小清河表层沉积物重污染区重金属赋存形态及风险评价

测定了小清河表层沉积物重污染区间隙水中重金属(Cu、As、Pb、Zn、Cr、Cd和Ni)的质量浓度,采用改进的BCR顺序提取法分析了沉积物中重金属的赋存形态,并分别基于美国水质基准(CCC、CMC)和风险评价编码法(RAC)、潜在生态风险指数法对间隙水和表层沉积物中重金属的毒性及生态风险进行评价.结果表明,小清河沉积物间隙水中的重金属基本不会对水生态系统产生毒性.除As外,表层沉积物中6种重金属的含量显著高于土壤背景值,呈现明显的累积效应.沉积物中Cu、As和Ni主要赋存于残渣态,Pb、Cr主要赋存于可氧化态和残渣态,Zn、Cd以酸可溶解态和可还原态为主.Cd、Zn、Cr和Pb的有效态含量高于残渣态,有较高的二次释放潜力.RAC的评价结果表明,沉积物中Cu、Pb、Cr和As处于无风险到低风险级,Ni处于低风险到中等风险级,Cd处于中等到高风险级,Zn处于中等到极高风险级,不同重金属RAC的平均值依次为CdZnNiAsCuCrPb.潜在生态风险指数法的评价结果表明,沉积物中除Cd有强~很强生态风险外,其他6种重金属均表现为低生态风险,RI值介于136.83~264.83,研究区采样点处于中等~强生态风险.     

镉-八氯代二苯并呋喃复合污染土壤中紫茉莉对镉的修复能力

针对土壤重金属-持久性有机物复合污染日益严重的现象,本研究以镉(Cd)和1,2,3,4,6,7,8,9-八氯代二苯并呋喃(OCDF)为典型的重金属和持久性有机污染物,选取紫茉莉为修复植物,通过温室盆栽实验研究Cd-OCDF复合污染土壤中植物的耐性以及有机物对植物提取土壤中Cd能力的影响.结果表明种植3个月期间,紫茉莉在Cd浓度≤200 mg·kg-1的复合污染土壤中具有较强的耐性,株高和生物量降低有限;与Cd单一污染相比,OCDF对紫茉莉株高、根部生物量无显著影响,Cd浓度200 mg·kg-1,OCDF浓度500μg·kg-1时,OCDF存在使紫茉莉地上生物量降低22.19%,其它处理组,OCDF对紫茉莉地上生物量无显著抑制作用,反而某些处理组增加紫茉莉地上生物量.Cd-OCDF复合污染效应与Cd单一污染相比,Cd浓度为200 mg·kg-1,OCDF浓度为100μg·kg-1时,紫茉莉根部Cd积累量降低了34.44%,Cd浓度为400 mg·kg-1,OCDF浓度为100μg·kg-1时,根部和叶部Cd积累量分别降低了7.93%和18.09%;其它处理组,OCDF不同程度地提高了紫茉莉根、茎、叶提取和积累土壤中Cd的能力.可见,用紫茉莉修复高浓度Cd-OCDF复合污染土壤中的Cd具有实践上的可行性.     

共生细菌对盐生小球藻亚砷酸盐代谢的影响

为探讨共生细菌对盐生小球藻（Chlorella salina）亚砷酸盐（As（III））富集和形态转化的影响,从C.salina培养液中分离培养出一株共生细菌,并采用抗生素处理C.salina获得无菌藻,设置0,75,150,300,750 μg/LAs（III）溶液处理带菌和无菌的C.salina,7d后测定C.salina对As（III）的吸收、吸附和富集量,以及培养液和藻细胞内As的形态,计算带菌和无菌C.salina对As（III）的氧化率和去除率;使用不同浓度的As（III）处理共生细菌7d,并以300μg/L的As（III）处理共生细菌不同时间,计算两种情况下共生细菌对培养液中As（III）的氧化率和去除率.结果表明：C.salina的共生细菌为根癌农杆菌（Agrobacterium tumefaciens WB-1）;与无菌C.salina相比,带菌C.salina生长更快、对As（III）的耐性更强.带菌C.salina对As（III）的富集量为103.10~448.12mg/kg、氧化率为78.93%~96.88%、去除率为18.92%~55.21%,显著高于无菌C.salina的富集量（11.68~91.39mg/kg）、氧化率（14.46%~26.39%）和去除率（12.82%~29.15%）,也高于A.tumefaciens WB-1对As（III）的氧化率（4.51%~30.61%）和去除率（1.86%~16.19%）.此外,带菌C.salina胞内还检测到少量的As（III）和甲基砷,而在无菌C.salina胞内没有甲基砷存在.共生细菌促进了盐生小球藻对As（III）的富集和形态转化.     

