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.     

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.     

Preliminary Evaluation of the Use of Phosphogypsum for Reef Substrate. I. A Laboratory Study of Bioaccumulation of Radium and Six Heavy Metals in an Aquatic Food Chain

Phosphogypsum (PG), a solid by-product of phosphoric acid production, contains radionuclides and trace metals in concentrations which may pose a potential hazard to human health and the environment. to investigate the possibility of bioaccumulation of radium and six heavy metals over time when aquatic organisms experience both trophic and environmental exposure to PG, we designed a laboratory experiment representing three levels of an aquatic food chain. During the 135 day experiment, a meiobenthic copepod species (Amphiascoides atopus) was cultured in the presence of PG. the copepods were subsequently fed to grass shrimp (Palaemonetes vulgaris and P. pugio) which were in turn fed to gulf killifish (Fundulus grandis); both the grass shrimp and the killifish also experienced an environmental PG exposure. Other than elevated radium levels in the experimental grass shrimp, the experiment demonstrated little effect of environmental or trophic exposure to PG on microinvertebrates, macroinvertebrates, or fishes that could be attributed to PG. in all cases where increased concentrations were indicated within the experimental group, roughly equivalent increases in metal concentrations also occurred in the control group.     

PCDD/Fs emission, risk characterization, and reduction in China’s secondary copper production industry

Secondary copper production is one of the key polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) emission sources in China, but research and data on this issue are rare. In 2004, when the Stockholm Convention entered into force in China, PCDD/Fs emissions from secondary copper production contributed to 32.2% of the total release. In this paper, PCDD/Fs emission dynamics from secondary copper industry were discussed and cumulative risks were characterized. From 2004 to 2009, industrial policies played an indirect role in PCDD/Fs reduction, but its effects are still limited. The Yangtze River Delta, Pearl River Delta and central regions were among the top three of dioxin emissions from secondary copper production in China. Shanghai, Shandong, Zhejiang, and Jiangxi had comparatively higher accumulated risk and were recommended as the priority regions for promoting PCDD/Fs emission control in China. From 2009 to 2015, the PCDD/Fs emission dynamics in the secondary copper industry were presented through simulation. PCDD/Fs emission equations were established, resulting in the recommendation of control technology conversion rate at 30% for small scale smelters and 51%–57% for large and medium-sized enterprises in 2015. In conclusion, both indirect policy and direct control technology retrofitting should be integrated for more effective PCDD/Fs emission reduction in secondary copper industry.     

不同钝化材料对红壤中铜有效性的影响及机理

选取3种钝化材料（赤泥、硼泥、钙镁磷肥）,通过盆栽试验,观测了在不同铜污染水平红壤上,3种钝化材料对小油菜（Brassica campestris,L var Conmunis）吸收铜的影响。结果表明：在铜污染红壤上,3种钝化材料降低土壤EDTA提取态铜含量的效果显著。其中,在高铜污染水平红壤上,施用高量赤泥、硼泥处理降低效果最为明显,较污染对照降低了41.48%、44.44%。在低铜污染水平红壤上,施用高量赤泥处理降低效果最为明显,较对照处理降低了35.83%。施用3种钝化材料均能促进小油菜生长,增加小油菜的生物量,降低小油菜对铜的吸收量。其中,低铜污染水平红壤上,施用高量赤泥、高量硼泥与硼泥-赤泥联合施用处理降低铜含量的效果最为明显,与污染对照相比,小油菜铜含量分别降低82.64%,72.71%,85.14%;在高铜污染水平红壤上,施用高量赤泥与硼泥、赤泥联合施用处理降低小油菜铜含量的效果最为明显,小油菜铜含量分别为36.37,36.32 mg.kg^-1。结果表明,用量为45 000 kg.hm^-2的赤泥是最佳的功能钝化材料。     

土壤跳虫(Folsomia candida)对食物中铜污染物的吸收和排泄

重金属污染物在生物体内的累积、迁移和传递已成为当今的研究热点。土壤弹尾目昆虫作为土壤生态系统的重要组成部分,针对其对重金属的吸收、积累和排泄的动态过程以及相应解毒机制的研究意义重大。本研究通过弹尾目跳虫(Folsomia candida)对Cu的吸收-排泄效率实验发现,跳虫体内Cu含量随暴露时间的延长而显著增加(r~2=0.8878,F_(1,5)=29.59,P<0.01);跳虫体内Cu含量随排泄时间的延长而明显逐渐降低(r~2=0.7836,F_(1,3)=7.13,P<0.01)。跳虫对Cu的吸收-排泄Budget实验表明,只有少量的Cu被跳虫摄取到体内,其中小部分被体内组织消化吸收,大部分则可能通过中肠细胞的褪皮作用和产卵等方式排出体外。可见,褪皮和排卵是跳虫排泄重金属Cu的重要途径,跳虫对Cu具有较低的吸收率(8.13%)和较高的排泄率(57.3%),表明跳虫对Cu可能有较高的耐受性。     

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb(II) and Cu(II) ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 mol·L^-1 CaCl₂ as background electrolyte. The desorption isotherms of Pb(II) and Cu(II) were similar to the adsorption isotherms, which can be fitted well by Freundlich equation (R₂>0.96). The soil in the three sites had greater sorption capacities for Pb(II) than Cu(II), which was affected strongly by the soil characteristics. In the binary metal solution containing 1∶1 molar ratio of Pb(II) and Cu(II), the total amount of Pb(II) and Cu(II) adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared (FT-IR) spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.     

氧化铜纳米颗粒(CuO NPs)对土壤环境因子与砷生物有效性的影响

氧化铜纳米颗粒（CuO NPs）可以通过农药和肥料施用、意外泄露或污水灌溉进入As污染农田土壤,从而对土壤环境因子和As生物有效性产生影响.本试验选取两种不同类型土壤（安徽宿松黄棕壤和黑龙江海伦黑土）进行人工As污染,添加不同浓度的CuO NPs,探究90 d淹水-落干过程中CuO NPs对As污染农田环境因子和As生物有效态的影响.结果表明,CuO NPs进入土壤后12 h内快速溶解产生Cu²⁺,且在黄棕壤中的溶解速度较黑土迅速.CuO NPs可在短时间内降低土壤pH,提高土壤氧化还原电位（E_h）,降低土壤电导率（EC）,但随着培养时间增加土壤EC逐渐提高.一定时间内CuO NPs在两种类型土壤中可降低51.0%~82.5%土壤浸出液中的As和15.7%~66.5%的As生物有效性,减少淹水时Fe （II）的含量.但在土壤落干时期产生一定的“纳米效应”从而促进了Fe （II）的产生.研究表明,CuO NPs进入As污染农田改变了土壤环境因子,一定时间内降低了土壤As生物有效性.