氢化物原子荧光光谱法测定水中痕量砷（Ⅲ）和砷（Ⅴ）

应用氢化物发生无色散原子荧光法测定水中痕量As(Ⅲ)和As(Ⅴ).在pH5.6—6.0时,As(Ⅲ)与KBH_4作用生成气态氢化物(AsH_3),被原子荧光仪测定.在此酸度下,AS(Ⅴ)不发生反应.在2NHCl溶液中,用硫脲和抗坏血酸还原As(Ⅴ)为As(Ⅲ),同法测总砷,用差减法求得As(Ⅴ).方法检出限0.1ppb,相对标准偏差4.6—5.8％,回收率93—104％.     

不同产地的几种海藻中砷的形态和含量分析

采用干法消解和盐酸浸提处理、氢化物原子荧光光谱法对不同产地的几种海藻中的砷进行了形态和含量分析.结果表明,在实验浓度范围内,最低检出限达到0.147μg·1-1,线性相关系数0.9990以上,四种褐藻的精密度在0.74%-4.93%之间,回收率在91.64%-101.62%之间.四种褐藻的总砷和无机砷含量分别在16.58μg·g-1和5.104μg·g-1以上,其中羊栖菜的总砷和无机砷含量最高.     

利用高效液相色谱-动态反应池模式-等离子体质谱法测定水稻中的砷形态

利用HPLC-DRC-ICP-MS测定了水稻中4种砷的形态As(Ⅲ)、DMA(Ⅴ)、MMA(Ⅴ)、As(Ⅴ),比较了两种提取剂的优劣.结果表明,三氟乙酸提取剂在提取率及加标回收率两方面均优于甲醇-水.HPLC-DRC-ICP-MS具快速、可自动分析的特点,提取液中上述4种不同形态的砷可在7min内采用等度洗脱法得以有效地分离,其检测限低于0.1 mg·kg-1.     

微波辅助提取-氢化物发生原子荧光光谱法测定土壤中As（Ⅲ）和As（Ⅴ）

建立了微波辅助提取,采用氢化物发生原子荧光光谱法不进行价态分离,直接测定土壤中As（Ⅲ）和As（Ⅴ）的方法。通过加入抗坏血酸作为抗氧化剂,以磷酸溶液、L-半胱氨酸分别为提取剂和还原剂,在不还原与还原两种情况下分别进行测量,根据荧光强度与As（Ⅲ）和As（Ⅴ）的质量浓度关系方程式计算提取液中它们的质量浓度。对实验条件进行优化后,As（Ⅲ）、As（Ⅴ）的方法检出限均可达到0.05μg.g-1,实验精密度（RSD,n=11）分别为1.3%和2.1%,样品加标平均回收率分别为As（Ⅲ）为93.2%~110.0%,As（Ⅴ）为92.6%~104.0%。该方法不需要高效液相色谱等大型设备、简单可靠、易于操作、分析速度快、精密度高,具有在各分析测试实验室推广应用价值。方法已用于实际土壤样品中不同价态无机砷质量分数的测定。     

化工厂区域土壤中砷的化学形态与分布特征

本文通过对大连化工厂区域土壤样品中砷的水溶态、碳酸铵交换态、盐酸溶解态、氢氧化钠溶解态、残渣态的析,以及各种形态中三价、五价砷的测定,评价该区砷的分布特征和污染现状,为研究砷在环境中的迁移规律和污染防治提供科学依据.     

砷形态在湖水中垂直分布的研究

本文以天津水上公园湖泊作为研究现场，通过采样分析，研究了湖水中砷酸盐、亚砷酸盐、一甲基胂酸盐和二甲基胂酸盐的垂直分布及其影响因素。结果表明水上公园湖泊中砷酸盐是溶解态砷的主要存在形式，其垂直分布与悬浮物、叶绿素ａ、磷酸盐的浓度、水文等诸因素密切相关；一甲基胂酸盐含量保持相对稳定；光致转化是影响水中亚砷酸盐垂直分布差异的一个因素。     

基于反相色谱原理HPLC-ICP-MS法同时分离测定环境水中的6种形态砷和3种形态汞

本文建立了使用HPLC-ICPMS联用同时分离测定环境水中的亚砷酸[As(Ⅲ)]、砷酸[As(Ⅴ)]、一甲基砷酸(MMA)、二甲基砷酸(DMA)、砷甜菜碱(AsB)、砷胆碱(AsC)和无机汞(iHg)、甲基汞(MeHg)、乙基汞(EtHg)的方法.该方法结果显示,6种形态砷和3种形态汞的线性相关系数大于0.999,加标...     

