某湿地生态保护区水体中铜的生态风险评价及管理限值研究

铜是生物必需的微量元素,但过量暴露会对生物产生毒害效应。针对我国南方城市某湿地生态保护区水体重金属污染问题,参照《澳大利亚和新西兰淡水和海水水质指南》,应用物种敏感度分布(speeies sensitivity distribution,SSD)方法和联合概率曲线(joint probability curve,JPC)方法评价水体中铜的生态风险评价,在此基础上提出水体中铜浓度的管理限值。根据该湿地生态保护区生物调查历史数据以及其他文献数据,整理了415个本地物种的清单,通过美国环境保护署ECOTOX数据库以及其他文献共获取了13个物种的毒性数据,构建了Weibull分布、对数正态分布、正态分布、对数Logistic分布、Logistic分布、BurrⅢ型分布和Gumbel分布等7个SSD模型。结果表明,利用13个本地物种铜毒性数据构建的SSD模型具有合理性,不同模型计算得到的湿地生态保护区水体中铜的总体风险期望值为0.054~0.121。其中,BurrⅢ型分布模型的拟合效果最好,据此推导得到以保护水生生态系统为目标的铜的高可靠性与中等可靠性触发值分别为2.55μg·L~(-1)和1.41μg·L~(-1)。考虑到管理目标的可达性和现状的生态风险水平,提出该湿地生态保护区水体中铜浓度的管理限值为3μg·L~(-1)。     

外源NO介导Cu~(2+)胁迫下番茄幼苗活性氧与内源NO代谢的研究

采用营养液培养方法,研究Cu~(2+)胁迫下外源一氧化氮(nitric oxide,NO)介导的番茄幼苗活性氧及NO代谢途径。结果表明:在Cu~(2+)胁迫下,番茄叶片和根系氧自由基含量增加,NO释放量以及硝酸还原酶(nitrate reductase,NR)和一氧化氮合酶(nitric oxide synthase,NOS)活性降低。外源NO能提高Cu~(2+)胁迫下番茄叶片NR和NOS活性,促进NO的产生,根系NOS活性及NO产量也同时上升。外源NO使精氨酸含量显著增加,而Hb(牛血红蛋白,NO清除剂)可部分抵消NO的促进作用,使Cu~(2+)+SNP+Hb处理下番茄精氨酸含量显著下降。可见,外源NO的加入可通过酶促和非酶促途径促进Cu~(2+)胁迫下NO的合成,介导NO信号调控网络,调节内源NO、精氮酸和活性氧代谢途径,从而缓解过多Cu~(2+)引起的氧化伤害。     

Polychlorinated dibenzo p-dioxins and dibenzofurans emissions in a primary copper smelter in China

Metallurgical production is the largest polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) emission source in China. However, PCDD/F monitoring and research are rarely conducted on primary metallurgical production. In this study, a demonstration primary copper smelter in China was selected to investigate PCDD/F characteristics and control. Samples were collected from major PCDD/F release points in the smelter process (fly ashes and waste water sludge). Specific analysis of PCDD/F congeners was carried out using a high resolution gas chromatography/high resolution mass spectrometry method. The results showed that PCDD/Fs might be unintentionally produced in the primary copper smelter processes, with sample concentrations of 180–6110 pg/g dry wt; highly chlorinated PCDD/F homologues were predominant. The toxicity of all the samples was calculated to be 120 pg WHO TEQ/g, fly ashes from the refining process furnaces air pollution control device and sludge were hazardous waste with higher PCDD/F toxicity. Both precursor formation and de novo synthesis were found to contribute to PCDD/F formation in the smelter process. PCDD/F characteristics and formation were compared with reported secondary copper smelters. Life-cycle control of PCDD/F was proposed for retrofitting of this smelter and for similar plants in China's primary copper production sector, including control at the PCDD/F formation, removal and disposal stages.     

