利用主动土壤干燥-微波消解技术和原子荧光分光光度法分析土壤中砷的研究

研究利用主动土壤干燥技术,配合微波消解、原子荧光分光光度法,在短时间内完成大量不同用途土壤,如湿地、山林、农田耕地、沙石地等样品中砷的测定。采集的新鲜土壤样品经初筛,过滤、筛分等处理后,利用主动烘干技术,模拟自然干燥状态,可以快速烘干不同含水量的大量样品。该方法避免了因自然风干产生的实验室间的交叉污染,可以短时间处理大量样品;利用微波消解法进行前处理,再利用原子荧光分光光度法进行样品测定。该研究对52个土壤样品中的砷进行了测定,砷含量在2.70~27.3mg/kg。方法的最低方法检出限可以达0.001mg/kg。     

原子荧光法测定水中砷含量的不确定度评定

以氢化物-原子荧光法测定水中砷含量为例,应用不确定度理论,从测试过程和计算方法的角度分析了测量不确定度的各种影响因素:标准物质、溶液稀释情况、工作曲线的非线性以及原子荧光光度计的测量性能等,对各测量不确定度分量进行计算和评定。结果表明:原子荧光法测定水中砷含量的测量不确定度的主要影响因素是工作曲线的非线性和原子荧光光度计的测量性能,其次是标准储备液的逐级稀释,当水样稀释倍数非常低时,因水样稀释引入的不确定度可忽略不计。砷含量的扩展不确定度为1.2μg/L,置信水平为95%。     

Spatiotemporal distribution of arsineic species of oysters (Crassostrea gigas) in the coastal area of southwestern Taiwan

This study investigated total arsenic (As) and As species contents of oysters (Crassostrea gigas) in different production areas, seasons and sea locations on the southwestern coast of Taiwan. Analytical results indicate that contents of total As, arsenite, arsenate, dimethylarsinic acid, monomethylarsonic acid and arsenobetaine in oysters are 9.90 ± 3.68, 0.091 ± 0.104, 0.033 ± 0.038, 0.529 ± 0.284, 0.037 ± 0.046 and 3.94 ± 1.33 mg/g (dry wt), respectively. A ratio of inorganic As concentrations to total As concentrations is 1.26%. Total As contents of oysters cultured in the outer sea are statistically significantly lower than those of oysters cultured in the inner sea. The total As contents of oysters is the highest in Putai, where the blackfoot disease prevails. The low As contents in oysters is attributed to the low temperature in winter, which slows the metabolism of oysters. A maximum value is 33.37 μg/g (dry) in Putai in spring, because a considerable amount of aquacultural waste water with high As contents is discharged into adjacent drainage channels and rivers there during that season.     

全自动石墨消解-原子荧光法测定土壤中砷和汞

采用全自动石墨消解仪代替水浴锅加热王水消解法处理土壤样品,用原子荧光法测定消解液中的砷和汞。该方法在0μg/L~20.0μg/L范围内线性良好,测定有证标准土壤样品的结果均在标准值允许范围内,砷、汞测定结果的RSD分别为2.5%~4.8%、2.9%~5.4%,比王水消解法的测定结果更靠近标准值,实际土壤样品的加标回收率分别为94.6%~104%、92.6%~105%。     

水浴消解-原子荧光法测定土壤中的砷汞

建立了王水水浴消解-原子荧光法测定土壤中砷汞的方法,确定还原剂为硼氢化钾,测砷和汞时硼氢化钾的最优质量分数分别为2%和0.05%,载流为5%盐酸。该法砷和汞分别在质量浓度0.0~40.0μg/L和0.00~4.00μg/L范围内线性良好,相关系数均0.999 5,砷和汞的检出限分别为0.009和0.001 mg/kg,相对标准偏差分别为3.90%和2.67%,加标回收率分别为94.1%~107.6%和92.0%~104.0%。采用本法对国家标准土壤样品和东海县部分农田土壤样品进行测定分析,结果良好,表明该法操作简单、灵敏度高、实用性好,适用于土壤中砷和汞的测定。     

Levels and speciation of arsenic in the atmosphere in Beijing, China

Arsenic levels and speciation in the total suspended particles (TSPs) were quantitatively determined by high performance liquid chromatography on-line coupled with hydride generation atomic fluorescence spectrometry in Beijing, China from February 2009 to March 2011. The high TSP levels fluctuated between 0.07 and 0.79 mg m⁻³, with a mean level of 0.32 ± 0.17 mg m⁻³. The total arsenic concentrations ranged from 0.03 to 0.31 μg m⁻³ (mean: 0.13 ± 0.06 μg m⁻³) in Beijing‘s air. The concentrations of As(III) and As(V) ranged from 0.73 to 20 ng m⁻³ (mean: 4.7 ± 3.6 ng m⁻³) and from 14 to 2.5 × 10² ng m⁻³ (mean: 67 ± 35 ng m⁻³), respectively. As levels and speciation demonstrated relative higher levels in spring and autumn and lower values in summer and winter. As(V) accounted for 81-99% of the extractable species in the TSP samples which showed that As(V) was the major fraction of the extractable As. Organoarsenic species, monomethylarsonate (MMA) and dimethylarsinate (DMA) were not found in all samples. Higher values of enrichment factors demonstrated that arsenic in TSP mainly come from anthropogenic sources. High As and its species levels in air and respiratory exposure (0.30-0.84 μg d⁻¹) attributed to higher excess cancer risk ((4.2 ± 2.0) × 10⁻⁴) for people in Beijing.     