黄河(内蒙古段)水体及悬浮物中砷的形态分布

以系统形态分析结合上浮水和悬浮物中砷的总量及形态分布特征,评价了黄河(内蒙古段)水体中砷的潜在危害程度.结果表明,水和悬浮物中砷的总含量出现了比较一致的沿河变化趋势,说明水中的砷主要是泥沙携带的砷,水中含砷量的高低取决于水中悬浮物即泥沙的含量.悬浮物中的砷以Ca-As为主,O-As次之,其它三种形态砷的含量均很低,与黄土中各形态砷的含量比较接近,进一步说明了黄河水体中的砷主要来源于自然界.     

色谱自动进样瓶可溶出砷对样品砷形态测定的影响

选用几种常用玻璃色谱自动进样瓶(简称色谱瓶),包括硼硅玻璃、一级水解级玻璃和高白料玻璃色谱瓶,以及聚丙烯材质的色谱瓶,1%HNO3对色谱瓶浸提后用ICP-MS和HPLC-ICP-MS测定浸提液中砷的总量和形态,并研究了10%HNO3对色谱瓶的清洗效果;此外还探讨了温度及时间对玻璃色谱瓶中砷释放的影响.结果表明,玻璃色谱瓶中砷普遍存在,其中硼硅玻璃色谱瓶浸提液中砷浓度低于1μg·L-1,用10%HNO3酸泡24 h能够全部清除;而一级水解级玻璃和高白料玻璃色谱瓶浸提液中砷的浓度则高达45.67μg·L-1和70.25μg·L-1,酸泡24 h后也有较高的残留量,浓度分别为1.63μg·L-1和0.94μg·L-1.高温能促进玻璃色谱瓶中砷的释放;玻璃色谱瓶中砷的释放量随时间的延长而增加,但短时间内即达到平衡.形态分析结果表明,玻璃色谱瓶浸提液中砷形态为As(Ⅴ),没有检测到As(Ⅲ)、二甲基砷酸(DMA)和甲基砷酸(MMA).同时,聚丙烯色谱瓶浸提液中砷总量低于检测限,因而在进行砷形态测定时,建议使用聚丙烯色谱瓶或者经10%HNO3清洗后的硼硅玻璃色谱瓶,以避免玻璃色谱瓶中As(Ⅴ)的污染.     

锰对土壤砷形态转化及水稻吸收砷的影响

土壤中铁锰氧化物是影响土壤砷形态及其生物有效性的重要因素。通过盆栽试验法,利用土壤理化性质相近而锰质量分数相差大的两种自然土壤混合得到土壤锰质量分数(mg·kg^-1)分别为580(Mn1)、980(Mn2)、1900(Mn3)、3030(Mn4)、4230(Mn5)的5个土壤,种植水稻(Oryza sativa L.)后,分别在水稻分蘖期、抽穗期和成熟期采集土壤孔隙水、水稻和土壤样品进行分析,探讨锰质量分数对土壤中铁、锰氧化物形态和砷形态转变及其对水稻吸收砷的影响和作用机制。结果表明,随着土壤锰质量分数增加,土壤Eh呈升高趋势;土壤中无定形铁氧化物、锰氧化物和游离态锰氧化物质量分数增加,成熟期Mn1和Mn5处理土壤无定形态铁氧化物、锰氧化物分别比分蘖期增加11.9%、40.5%和3.6%、35.7%;随着土壤锰质量分数增加,土壤中非专性吸附砷和专性吸附砷比例呈下降趋势,土壤砷更大比例以无定形铁氧化物结合态、晶质铁氧化物结合态和残渣态存在,从水稻分蘖期到成熟期处理Mn1土壤晶质铁氧化物结合态砷和残渣态砷的质量分数共减少了2.7%,Mn2至Mn5处理晶质铁氧化物结合砷...     

Arsenic speciation in rice consumed in south-western Nigeria,and estimation of dietary intake of arsenic species through rice consumption

This study determined concentrations and speciation of arsenic (As) in rice samples obtained from the cities of Akure, Ore, Ondo and Ikare in Ondo State, south-western Nigeria. The estimated dietary intake of As from rice consumption for total As and the identified As species were compared with the As benchmark dose lower confidence limit. Analyses of rice from the four cities identified three As species: inorganic As, monomethylarsonic, acid and dimethylarsinic acid. Concentrations of total As and the As species differed significantly across the sampling locations (by a factor of 2.5 for total As). Mean levels (±S.D.) were 58.8 ± 0.7 µg/kg total As, 47.0 ± 0.6 µg/kg inorganic As, 0.33 ± 0.03 µg/kg monomethylarsonic acid, and 11.5 ± 0.1 µg/kg dimethylarsinic acid. The estimated mean dietary intakes were 4.1 µg/d total As, 3.3 µg/d inorganic As, 0.02 µg/d monomethylarsonic acid, and 0.8 µg/d dimethylarsinic acid. These values are below the benchmark dose lower confidence limit and comparable to, or lower than, those reported for other countries. Thus, consumption of rice cultivated in south-western Nigeria does not appear to have inherent As-associated health risks.     