Spatial distribution of copper in relation to recreational boating in a California shallow-water basin

The overall effect of the number of boats on the copper (Cu) levels in the water column and sediment, along with their spatial variability within Shelter Island Yacht Basin (SIYB), San Diego Bay, California was examined. We identified a horizontal gradient of increasing dissolved Cu and Cu in sediment from outside to the head of SIYB which was coincident with the increasing number of boats. Spatial models of Cu distribution in water and sediment indicated the presence of ‘hotspots’ of Cu concentration. From outside to the head of SIYB, dissolved Cu ranged from 1.3 μ g L^?1 to 14.6 μ g L^?1 in surface water, and 2.0 μ g L^?1 to 10.2 μ g L^?1 in bottom water. Cu in sediment exceeded the Effect Range Low of 34 mg kg^?1 (i.e. where adverse effects to fauna may occur), with a peak concentration of 442 mg kg^?1 at the head of the basin. Free Cu⁺⁺ in surface water was several orders of magnitude higher than in sediment porewater. High-resolution data of Cu species together with probability maps presented in this paper will allow managers to easily visualise and localise areas of impaired quality and to prioritise which areas should be targeted to improve Cu-related conditions.     

Bioaccumulation and toxic effects of copper on growth and oxygen consumption by the postlarvae of Penaeus indicus

The aim of this study was to assess the toxic impact of copper on postlarvae (PL) of the penaeid shrimp Penaeus indicus. Tolerance, growth, oxygen consumption and metal accumulation were investigated in these PL on exposure to copper. Tolerance studies were conducted for 96 h to assess the tolerance limits of P. indicus PL exposed to different concentrations of copper using static renewal bioassay tests. Using the Probit method, the regression equation was calculated as Y=0.4899+2.3562 X, with a correlation coefficient of 0.9707. The 96 h LC₅₀ was 0.8204 ppm. The effect of sublethal (one-fifth of 96 h LC₅₀) copper on PL for short- and long-term exposures revealed a significant (p<0.05) decrease in the rate of oxygen consumption, metabolic rate, mean length, wet and dry weight of the exposed PL over their respective controls which can be attributed to a gradual and time-dependent accumulation of the metal, as noticed in the exposed PL through accumulation studies. Overall, the data suggest that on chronic exposure even sublethal concentrations of copper can reduce the metabolic rate and growth in P. indicus PL. This is perhaps the first attempt to use the wild P. indicus PL as a bioindicator of copper toxicity.     

Application of rotating cylinder method for ecotoxicological evaluation of antifouling paints

The environmental impact of two biocide-free antifouling paints, fluoropolymer and silicone types, painted on a test cylinder was assessed using a battery of ecotoxicity test and chemical analyses for organic micro-pollutants such as perfluoroalkyl substances (PFAS). A biocide paint containing zinc pyrithione (ZnPT₂) and cuprous oxide was assessed as a positive control. A standardized laboratory rotating-cylinder method using each test cylinder with artificial seawater was performed for 45 days. After 1?h rotation, the leaked seawater was subjected for bioassay and chemical analyses twice weekly. The seawater extracts from the biocide paint showed adverse effects on bacteria, algae, and crustaceans, but those from the biocide-free paints did not. The leakage seawater from biocide-free paints, after 7-day continuous rotation, contained the same concentration levels of PFAS as blank seawater used to conduct the tests. Thus, no significant toxicities of the biocide-free paints were found under the conditions of this study. Simultaneous analysis of ZnPT₂ and copper pyrithione (CuPT₂) was developed using an HPLC with a polymeric resin column, showing that ZnPT₂ was converted to CuPT₂ by trans-chelation in the leakage seawater from the positive control paint. The experimental results using a laboratory rotating-cylinder method demonstrated that biocide-free paints did not markedly affect three species tested and no PFAS was detected. In contrast, biocide paint was significantly toxic to test species and toxicity of the extract on bacteria was partly responsible for CuPT₂ produced in leakage seawater. Thus, a laboratory rotating-cylinder method may be applied for ecotoxicological assessment of antifouling paints.     

