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.     

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.     

Does copper reduce cadmium uptake by different rice genotypes？

A hydroponics experiment was conducted to investigate the effect of copper （Cu） on cadmium （Cd）, calcium （Ca）, iron （Fe）, and zinc （Zn） uptake by several rice genotypes. The experiment was carried out as a 2×2×4 factorial with four rice genotypes and two levels of Cu and Cd in nutrient solution. Plants were grown in a growth chamber with controlled environment. The results showed a significant difference between the biomass of different rice genotypes （P 〈 0.001）. The Cd and Cu concentration in the solution had no significant effect on the biomass. The addition of Cu significantly decreased Cd uptake by shoots and roots of rice （P 〈 0.001）. The Cd concentration did not significantly influence Ca uptake by plants, whereas the Cu concentration did （P = 0.034）. There was a significant influence of Cd on Fe uptake by shoots and roots （P 〈 0.001, P = 0.003, respectively）. Zn uptake decreased significantly as the addition of Cd and Cu increased in shoots. We concluded that Cu had significant influence on Cd uptake. The possible mechanisms were discussed.     

土壤对铜和镉的静态吸附研究

通过静态吸附实验研究了德兴矿区大坞河下游下沽口土壤对铜和镉的吸附特点并采用Freundlich等温吸附方程进行拟合,探讨了pH值变化对铜和镉在土壤样品中分配系数的影响。结果表明：土壤铜和镉的吸附特性均符合Freundlich等温吸附方程,得到的金属铜和镉的Kf值分别为354．08、34．132;随着pH值的升高,铜和镉在土壤中的分配系数逐步增大,随后降低,pH值与分配系数关系曲线为单峰曲线。     

铜尾矿区9种优势植物体内重金属和氮磷含量研究

以杨山冲铜尾矿废弃地人工覆土上生长的9种优势植物为研究对象,探讨不同植物对尾矿基质中重金属和氮磷的吸收特性以及与基质理化性质之间的关联。土壤样品采集时沿基质垂直方向分为4层：A层（覆土层0~5 cm）、B层（覆土层5~20 cm）、C层（尾砂层20~25 cm）、D层（尾砂层25~40 cm）,植物样品采集时草本植物分地上和地下2部分、木本植物分根、茎和叶3部分采集。结果表明：随着9种植物生长,A层和B层基质理化性质得到明显的改善。主要表现在A层中w（总氮）、w（氨氮）、w（硝氮）、w（有效磷）和w（有机质）显著高于C、D层（P〈0.05）,B层中w（有效态Cu）、w（有效态Zn）显著低于A、C、D层（P〈0.05）。9种优势植物对Cu、Pb、Zn的吸收和积累能力具有明显差异性,其中草本植物以根系积累为主,木本植物以叶片积累为主。草本植物对尾矿基质表现出较强的适应性和耐性,其中毛叶荩草（Arthraxon prionodes）根系中Cu、Pb、Zn的富集量均最大,耐性表现最突出,是较为理想的铜尾矿基质的修复物种。另外,本研究还发现,9种植物体内氮磷质量分数也各不相同,其中木本植物叶中氮磷质量分数均大于根、茎。木本植物体内w（总氮）与w（总磷）、w（Cu）、w（Zn）相关性较好,草本植物体内w（Cu）、w（Pb）、w（Zn）之间相关性较好,表明彼此之间存在一定的促进作用。