In 79 groundwaters reported here from the lower Indus River plain in southern Sindh Province, concentrations of As exceeded the WHO guideline value for drinking water of 10 μg/L in 38%, with 22% exceeding 50 μg/L, Pakistan's guideline value. The As pollution is caused by microbially‐mediated reductive dissolution of sedimentary iron oxyhydroxides in anoxic groundwaters; oxic groundwaters contain <10 μg/L of As. In the upper Indus River plain, in Punjab Province, localized As pollution of groundwater occurs by alkali desorption as a consequence of ion exchange in groundwater, possibly supplemented by the use for irrigation of groundwater that has suffered ion exchange in the aquifer and so has values >0 for residual sodium carbonate. In the field area in southern Sindh, concentrations of Mn in groundwater exceed 0.4 mg/L in 11% of groundwaters, with a maximum of 0.7 mg/L, as a result of reduction of sedimentary manganese oxides. Other trace elements pose little or no threat to human health. Salinities in groundwaters range from fresh to saline (electrical conductivity up to 6 mS/cm). High salinities result from local inputs of waste water from unsewered sanitation but mainly from evaporation/evapotranspiration of canal water and groundwater used for irrigation. The process does not concentrate As in the groundwater owing to sorption of As to soils. Ion exchange exerts a control on concentrations of Na, Ca, and B but not directly on As. High values of Cl/Br mass ratios (most ?288, the marine value) reflect the pervasive influence on groundwater of sewage‐contaminated water from irrigation canals through seepage loss and deep percolation of irrigation water, with additional, well‐specific, contributions from unsewered sanitation.     

大同盆地浅层含水层沉积物中砷的生物可利用性评价

以采自大同盆地野外试验场的含水层沉积物为研究对象,调查高砷含水层中生物可利用性砷的含量及其影响因素。经实验室测定,沉积物总体呈碱性,Al、Fe等金属元素含量较高。利用连续提取法发现沉积物中砷结合形态主要为无定形和低结晶铁铝氧化物结合态,其次是残余态砷。其中铁铝氧化物形态的砷所占比例达53.54%,非专性吸附态和专性吸附态占14.33%,生物可利用形态的砷较少,这与体外模拟方法测定的生物可利用性砷含量较低吻合。体外模拟实验还发现：肠阶段生物可利用性砷含量比胃阶段低,生理学提取法(PBET)和体外消化法(IVG)测定的生物可利用性砷差异较小。