Identification and assessment of environmental burdens of Chinese copper production from a life cycle perspective

The environmental burdens of Chinese copper production have been identified and quantified in the context of typical technologies, materials supplies and environmental emissions by a life cycle approach. Primary and secondary copper production using copper ores and scraps, respectively, were analyzed in detail. The flash and bath smelting approaches and the recycling of copper scraps were selected as representative copper production processes. A quantitative analysis was also conducted to assess the influence of material transport distance in copper production. Life cycle assessment （LCA） results showed that resources depletion and human health contribute significantly to environmental burdens in Chinese copper production. In addition, the secondary copper production has dramatically lower environmental burdens than the primary production. There is no obvious distinction in overall environmental burdens in primary copper production by flash or bath smelting approach. However, resources depletion is lower and the damage to human health is higher for flash smelting approach. Ecosystem quality damage is slight for both approaches. Environ- mental burdens from the mining stage contribute most in all life cycle stages in primary copper production. In secondary copper production, the electrolytic refining stage dominates. Based on the life cycle assessment results, some suggestions for improving environmental performance were proposed to meet the sustainable development of Chinese copper industry.     

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.     

精炼铜行业的生命周期节能减排目标评价

按照生命周期评价方法,建立了精炼铜的生命周期模型,采用生命周期节能减排评价指标(ECER),对比评价了原生铜和再生铜生产的生命周期节能减排效果,计算了改变再生铜市场份额所能带来的节能减排削减幅度,并与精炼铜行业实现节能减排政策目标所需的综合削减幅度进行了对比.结果表明,再生铜比原生铜的ECER指标小62.5％,因此废铜的再生循环明显有利于节能减排政策目标的实现.但是,当再生铜市场份额由2010年的38.5％提升至《有色金属“十二五”发展规划》中要求的40％时,其综合削减幅度仅为13％,远未达到铜冶炼行业的目标综合削减幅度27.8％.因此,精炼铜行业不仅需要更大幅度地提高铜再生比例,同时还需要采用更多清洁技术和改进措施.本文方法可用于计算各种行业的节能减排目标综合削减幅度,从而帮助判断各种改进方案和措施是否足以达到节能减排宏观政策目标的要求.     

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.     

Extremely high secondary production of introduced snails in rivers.

The functional importance of invasive animals may be measured as the degree to which they dominate secondary production, relative to native animals. We used this approach to examine dominance of invertebrate secondary production by invasive New Zealand mudsnails (Potamopyrgus antipodarum) in rivers. We measured secondary production of mudsnails and native invertebrates in three rivers in the Greater Yellowstone Area (Wyoming, USA): Gibbon River, Firehole River, and Polecat Creek. Potamopyrgus production was estimated by measuring in situ growth rates and multiplying by monthly biomass; native invertebrate production was estimated using size frequency and instantaneous growth methods. Mudsnail growth rates were high (up to 0.06 d(-1)) for juvenile snails and much lower for adult females (0.003 d(-1)). Potamopyrgus production in Polecat Creek (194 g x m(-2) x yr(-1)) was one of the highest values ever reported for a stream invertebrate. Native invertebrate production ranged from 4.4 to 51 g x m(-2) x yr(-1). Potamopyrgus was the most productive taxon and constituted 65-92% of total invertebrate productivity. Native invertebrate production was low in all streams. Based on a survey of production measures from uninvaded rivers, the distribution of secondary production across taxa was much more highly skewed toward the invasive dominant Potamopyrgus in the three rivers. We suggest that this invasive herbivorous snail is sequestering a large fraction of the carbon available for invertebrate production and altering food web function.     