砷-硒交互作用对水稻吸收转运砷和硒的影响

采用溶液培养法,研究了两种形态无机As与四价Se交互作用对水稻吸收转运As和Se的影响.结果表明,不同形态As与Se交互作用对水稻吸收转运As和Se影响较大,Se(Ⅳ)显著地提高水稻根系而降低水稻茎叶对As的吸收积累.与对照处理相比,在1.0μmol·L-1As(Ⅲ)和As(Ⅴ)处理下添加1.0μmol·L-1Se(Ⅳ)分别导致水稻根系As含量提高59.5%和21.3%,而水稻茎叶As浓度减少10.4%和21.9%.As(Ⅲ)或As(Ⅴ)处理显著降低水稻茎叶对Se的吸收积累,但As(Ⅴ)处理对水稻根系积累Se没有影响.在1.0μmol·L-1Se(Ⅳ)处理下,添加1.0μmol·L-1As(Ⅲ)和1.0μmol·L-1As(Ⅴ)导致水稻茎叶Se浓度分别比对照处理降低41.9%和30.3%.Se(Ⅳ)与As(Ⅲ)或As(Ⅴ)对水稻转运As、Se的能力具有交互拮抗作用.研究结果表明,在As污染农田中,可通过施用Se肥来提高植物的Se营养,降低植物对As的吸收积累,从而降低As对人体健康的危害.     

珠江三角洲稻田土壤砷及其向水稻籽粒迁移特征

采集珠江三角洲区域水稻(Oryze sativa L.)植株的根系、秸秆、稻谷和对应的耕层土壤(0～15锄)样品,分析土壤和水稻植株中砷含量,初步研究土壤砷与土壤基本理化性质的关系及砷在土壤-水稻系统中的迁移规律.结果表明,土壤砷含量在1.83～18.14 mg·kg~(-1)之间,土壤砷与土壤有机质、砂粒含量呈显著负相关,与土壤粉粒含量呈显著正相关.糙米中的砷含量在0.21～0.43mg·kg~(-1)之间,均未超过国家食品卫生标准(0.7mg·kg~(-1)),砷在水稻植株中的分布规律为根>秸秆>颖壳>糙米.糙米砷含量与秸秆砷含量呈极显著正相关,与秸秆中P/As、Si/As摩尔比呈极显著负相关,因此,降低秸秆中As的积累、增加秸秆中P、Si的积累可降低水稻籽粒中的砷含量.     

灭线磷在稻田土壤和田水中的降解动态和残留分析

采用气相色谱法研究了10%灭线磷GR(颗粒剂,下同)中灭线磷在广东省、湖北省两地水稻田土壤和田水中的残留降解动态和最终残留量.研究结果表明灭线磷在土壤和田水中的添加回收率分别为82.85%～93.70%和85.03%～98.17%.灭线磷在稻田土壤和田水中降解动态符合一级动力学指数模型,在广东省和湖北省稻田土壤中的半衰期分别为9.73 d、10.70 d,田水中的半衰期分别为0.83 d、0.85 d.10%灭线磷GR以(1800 g(a.i.)·m~(-2)和2700 g(a.i .)·hm~(-2)两个剂量施药后,灭线磷在广东省土壤中的最终残留质量分数为0.002 3～0.0034mg·kg~(-1);2700 g(a.i.)·hm~(-2)施药后,灭线磷在湖北省土壤中的最终残留质量分数为0.001 7 mg·kg~(-1),1800 g(a.i.)·hm~(-2)施药后,在土壤中未检测出灭线磷.     

