Influence of soil properties on heavy metal sequestration by biochar amendment: 1. Copper sorption isotherms and the release of cations

The amendment of carbonaceous materials such as biochars and activated carbons is a promising in situ remediation strategy for both organic and inorganic contaminants in soils and sediments. Mechanistic understandings in sorption of heavy metals on amended soil are necessary for appropriate selection and application of carbonaceous materials for heavy metal sequestration in specific soil types. In this study, copper sorption isotherms were obtained for soils having distinct characteristics: clay-rich, alkaline San Joaquin soil with significant heavy metal sorption capacity, and eroded, acidic Norfolk sandy loam soil having low capacity to retain copper. The amendment of acidic pecan shell-derived activated carbon and basic broiler litter biochar lead to a greater enhancement of copper sorption in Norfolk soil than in San Joaquin soil. In Norfolk soil, the amendment of acidic activated carbon enhanced copper sorption primarily via cation exchange mechanism, i.e., release of proton, calcium, and aluminum, while acid dissolution of aluminum cannot be ruled out. For San Joaquin soil, enhanced copper retention by biochar amendment likely resulted from the following additional mechanisms: electrostatic interactions between copper and negatively charged soil and biochar surfaces, sorption on mineral (ash) components, complexation of copper by surface functional groups and delocalized π electrons of carbonaceous materials, and precipitation. Influence of biochar on the release of additional elements (e.g., Al, Ca) must be carefully considered when used as a soil amendment to sequester heavy metals.     

Improvement of Vicia-micronucleus test for assessment of soil quality: a proposal for international standardization

The Viciafaba root tip micronucleus test is one of the most employed plant genotoxicity assays, and has been used on various types of contaminated materials. This test has been standardized by AFNOR, the French member organization of ISO. However, this test is usually performed with a water extraction step but soil genotoxicity assessment would be more relevant when performed directly in the soil itself. In order to harmonize these protocols, an ISO standard for the V.faba micronucleus test in both liquid phase (exposure of plants to different liquid matrix, including soil water extracts) and solid phase (direct exposure of plants to the soil) would be very useful. In this context, we compared two exposure durations in the solid phase (48 h and 5 d) for the V.faba micronucleus test with two different well-known genotoxicants, maleic hydrazide and copper sulfate. We concluded that these two durations induced equivalent sensitivity: the micronucleus frequency was significantly increased with 5 μmol maleic hydrazide per kg dry soil and with 2 mmol copper sulfate per kg dry soil with both exposure durations. However, exposing roots to soil during 48 h is more practical. Moreover, organically and conventionally cultured seeds were employed to determine whether the seed provenance influenced the test sensitivity. Organic seeds were less sensitive to copper, possibly because copper-based treatments are permitted, and often applied, in organic farms. Therefore, in the absence of completely non-treated seeds, organically-cultured seeds did not appear to offer any advantages over conventional seeds.     

Impacts of boat paint chips on the distribution and availability of copper in an English ria

Discarded paint chips collected from a leisure boat maintenance facility on the Kingsbridge estuary, SW England, have been fractionated to <63 microm and chemically characterised. At about 16% by weight, Cu was the most abundant metallic component, reflecting its biocidal application in antifouling paint. Bioavailability of Cu in the chips, determined by protein digestion, was about 4%, and sea water leachability was about 8%. Copper concentrations in fractionated intertidal sediment from the estuary were highly variable (<10-460 microg g(-1)). Specifically, greatest concentrations and greatest variability among replicates were found in samples collected near boat maintenance facilities. Bioavailability of Cu in sediment averaged 7% but was also variable. We attribute Cu "hot spots" to heterogeneous contamination of local sediment by small quantities of paint chips. Contamination may arise directly, from relatively inert particulates, or indirectly, via release of Cu from chips to interstitial waters and its subsequent adsorption to local sediment.     

Optimization of the continuous biosorption of copper with sugar-beet pectin gels

Sugar-beet pectin xerogels obtained from residues of the sugar industry are an adequate material for metal recovery from effluents in continuous systems. The xerogels were used as a biosorbent for copper removal in a fixed-bed column. The performance of the system was evaluated in different experimental conditions: flow rate, bed height, inlet metal concentration and feeding system (drop and reverse). The effect on the biosorption parameters (saturation time, amount of adsorbed and treated metal, column performance and metal uptake) and the shape of the breakthrough curves was determined. The saturation time increased with increasing bed height but decreased with increasing feed flow rate and inlet metal concentration. Preferential flow channels greatly influenced the metal uptake and column performance. Copper was completely desorbed with 0.1 M HNO₃. Additionally, the column data fitted both the linear and nonlinear expressions of the Thomas model.     

Batch and continuous biosorption of Cu by immobilized biomass of Arthrobacter sp.

The ability of free and polysulphone immobilized biomass of Arthrobacter sp. to remove Cu²⁺ ions from aqueous solution was studied in batch and continuous systems. The Langmuir and Freundlich isotherm models were applied to the data. The Langmuir isotherm model was found to fit the sorption data indicating that sorption was monolayer and uptake capacity (Q^o) was 175.87 and 158.7 mg/g for free and immobilized biomass respectively at pH 5.0 and 30 °C temperature, which was also confirmed by a high correlation coefficient, a low RMSE and a low Chi-square value. A kinetic study was carried out with pseudo-first-order reaction and pseudo-second-order reaction equations and it was found that the Cu²⁺ uptake process followed the pseudo-second-order rate expression. The diffusivity of Cu²⁺ on immobilized beads increased (0.402 × 10⁻⁴ to 0.435 × 10⁻⁴ cm²/s) with increasing concentration from 50 to 150 mg/L. The maximum percentage Cu²⁺ removal (89.56%) and uptake (32.64 mg/g) were found at 3.5 mL/min and 20 cm bed height. In addition to this the Bed Depth Service Time (BDST) model was in good agreement with the experimental data with a high correlation coefficient (>0.995). Furthermore, sorption and desorption studies were also carried out which showed that polysulphone immobilized biomass could be reused for up to six sorption–desorption cycles.     