表面涂层影响铜纳米材料和溶解性铜对大型溞的蓄积动力学和急性毒性

本研究评价了未涂覆或有三种不同表面涂层（即羧基化，聚乙二醇化和氨基团）的氧化铜纳米材料（CuO-NMS）对大型溞（Daphnia magna）的急性毒性和累积动力学。首先利用生物动力学模型确定了溶解铜和CuO-NMS水溶液对大型溞的吸附和消除速率常数。然后评估模型参数与急性毒性终点之间的关系，以考察累积动力学参数是否可作为急性毒性的预测指标。采用朗格缪尔方程表征铜纳米材料和氯化铜（溶解铜对照）的生物吸附动力学。得到的吸收速率依次为：CuO-NMs>NH3-CuO-NMs>Cu水溶液>PEG-CuO-NMs>COOH-CuO-NMs。采用单室模型测定大型溞对铜的去除率。估算了每种被测化学物质的不同消除速率常数。结果显示，容易被生物吸收的物质也更容易从生物体中去除。纳米材料在悬浮液中的吸附和净化性能与Zeta电位值和纳米材料团聚体直径有关。而生物吸附和毒性之间没有联系。水性暴露于较难生物吸附的CuO-NMs比易被生物吸附的CuO-NMs更易诱发不良反应。本文提出了纳米材料在介质中的某些物理化学性质，包括Zeta电位和团聚体直径，可以导致较高的生物吸附，但不一定影响毒性。总而言之，纳米材料与生物体的相互作用模式似乎很复杂，取决于生物体内纳米材料的化学形态和物理化学性质。     

A simulation analysis of continental shelf food webs

Energy flow through continental shelf food webs was examined using a simulation model. The model structure expands the two traditional marine food chains of phytoplankton-zooplankton-pelagic fish and benthos-demersal fish into a complex web which includes detritus, dissolved organic matter (DOM), bacteria, protozoa, and mucus net feeders. Simulation of energy flux for different shelf systems using the expanded web revealed that heterotrophic microorganisms and their predators account for a significant component of the energy flux in the continental shelf ecosystem. Contrary to previous models, where all phytoplankton were considered to be grazed by zooplankton, our simulation results indicate that only slightly more than 50% of the annual net primary production is grazed. A substantial quantity of the phytoplankton production directly becomes detritus. Bacteria mineralize detritus and DOM produced by phytoplankton and other components of the food web, converting these to biomass with high efficiency. Consequently, the model predicts that planktonic bacterial production is equivalent to zooplankton production. Exclusion of the bacteria requires the assumption that all DOM is either exported from the system or consumed by another component of the food web. Neither of these assumptions can be supported by present knowledge of the dynamics of DOM in the sea. Model simulations were also employed to test the hypothesis that production exceeds consumption on continental shelves, resulting in exports of 50% of the annual primary production. Simulations of shelves with high rates of primary production resulted in a particulate export of 27% and realistic estimates of secondary production. Results of other simulations suggest that shelves with lower primary production cannot export production and still maintain the macrobenthos and their predators. General properties about continental shelves can also be inferred from the model. From simulations of shelves of differing primary production, nanoplankton are predicted to account for a greater proportion of the primary production in nutrient limited systems. Benthic production appears to be related to both the quantity of primary production and the sinking rates of the phytoplankton. The model indicates that zooplankton fecal inputs to the shelf benthos are only a small portion of the total detrital flux, leading to the prediction that fecal pellets are of little significance in determining benthic production. Finally, the model generates production efficiencies that are highly variable depending on the type of system and kind of populations involved. We argue that the assumed ecological efficiency of 10% should be abandoned for continental shelves and other ecosystems.     

Bioavailability of dissolved copper to the American oyster Crassostrea virginica. I. Importance of chemical speciation

The effect of complexation on the accumulation of dissolved copper by the American oyster Crassostrea virginica was determined in chemically defined exposure media. The speciation of copper was varied by varying the concentrations of total copper and model chelator, nitrilotriacetic acid (NTA). Accumulation of copper in 14-d experiments was related to the cupric ion activity and not the concentration of chelated copper. Rapid accumulation of copper occurred at cupric ion activities above 10^-10 M and there was no measurable accumulation at 10^-11 M.Southeast Fisheries Center Contribution No. 81-45B. Reprint request should be addressed to this author     

Amelioration of free copper by hydrothermal vent microbes as a response to high copper concentrations