Cu(Ⅱ)印迹[CTS/PVP]和[CTS/PVP/C]材料的制备及表征

以壳聚糖(CTS)、聚乙烯吡咯烷酮(PVP)、活性炭(C)为基材,Cu(Ⅱ)为印迹离子,制备了CTS/PVP共混印迹球[Cu(Ⅱ)-IICP]和CTS/PVP/C共混印迹球[Cu(Ⅱ)-IICPC].以Cu(Ⅱ)的吸附量作为评价指标,对两种共混印迹球的制备条件进行了优化.研究结果表明,当CTS/PVP的质量比为6∶4,活性炭质量分数为0.6%,Cu(Ⅱ)模板剂质量分数为0.05%,所制备的两种共混印迹球吸附性能较佳,且对Cu(Ⅱ)有较好的选择吸附性.物理吸附分析结果表明,与未印迹相比印迹材料的比表面积明显增大.FTIR谱图分析,Cu(Ⅱ)模板主要与CTS和PVP中的—NH2和—OH发生了配位作用.XRD谱图分析结果表明,CTS与PVP、C、Cu(Ⅱ)之间发生了相互作用,改变了CTS原有的晶体结构,使其结晶度降低.     

Producing Cu-loaded algae for feeding experiments: effects of copper on Parachlorella kessleri

Microalgae require several essential metals for optimum growth, which at elevated concentrations may interfere with biochemical and physiological processes, one of them being copper (Cu). The aim of this study is to raise Cu-loaded Parachlorella kessleri as feed for mussels. In order to spike the algae with Cu without lowering their nutritional quality, it is important to know the highest Cu-concentration at which the main parameters remain unaffected, especially in respect to proteins and polysaccharides. The dependence of growth rate, biomass, chlorophyll-a and -b, pheophytin-a, protein, and polysaccharide contents on Cu concentrations are determined. The tests show that P. kessleri is largely unchanged in its nutritional value when exposed to Cu at levels of up to 6?µmol?L^?1. Above 10?µmol?L^?1, toxic effects become obvious, with chlorophyll contents and growth rate being the most sensitive indicators.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part V†: Hypotheses and summary

The hypotheses on the de novo syntheses of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo‐p‐dioxins (PCDDs), based on known literature, are presented. Polychlorinated benzenes and polychlorinated phenols are probably key intermediates.

In the present article, hypotheses that may account for the presence of polychlorinated dibenzofurans (PCDFs) and dibenzo‐p‐dioxins (PCDDs) in the effluents from municipal and industrial incinerators are put forward. These hypotheses are based on the previously surveyed literature (Ref. 203–206) and experimental results on laboratory scale and thermodynamic calculations are considered. The interconnections of various reaction steps are speculative and no technological information was added to account for conditions in real incinerators. Conclusion of the discussions on the related subject matter, presented in the Parts I‐IV (Ref. 203–206), are also described in this paper.     

Bioavailability of copper and cadmium in sediment of nanjing section of Changjiang river to aquatic organisms

Bioavailabilities of metals in sediment to aquatic organisms depend on the strength of metal bonding to particulates. The accumulation tests of Cu and Cd in carp and in snails have been studied in vitro with the solution containing semisynthetic sediment samples in which the contents of various speciation of metal in sediment have been extended. For carp, the accumulation of Cu and Cd is related to the concentration of dissolved metal which in turn is affected by the distributions of speciations in sediment under given environmental conditions. It is another pattern for snails, various speciations of metal in sediment can contribute indirectly to metal accumulation. The contribution ratio, or relative importance of various speciations of metal in sediment can be expressed by multiple linear regression formulas. The contribution of ion‐exchangable speciation and coprecipition with carbonate speciation is 10⁵ times larger than that of residue speciation in sediment.