Environmental impact of flood: the study of arsenic speciation in exchangeable fraction of flood deposits of Warta river (Poland) in determination of "finger prints" of the pollutants origin and the ways of the migration

The paper presents the application of the hyphenated technique - high-performance liquid chromatography with atomic absorption spectrometry detection with hydride generation (HPLC-HG-AAS) - in the determinations of inorganic forms of arsenic: As(III) and As(V) in the exchangeable fraction of flood deposits. The separation of analytical signals of the determined arsenic forms was obtained using an ion-exchange column in a chromatographic system with the atomic absorption spectrometer as a detector, at the determination limits of 5 ng g⁻¹ for As(III) and 10 ng g⁻¹ for As(V). Flood deposits were collected after big flood event in valley of the Warta river which took place in summer 2010. Samples of overbank deposits were taken in Poznań agglomeration and vicinity (NW Poland). The results of determinations of arsenic forms in the exchangeable fraction of flood deposits allowed indication of a hypothetical path of deposits migration transported by a river during flood and environmental threats posed by their deposition by flood.     

The influence of diet on intra and inter-individual variability of urinary excretion of arsenic species in Italian healthy individuals

To study the effect of eating foods with a high arsenic (As) content on the intra and inter-individual variability of urinary concentrations of the As species, daily urine samples were collected for 10 consecutive days from 12 healthy male subjects. A daily food diary was kept throughout the study period. Personal exposure to airborne As was measured once during the study. As³, As⁵, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in all urine samples by inductive coupled plasma mass spectrometry, and the sum of As³ + As⁵ + MMA + DMA (iAs) by hydride generation-atomic absorption spectrophotometry. Exposure to airborne As was below the limit of detection in all samplings. As³ was found in only 19.2% and As⁵ in only 3.3% of the urine samples, whereas high urinary concentrations of arsenobetaine were observed. With the exception of arsenobetaine, expressed as a percentage, a significant inter-individual variability was observed for all species of As, for iAs and for the MMA/DMA ratio (p < 0.001). Instead, the intra-individual variability was significant only for the MMA/DMA ratio (p < 0.001). Among foods with a high As content, only a heavy consumption of seafood was shown to influence inter-individual variability of DMA%, arsenobetaine expressed as μg g⁻¹ creatinine and iAs. In conclusion, even in populations with a high intake of organic As through foods, the finding of a significant inter-individual but no significant intra-individual variability of urinary species confirms the usefulness of urinary As speciation for biological monitoring of exposure to As.     

Partitioning of arsenic in soil-crop systems irrigated using groundwater: a case study of rice paddy soils in southwestern Taiwan

The accumulation of As in rice due to groundwater irrigation in paddy fields represents a serious health hazard in South and Southeast Asia. In Taiwan, the fate of As in long-term irrigated paddy fields is poorly understood. Groundwater, surface soil, and rice samples were collected from a paddy field that was irrigated with As-containing groundwater in southwestern Taiwan. The purpose of this study is to elucidate the source and sink of As in the paddy field by comparing the As fractions in the soils that were obtained by a sequential extraction procedure (SEP) with the As uptake of rice. The risks associated with eating rice from the field can thus be better understood. The concentration of As in groundwater varied with time throughout the growing seasons of rice, but always exceeded the permitted maximum (10 μg L⁻¹) for drinking water by the WHO. The As concentration increased with the concentration of Fe in the groundwater, supporting the claim that a large amount of As was concentrated in the Fe flocs collected from the internal wall of the groundwater pump. The results of the SEP revealed that As bound with amorphous and crystalline hydrous oxides exhibited high availability in the soils. The root of rice accumulated the largest amount of As, followed by the straw, husk, and grain. Although the As concentration in the rice grain was less than 1.0 mg kg⁻¹, the estimated intake level was close to the maximum tolerable daily intake of As, as specified by the WHO.     

Interactions of arsenic and phenanthrene on their uptake and antioxidative response in Pteris vittata L

The interactions of arsenic and phenanthrene on plant uptake and antioxidative response of Pteris vitatta L. were studied hydroponically. The combination of arsenic and phenanthrene decreased arsenic contents in fronds by 30-51%, whereas increased arsenic concentrations 1.2-1.6 times in roots, demonstrating the suppression of arsenic translocation compared to the corresponding treatment without phenanthrene. Under the co-exposure, As(III) concentrations in fronds deceased by 12-73%, and at higher arsenic exposure level (≥10 mg/L), As(V) in fronds and As(III) in roots increased compared to the single arsenic treatment. Arsenic exposure elevated phenanthrene concentrations in root by 39-164%. The co-existence of arsenic and phenanthrene had little impact on plant arsenic accumulation, although synergistic effect on antioxidants was observed, suggesting the special physiological process of P. vitatta in the co-exposure and application potential of P. vitatta in phytoremediation of arsenic and PAHs co-contamination.