We examined the effect of increased copper concentrations (0–10 μM) on hydrothermal vent micro- organisms and the production of copper (Cu)-binding ligands as a response. Hydrothermal vent microbes originated from diffuse fluids at the Lilliput mussel field and the Irina II site in the Logatchev hydrothermal vent field, both on the Mid-Atlantic Ridge. Parallel studies were also conducted with amino acids supplemented to the incubations in order to verify whether dissolved amino acids, present in hydrothermal fluids, can buffer the bioavailable copper and reduce the active production of Cu-binding ligands. In all incubations, ligand concentrations increased with rising copper concentrations, but microbial cell numbers remained constant. This study shows that microbes were able to cope with as much as 10 μM dissolved copper by buffering the free copper concentration. The presence of amino acids had no significant influence on the active ligand production. Our results imply that mediation of chemical speciation by vent microbes may have an important impact on hydrothermal trace metal fluxes into the ocean.     

Population dynamics and secondary production in an estuarine population of Caulleriella caputesocis (Polychaeta: Cirratulidae)

Between July 1978 and March 1980, the distribution, population dynamics and secondary production of Caulleriella caputesocis St. Joseph, 1864, in Southampton Water, South England, were investigated. The distribution of the polychaete was related to amount of silt and copper-content of the sediment, the highest densities occurring in sediment containing 60 to 100% silt and less than 50 ppm copper. Breeding occurred at a low level throughout the year, usually when the worms were over one year old, with peak breeding between May and September. C. caputesocis in Southampton Water is monotelic, and oocytes measured 120 to 160 m in diameter at spawning. Unshed oocytes were resorbed. Annual secondary production varied between 0.01 and 5.90 g C m^-2 yr^-1 and P:B ratio of the species ranged between 0.84 and 7.09.     

Mechanisms of copper tolerance in the marine fouling alga Ectocarpus siliculosus — Evidence for an exclusion mechanism

Copper-tolerant strains of the marine fouling alga Ectocarpus siliculosus (Dillw) Lyngb. have been recorded. The mechanisms of tolerance which may operate in a copper-tolerant strain were investigated by comparing the growth characteristics, copper content and extracellular organic production of tolerant and non-tolerant strains. Growth was measured by a wet-weight method. The copper content of dryashed cells was measured spectrophotometrically using tetraethylthiuram disulphide. The extracellular material is ultra-violet absorbing, and the production was measured by recording absorption at 265 nm. Evidence suggests that an exclusion mechanism is operating in the tolerant strain under investigation. The extracellular material, the cell wall or an associated organism make little or no contribution no this exclusion. Membrane and intracellular changes are believed to account for the tolerance in this strain of E. siliculosus.     

Copper(II) ions’ removal from aqueous solution using green horse-chestnut shell as a low-cost adsorbent

The adsorption of copper(II) ions from aqueous solutions by the green horse-chestnut shell was studied in a batch adsorption system. It was determined how the parameters of the adsorption process, such as time, pH, copper(II) ions concentration and sorbent dose, influence the effectiveness of copper(II) ions’ removal. The adsorption process was fast and equilibrium was established about 10?min, and near 95–97% of Cu(II) ions were removed from aqueous solution. Maximum copper(II) ions’ adsorption occurred at around pH 5. The adsorption kinetics are also described, using pseudo-first-order model and pseudo-second-order model of type 1 and 2. A comparison of the kinetics models on the overall adsorption rate showed that the adsorption system was best described by the pseudo-second-order model of type 1 (r²?=?0.999) for all initial concentrations. Another key part of this study was the use of the Freundlich model to determine the adsorption isotherm and the experimental data were in strong correspondence with this model.     

Toxicity of zinc,cadmium and copper to the shrimp Callianassa australiensis. III. Accumulation of metals

Callianassa australiensis (Dana) that survived 14 d acute lethality studies were analysed to determine the concentrations of zinc, cadmium and copper in the whole shrimp and in various parts of the body. Using regression analysis, the influence of each metal upon the uptake of the others was studied. Zinc and cadmium appeared to enhance the uptake of each other. In a mixture of zinc and copper, the uptake of zinc was enhanced and that of copper was inhibited. In a mixture of cadmium and copper, the uptake of copper was inhibited by the presence of cadmium, but cadmium uptake was unaffected in the presence of copper. In a mixture of all three metals, similar effects were observed except that zinc and copper, occurring together, appeared to have no effect upon cadmium uptake. Additional 14 d experiments with cadmium suggested that accumulation of this metal was a function of metal concentration in the water and of duration of exposure. The whole shrimp cadmium concentration also appeared to be a function of the size of the shrimp. The variation in concentration factors is described and the need for further research on the effects of combinations of metals on various organisms is emphasized.     