LED3A土柱淋洗Pb与Zn污染砂土的效果

为探究不同淋洗方式下螯合型表面活性剂LED3A（N-十二酰基乙二胺三乙酸钠盐）对重金属污染土壤的淋洗效果,采用室内土柱淋洗法研究了LED3A在不同流速条件下对Pb、Zn单一污染砂土的淋洗效果,并通过优化的BCR法分析了淋洗前、后土柱中不同深度处Pb、Zn的形态变化特征.结果表明:LED3A对Pb、Zn单一污染砂土的淋洗规律基本类似,淋出液中ρ（Pb）、ρ（Zn）随淋洗液累积孔隙体积数目的增加呈现急剧增大、达到峰值后逐渐降低的趋势;Pb、Zn的淋洗曲线中均存在不同程度的拖尾现象,且对称性较差;淋出液中ρ（Pb）、ρ（Zn）峰值和Pb、Zn最大累积去除率均随流速的增大而减小.随着淋洗深度和流速的增加,各形态Pb、Zn的去除率均呈现减小的趋势,LED3A对酸可提取态Pb、Zn的去除效果最为显著,去除率均大于50%;对氧化物结合态、有机结合态和残渣态Pb、Zn的去除率大小顺序与淋洗深度和流速有关;对比淋洗前、后土柱中重金属的形态分布可知,最易释放和被生物利用的酸可提取态的占比明显减少,不易或不能被生物利用的氧化物结合态、有机结合态和残渣态的占比明显增加.研究显示,LED3A低流速淋洗不仅能够去除一定量的土壤重金属,同时可有效降低残留重金属对环境的潜在风险.      

Response of the sediment geochemistry of the Changjiang River (Yangtze River) to the impoundment of the Three Gorges Dam

Based on the measurement of major and trace elements in suspended sediments in the low reaches of the Changjiang River during throughout a whole hydrologic year, the origins, seasonal variations, and fluxes of multielements and the human impacts on multielements transport processes have been analyzed along with the influence of weathering in the Changjiang River basin. The results show that most element contents were high in both autumn and winter and low in summer, which was largely caused by the dilution of discharge. Weathering detritus in the Changjiang River basin is the main source of most elements in suspended sediments. However, riverine pollution could bring more loadings of Cd, Pb, As and Zn into river water than it did a few decades ago. The annual average fluxes of Cd, Pb and Zn, which are major contamination elements, to the sea were 179 ± 21 tons/year, 7810 ± 675 tons/year, and 12,000 ± 1320 tons/year,respectively, in which approximately 8.7%, 11.9% and 2.7% of their loadings, respectively,were contributed by pollution inputs. Element exports mainly occurred in the summer(44.4%–57.4%) in the lower part of the Changjiang River. A general relationship between sediment retention and element content suggests a positive feedback mechanism for the decreased number of particles, in which element riverine loadings are reduced due to the enhanced trapping effect by the Three Gorges Dam(TGD). Compared to those in 1980,current element shares of the Changjiang River compared to the global budget have declined due to the construction of the TGD.     

