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.     

Assessment of As and Heavy Metal Contamination in the Vicinity of Duckum Au-Ag Mine, Korea

In order to assess the potential of As and heavy metal contamination derived from past mining activity and to estimate the human bioavailability quotients for As and heavy metals. Tailings, soils and crop samples were collected and analysed for As, Cd, Cu, Pb and Zn. The mean concentrations of As, Cd, Cu, Pb and Zn in the tailings were 68.5, 7.8, 99, 3,754 and 733 µg g^–1, respectively. Maximum Pb concentration in tailings was up to 90 times higher than its tolerable level. The concentrations of these metals were highest in the soils from the dressing plant area, and decreased in the order: farmland soil to paddy soil. In particular, some of the soils from the dressing plant area contained more than 1% of Pb and Zn. The pollution index ranged from 0.19 to 1.93 in paddy soils, and from 1.47 to 3.60 in farmland soils. The average concentrations of heavy metals in crops collected from farmland were higher than those in rice stalks or rice grains, and higher than the internationally accepted limits for vegetables. Element concentrations extracted from farmland soils within the simulated human stomach for 1 h are 9.4 mg kg^–1 As, 3.8 mg kg^–1 Cd, 37 mg kg^–1 Cu, 250 mg kg^–1 Pb and 301 mg kg^–1 Zn. In particular, the extracted concentrations of Cd, Pb and Zn are in excess of the tolerable levels. The results of the simple bioavailability extraction test (SBET) indicate that regular ingestion (by inhalation and from dirty hands) of soils by the local population could pose a potential health threat due to long-term toxic element exposure.     

土壤中铜、砷对水稻生长发育影响的研究

通过田间小区试验，研究了广州近郊冲积土添加重金属铜、砷对水稻生长发育的影响．结果表明，随着铜、砷浓度的增加，水稻的株高、生物产量和经济产量均明显下降；铜、砷在水稻各器官的含量分布是根＞茎叶＞糙米；糙米对铜、砷的吸收累积量很少，均未超过食品卫生标准．若以产量下降10％作为水稻受害的临界点，则铜的临界浓度为100mg／kg，砷为30mg／kg．     

砷在三种紫色土中的化学行为及其与作物效应的关系

通过水稻在不同砷浓度处理过的三种紫色土的盆栽试验,研究了砷的吸附特征,形态变化及其与砷的作物效应的关系,揭示了砷在不同土壤中对水稻毒害和在水稻体内累积程度不一样的原因是由于不同土壤的性质影响到砷的吸附和形态变化。其中砷在土壤中的形态变化是最重要的因素之一。在诸形态中,以A-As和Ca-As最为重要。土壤的碳酸盐体系可能是影响三种紫色土砷的化学行为及其生态效应的一个重要因素。     

Simultaneous oxidation of Mn(II) and As(III) on cupric oxide (CuO) promotes As(III) removal at circumneutral pH

Oxidation of Mn(II) or As(III) by molecular oxygen is slow at pH < 9, while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water. However, the reaction mechanisms on simultaneous oxidation of Mn(II) and As(III) on oxide mineral surface and their accompanied removal efficiency remain unclear. This study compared Mn(II) oxidation on four common metal oxides (γ-Al₂O₃, CuO, α-Fe₂O₃ and ZnO) and investigated the simultaneous oxidation and removal of Mn(II) and As(III) through batch experiments and spectroscopic analyses. Among the tested oxides, CuO and α-Fe₂O₃ possess greater catalytic activity toward Mn(II) oxidation. Oxidation and removal kinetics of Mn(II) and As(III) on CuO indicate that O₂ is the terminal electron acceptor for Mn(II) and As(III) oxidation on CuO, and Mn(II) acts as an electron shuttle to promote As(III) oxidation and removal. The main oxidized product of Mn(II) on CuO is high-valent MnO_x species. This newly formed Mn(III) or Mn(IV) phases promote As(III) oxidation on CuO at circumneutral pH 8 and is reduced to Mn(II), which may be then released into solution. This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn(II) and As(III) and suggests that CuO should be considered as an efficient material to remediate Mn(II) and As(III) contamination.     

Investigation and risk assessment modeling of As and other heavy metals contamination around five abandoned metal mines in Korea

Tailings, agricultural soils, vegetables and groundwater samples were collected from abandoned metal mines (Duckum, Dongil, Dongjung, Myoungbong and Songchun mines) in Korea. Total concentrations of arsenic (As) and heavy metals (Cd, Cu, Pb and Zn) were analyzed to investigate the contamination level. Several digestion methods (Toxicity characteristics leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), 0.1 N/1 N HCl) and sequential extraction analysis for mine tailings were conducted to examine the potential leachability of As and heavy metals from the tailings. The order of urgent remediation for the studied mines based on the risk assessment and remedial goals was suggested. The Songchun mine tailings were most severely contaminated by As and heavy metals. Total concentrations of As and Pb in the tailings were 38,600–58,700 mg/kg (av. 47,400 mg/kg) and 11,800–16,800 mg/kg (av. 14,600 mg/kg), respectively. Agricultural soils having high As concentrations were found at the all mines. Average concentrations of Cd in the vegetables exceeded the normal value at all mines areas, while As only at the Dongjung, Myoungbong, and Songchun mine area. One groundwater sample each from the Dongil and Myoungbong mines, and 4 groundwater samples from the Songchun mine had values above 10 μg/L of As concentration. The TCLP method revealed that only Pb in the Songchun tailings, 6.49 mg/L, exceeded the regulatory level (5 mg/L). Employing the 1-N HCl digestion method, the concentration of As in the Songchun mine tailings, 4,250 mg/kg, was up to 3,000 times higher than its Korean countermeasure standard. Results from the sequential extraction of As in the tailings showed that the easily releasable fraction in the Myoungbong and Songchun mine tailings was more than 30% and the residual fraction was less than 40%. Based on results showing the exposure health risk employing the hazard quotient and cancer risk of As, Cd and Zn, the Dongil mine needs the most urgent remedial action. The concentration reduction factor (CRF) of As in both soil and groundwater follows the order: Songchun>Dongjung>Dongil>Myoungbong>Duckum mine.     

Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study

Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono- and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5 mg/L Ca(ClO)₂. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (< 10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 μg/L–0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

原子荧光法测定水中砷监测质量控制指标研究

通过全国多家实验室测定的大量监测数据研究了原子荧光法测定水中砷的质量控制指标,并与《水和废水监测分析方法》(第4版)中的相关指标进行了比较,旨在为环境监测工作提供质量控制依据和质量控制指标。研究表明,标准样品实验室内相对偏差的控制范围为小于等于4%;浓度小于0.05 mg/L的实际样品的相对偏差小于等于10%,浓度大于等于0.05 mg/L时相对偏差小于等于5%。实验室间相对偏差的控制范围为小于等于10%。相对误差一般控制在±15%以内,加标回收率为90%～110%。     

等离子发射光谱-质谱(ICP-MS)直接用于饮用水中的砷、锑、硒测定研究

用等离子发射光谱和等离子发射光谱-质谱作比较,等离子发射光谱-质谱用于饮用水As、Sb、Se的测量时需考虑校正系数,通过不确定度分析,确定了ICP-MS测定方法不确定度大小,得出结论:不要氢化物发生器,不加EDTA作为掩蔽剂,也可以直接用于实际.