Physiological responses ofCalanus finmarchicus andMetridia longa (Copepoda: Calanoida) during the winter-spring transition

The effect of pH on the biological availability of copper to the brine shrimp Artemia franciscana was studied with acclimated and non-acclimated individuals for the pH range 5.5 to 8.5. A chemical speciation model was used to calculate the speciation of copper in a chemically-defined saline solution as a function of pH. The lipid solubility of inorganic copper species was determined in hexadecane/saline and octanol/saline extraction systems. Copper is absorbed across the gut epithelium and accumulation is proportional to time over a 120 min experimental period. The biological availability of copper decreases with a decrease in the pH of the salt solution and a concomitant increase of the cupric ion concentration. Acclimation to the experimental pH has a marked effect on the uptake process, which depends on the buffer used. There is no extraction of copper in hexadecane, but a small amount goes in octanol. There is, however, no direct relation between the accumulation of copper in the shrimps and the extraction of copper in octanol. Multiple regression of the accumulation rates for non-acclimated animals on the calculated copper species concentrations shows that much of the variation in accumulation rate with pH is explained when copper hydroxide and/or copper carbonate species are considered to be the biologically available forms. Alternatively, the observations can be interpreted as the result of competitive binding of protons and copper species for carrier systems.     

Midwest U.S. landscape change to 2020 driven by biofuel mandates

Meeting future biofuel targets set by the 2007 Energy Independence and Security Act (EISA) will require a substantial increase in production of corn. The Midwest, which has the highest overall crop production capacity, is likely to bear the brunt of the biofuel-driven changes. In this paper, we set forth a method for developing a possible future landscape and evaluate changes in practices and production between base year (BY) 2001 and biofuel target (BT) 2020. In our BT 2020 Midwest landscape, a total of 25 million acres (1 acre = 0.40 ha) of farmland was converted from rotational cropping to continuous corn. Several states across the Midwest had watersheds where continuous corn planting increased by more than 50%. The output from the Center for Agriculture and Rural Development (CARD) econometric model predicted that corn grain production would double. In our study we were able to get within 2% of this expected corn production. The greatest increases in corn production were in the Corn Belt as a result of conversion to continuous corn planting. In addition to changes to cropping practices as a result of biofuel initiatives we also found that urban growth would result in a loss of over 7 million acres of productive farmland by 2020. We demonstrate a method which successfully combines economic model output with gridded land cover data to create a spatially explicit detailed classification of the landscape across the Midwest. Understanding where changes are likely to take place on the landscape will enable the evaluation of trade-offs between economic benefits and ecosystem services allowing proactive conservation and sustainable production for human well-being into the future.     

Photosynthate partitioning by phytoplankton in a New Zealand coastal upwelling system

A stimulation model of copepod population dynamics (development rate, fecundity, and mortality) was used to compute the predatory consumption necessary to control population growth in three dominant copepod species (Pseudocalanus sp., Paracalanus parvus, and Calanus finmarchicus) on Georges Bank, given observed seasonal cycles of copepod and predator populations. The model also calculated secondary production of each species. Copepod development rate and fecundity were functions of temperature while mortality was a function of predator abundance and consumption rate. Daily inputs of temperature and predator abundance (chaetognaths, ctenophores, and Centropages spp.) were derived from equations fit to field data. Model runs were made with various consumption rates until the model output matched observed copepod seasonal cycles. Computed consumption rates were low compared with published values from field and laboratory studies indicating that, even at conservative estimates of consumption, predators are able to control these copepod populations. Combined annual secondary production by the small copepod species, Pseudocalanus sp. and P. parvus, was nearly twice that of the larger C. finmarchicus with P. parvus having the highest total annual production.     