Treatment of metal-chloride-enriched wastewater by simulated constructed wetlands

The ability of surface flow and subsurface flow simulated wetlands to remove heavy metals from a NaCI-enriched wastewater was examined, employing bulrush (Scirpus validus) and cattail (Typha angustifolia) plants, and two organically amended substrates (mixtures of mushroom compost and leaf litter,with topsoil) with a limestone liner. A simulated wastewater solution containing Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn as chloride salts was added to the wetlands at a rate of 0.3 l h^–1. During 12 weeks of surface flow, Fe was retained most efficiently (74%), and Mn the least (24%). Most metal retention occurred in residual forms, primarily in the upper 5 cm of the substrate. A subsequent 10 week subsurface flow treatment exhibited greater removal efficiencies for all metals, probably due to increased contact with the highly buffered lower substrate. During both treatments, bioaccumulation occurred in plants, but accounted for a very small portion of the total metal removal. Plant species did not significantly influence wetland performance with respect to metal retention. Substrate type did not affect removal efficiency for most metals, but did influence the forms of the metals retained in the wetland.To whom correspondence should be addressed.     

In-situ electrochemical measurements of total concentration and speciation of heavy metals in acid mine drainage (AMD): assessment of the use of anodic stripping voltammetry

We assessed the use of anodic stripping voltammetry (ASV) for in-situ determinations of both total concentration and speciation of dissolved heavy metals (Cd, Cu, Pb and Zn) in acid mine drainage (AMD). In the Kwangyang Au–Ag mine area of South Korea, different sites with varying water chemistry within an AMD were studied with a field portable anodic stripping voltammeter. Anodic stripping voltammetry after wet oxidation (acidification) was very sensitive enough to determine total concentration of dissolved Cd because Cd was dominantly present as ‘labile’ species, whilst the technique was not so effective for determining total Cu especially in the downstream sites from the retention pond, due to its complexation with organic matter. For dissolved Pb, the concentrations determined by ASV after wet oxidation generally agreed with those by ICP-AES. In the downstream samples (pH>5), however, ASV data after wet oxidation were lower than ICP-AES data because a significant fraction of dissolved Pb was present in those samples as ‘inert’ species associated with colloidal iron oxide particles. The determination of total dissolved Zn by ASV after wet oxidation appeared to be unsatisfactory for the samples with high Cu content, possibly due to the interference by the formation of Zn–Cu intermetallic compounds on the mercury coated electrode. In AMD samples with high dissolved iron, use of ultraviolet irradiation was not effective for determining total concentrations because humate destruction by UV irradiation possibly resulted in the removal of a part of dissolved heavy metals from waters through the precipitation of iron hydroxides.     

Effect of natural organic matter on arsenic release from soils and sediments into groundwater

Arsenic (As) contamination in groundwater has received significant attention recently. Natural and anthropogenic sources contribute to the worldwide occurrence of As contamination. As speciation is an important factor related to its toxic and mobile behavior. The release of As from soils and sediments into groundwater is governed by several geophysicochemical processes, of which, As sorption behavior is of principle significance. This review paper summarizes existing information regarding the effects of natural organic matter (NOM) on the fate and mobility of As species in the environment. NOM may enhance the release of As from soils and sediments into the soil solution, thereby facilitating As leaching into the groundwater. The main influencing mechanisms include competition for available adsorption sites, formation of aqueous complexes, and/or changes in the redox potential of site surfaces and As redox speciation. NOM may also serve as binding agents, thereby reducing As mobility. However, comparably little research has been performed on this aspect. Since most investigations have been done on purified minerals under laboratory conditions, further research involving various geological materials under natural environmental conditions is required. Development of proper geochemical conceptual models may provide means of predicting the role of NOM in arsenic leaching and/or immobilization.     

Binding of Pb(II) in the system humic acid/goethite at acidic pH

The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.     

Copper complexation by tannic acid in aqueous solution

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon (OC)/l was investigated in a nine-step titration experiment (Cu/OC molar ratio = 0.0030–0.0567). We differentiated between soluble and insoluble Cu species by 0.45 μm filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations (‘free’ Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (>0.45 μm) was the dominant Cu species for Cu/OC = 0.0030–0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 × 10⁻⁶– 5.58 × 10⁻⁶ cm² s⁻¹).