Environmental geochemistry study of arsenic in Western Hunan mining area,P.R. China

The geochemical characteristics of arsenic in the soil of the Western Hunan mining area of P.R. China were systematically studied. The results show that the strata of Western Hunan are rich in arsenic and that Western Hunan is a geochemically abnormal region for arsenic. The experimental study on speciation in the strata also indicates that the speciation of arsenic in the Neoproterozoic-Cambrian strata are mainly easily transferred speciation (exchangeable, carbonate-bound, sulfides-bound), which are approaching or exceed 60%. Arsenic content in the main soil of Western Hunan is in the range of 8.8–22.8 μg g⁻¹, the mean value is 16.1 μg g⁻¹, which is larger than the arsenic background value of Hunan soil. The distribution of rock with high arsenic content or high easily transferred arsenic speciation is consistent with the distribution of high arsenic content soil. In the mining region, part soils and river/brook waters were polluted by mine tailings and mining/smelting waste water. The arsenic content in polluted paddy soils and river/brook water is 46.26–496.19 μg g⁻¹, 0.3–16.5 mgL⁻¹, respectively. The positive abnormality and pollution of arsenic in the soil and water affects the arsenic content of the crop and the inhabitants’ health.     

Determination of total hydrocarbon concentration in coastal waters and sediments off the east coast of Peninsular Malaysia

To determine the level of total hydrocarbon concentrations (THCs) along the eastern coastal regions of Peninsular Malaysia, samples of subsurface seawater (1 m) and surface sediments were collected from several sampling stations between June and August 1993. THCs in seawater and sediments as determined by fluorescence spectroscopy ranged from 1.4 to 21.8 µg L-1 (Seligi crude oil equivalents) and from 0.79 to 20.0 mg kg-1 (dry weight Seligi crude oil equivalents) respectively. In comparison to results obtained in similar surveys in Malaysian waters, the levels of THCs found in the present study were significantly lower indicating lower hydrocarbon contamination in the area studied.     

砷污染土壤对不同品种水稻生长的影响

重金属如何影响水稻(Oryza sativa L.)的生长及产量一直是粮食生产中的研究重点。利用盆栽实验,首次比较了砷(As)对三个品系(杂交稻、常规稻和糯稻)共20个品种水稻生长的影响,以期选定适合在As污染区种植的水稻品种。结果显示,不同品系水稻在As污染土壤中的生长显著不同,杂交稻的生长优于糯稻和常规稻,但糯稻和常规稻差异不显著,表明杂交稻更适宜在砷污染土壤种植。同一品系内不同品种水稻的生长也有较大差异,杂交稻II优804的干物质积累量最高,每株达到0.055g。     

Determination of mercury and arsenic levels in fish caught in the Beheshtabad River,Chaharmahal and Bakhtiari Province,Iran

Mercury and arsenic pollution has been recognized as a potential environmental and public health problem for over 40 years. The major source of exposure to mercury for humans is the ingestion of fish. This study was conducted with the aim of determining the levels of mercury and arsenic in the muscles of four fish species caught in the Beheshtabad River and comparing the results with the maximum tolerance levels for mercury and arsenic. The samples of 90 fish were used for the determination of both the metals by graphite furnace atomic absorption spectrometry. The results showed that the concentrations ranged from 1.5 to 3.8 µg kg^?1 for mercury and from 35 to 70 µg kg^?1 for arsenic, with means of 2.7 ± 0.5 and 57 ± 12 µg kg^?1, respectively. Both mean levels were lower than the threshold limits acceptable by WHO standards.     

Efficacy of rapeseed residue and eggshell waste on enzyme activity and soil quality in rice paddy

Addition of plant residue into soils improves soil physiochemical properties and its fertility. Rapeseed residue is an emerging N source to paddy soils via rice-rape double-cropping practice. The objective of this study was to evaluate the effects of rapeseed residue and eggshell waste on chemical changes and enzyme activity in the rice paddy soil. The powdered eggshells at 0, 1, 3, and 5% were applied once to 7.0 kg paddy repacked soils in each pot treated with the rapeseed residue or the conventional N, P, and K fertilisers. Eight rice seedlings (Oriza sativa L. cv. Ilmibyeo) (40 days after sowing) were transplanted to the treated each pot. The contents of total C (TC) and N (TN), and organic matter (OM) were significantly increased in soils treated with the rapeseed residue compared to the N, P, and K fertilisers. With the addition of eggshell containing ～92% CaCO₃, a considerable increase of soil pH was observed in soils treated with the rapeseed residue and the N, P, and K fertilisers, compared to the untreated soil. Activities of β-glucosidase, urease, and arylsulfatase enzymes were higher in soils treated with the rapeseed residue than soils treated with the N, P, and K fertilisers. The eggshell additions at 1, 3, and 5% into soils treated with the rapeseed residue increased enzyme activity mainly resulting from N mineralisation, whereas no change in enzyme activity was observed in the soils treated with the NPK fertiliser. The combined use of the rapeseed residue and the eggshells can be beneficial to improve soil environment.