Copper tolerance in a population of Silene vulgaris ssp. maritima (A. & D. Love) at Dolfrwynog Bog near Dolgellau,North Wales

Clones of Silene vulgaris ssp. maritima individuals from Dolfrwynog Bog, North Wales and from a coastal control site were propagated under standardised environmental conditions. After five months, cuttings were taken and tested for copper tolerance by means of root extension analysis in solutions of various different copper concentrations. Indices of tolerance suggested that individuals from the Dolfrwynog population were more resistant to elevated copper concentrations than were the control population individuals. Due to the initial five months under standardised conditions, it was assumed that the cloned plant material would have lost all plastic adaptive responses to its native environment. If this assumption was valid then the differences in copper tolerance observed between the two populations had a genetic basis and the Dolfrwynog Bog population is a copper tolerant ecotype.     

Mechanisms for copper tolerance in Amphora coffeaeformis-internal and external binding

Growth of the ship-fouling diatom Amphora coffeaeformis and accumulation of copper in the cells were evaluated for cultures exposed to copper. Comparisons with literature reports for other species revealed that A. coffeaeformis shows no ability to maintain normal growth rates in the presence of high cellular copper levels. This suggests that internal binding is not the principal copper tolerance mechanism for this species. In addition, the copper complexing capacity of A. coffeaeformis exudates was evaluated. Significant complexing by these exudates was demonstrated by DPASV analysis. When added to the culture medium of another species (Thalassiosira profunda), A. coffeaeformis exudates were also able to reduce copper toxicity and accumulation in the cells of that species. However, the copper tolerance of A. coffeaeformis was greater than that acquired by T. profunda grown with A. coffeaeformis exudates; thus exudate production was deemed not to be a primary tolerance mechanism. Comparison of copper accumulations inside and outside cells of A. coeffeaeformis suggests that binding at the cell surface or to mucilage may be an important factor in the tolerance of this species to copper.     

Population dynamics and secondary production in an estuarine population of Nephtys hombergii (Polychaeta: Nephtyidae)

From July 1978 to March 1980, a study was made on the distribution, population dynamics and secondary production of Nephtys hombergii Audouin et Edw. occurring in the sublittoral industrialised region of Southampton Water in south England. The distribution of the worm was related to the silt content and copper level of the sediment, the greatest densities of N. hombergii being found in sediment containing 60 to 100% silt. Breeding occurred at a low level throughout the year, with a maximum in July to September and November to January in the second year of growth. Spawning occurred when the oocytes measured 200m in diameter, and unshed gametes were resorbed. Annual production varied between 0.092 and 4.32 g C m^-2 yr^-1 (ash-free dry weight) and amounted to 1.9–39.4% of the total macrofaunal production at the sampling stations. The production:biomass (P:B) ratio of the species varied between 1.6 and 2.9.     

A comparative study of modified and unmodified maize tassels for removal of selected trace metals in contaminated water

Powdered maize tassels were studied and found to exhibit metal sorption properties due to the availability of functional groups. The tassels have a high amount of soluble organic substances that can dissolve in aqueous media, contributing to secondary pollution during a water treatment process. A chelating agent was chemically attached on the maize tassels with a view to increase the sorption capacity, minimize leaching, and enhance the tassels’ stability. Thermogravimetric analysis confirmed that modification improved their thermal stability to withstand temperatures above 600°C as well as reduced the “secondary pollution”. The modified sorbent was employed for the sorption of lead, copper, and cadmium ions in both the model solutions and the real samples. The contact time and pH were optimized after which Langmuir and Freundlich isotherms were applied to the data. The sorption capacities for Cu²⁺, Cd²⁺, and Pb²⁺ improved from 3.4, 0.8, and 1.7?g?kg^?1, respectively, to 6.3, 2.6, and 2.6?g?kg^?1 in the same order. The sorbent was shown to remove up to 95% of the metals in less than 10 min. This study has a potential application for the remediation of polluted waters.