The copper tolerance strategies and the role of antioxidative enzymes in three plant species grown on copper mine

This study was undertaken to identify the strategies and the status of antioxidant enzyme activities involved in three plant species tolerance against Cu-toxicity in copper mine. The following methods were used for evaluations in three wild type species; Datura stramonium, Malva sylvestris and Chenopodium ambrosioides. The level of chlorophyll and the activities of superoxide dismutase (SOD), glutathione peroxidase (GPX) and catalase (CAT) by spectrometry, malondialdehyde (MDA) and dityrosine by HPLC and the levels of Cu in tissues and soils by atomic absorption spectrometry (AAS).

Analysis showed that total and available copper were at toxic levels for plants growing on contaminated soil (zone 1). However, there were not any visual and conspicuous symptoms of Cu toxicity in plant species. Among three species, excess copper was transferred only into the D. stramonium and C. ambrosioides tissues. The C. ambrosioides accumulated Cu in roots and then in leaves, in which the leaves chloroplasts stored Cu around two times of vacuoles. In D. stramonium most of Cu was accumulated in leaves in which the storage rate in vacuoles and chloroplasts were 42% and 8%, respectively. In zone 1, the chlorophyll levels increased significantly in leaves of C. ambrosioides with respect to the same plant growing on uncontaminated soil (zone 2). There was insignificant decrease in chlorophyll content of D. stramonium leaves, collected from zone 1 with respect to zone 2. The D. stramonium and C. ambrosioides in zone 1, both revealed significant increase in their tissues antioxidant enzyme activities in comparison with the same samples of zone 2. There was significant elevation in oxidative damage biomarkers; MDA and dityrosine, when the aerial parts of D. stramonium in zone 1 were compared with the same parts of zone 2.

We concluded that there were different tolerance strategies in studied plant species that protected them against copper toxicity. In M. sylvestris, exclusion of Cu from the roots or its stabilization in the soil restricted Cu toxicity effects. On the other hand D. stramonium and C. ambrosioides, elevated their antioxidative enzyme activities in response to cu-toxicity. In addition, the species D. stramonium accumulated excess of Cu in leaves vacuoles.     

Tracking effective measures for closed-loop recycling of automobile steel in China

Closed-loop recycling of steel in automobiles is particularly difficult because of the low tolerance for impurities and the use of composites of various types of steel products. Technologies that reduce impurities or increase impurity tolerance must be developed and introduced to the steel recycling system at the appropriate time. This study evaluated the feasibility of closed-loop recycling in the automobile industry in China. Material pinch analysis combined with dynamic modeling of the life cycle of steel sheets used in the manufacture of automobiles was employed to estimate the amount of steel sheet scrap available for closed-loop recycling and the amount of copper contamination in the scrap. The results indicate that by 2050, more than half of the old steel sheet scrap generated annually will have to be down-cycled because of its high copper contamination. However, scenario analyses of three types of technologies for mitigating the problem of copper contamination showed the potential for increasing the amount of old scrap used in closed-loop recycling. In particular, improving copper tolerance in the steel production process could be effective both now and in 2050.     

Modelling future copper ore grade decline based on a detailed assessment of copper resources and mining

The concept of “peak oil” has been explored and debated extensively within the literature. However there has been comparatively little research examining the concept of “peak minerals”, particularly in-depth analyses for individual metals. This paper presents scenarios for mined copper production based upon a detailed assessment of global copper resources and historic mine production. Scenarios for production from major copper deposit types and from individual countries or regions were developed using the Geologic Resources Supply-Demand Model (GeRS-DeMo). These scenarios were extended using cumulative grade-tonnage data, derived from our resource database, to produce estimates of potential rates of copper ore grade decline.The scenarios indicate that there are sufficient identified copper resources to grow mined copper production for at least the next twenty years. The future rate of ore grade decline may be less than has historically been the case, as mined grades are approaching the average resource grade and there is still significant copper endowment in high grade ore bodies. Despite increasing demand for copper as the developing world experiences economic growth, the economic and environmental impacts associated with increased production rates and declining ore grades (particularly those relating to energy consumption, water consumption and greenhouse gas emissions) will present barriers to the continued expansion of the industry. For these reasons peak mined copper production may well be realised during this century.     

On modelling the global copper mining rates,market supply,copper price and the end of copper reserves

The world supply and turnover of copper was modelled using simple empirical estimates and a COPPER systems dynamics model developed for this study. The model combines mining, trade markets, price mechanisms, population dynamics, use in society and waste as well as recycling, into a whole world system. The degree of sustainability and resource time horizon was estimated using four different methods including (1) burn-off rates, (2) peak discovery early warning, (3) Hubbert's production model, and (4) COPPER, a system dynamics model. The ultimately recoverable reserves (URR) have been estimated using different sources that converge around 2800 million tonne, where about 800 million tonne have already been mined, and 2000 million tonne remain. The different methods independently suggest peak copper mine production in the near future. The model was run for a longer period to cover all systems dynamics and delays. The peak production estimates are in a narrow window in time, from 2031 to 2042, with the best model estimate in 2034, or 21 years from the date of writing. In a longer perspective, taking into account price and recycling, the supply of copper to society is estimated to run out sometime after 2400. The outputs from all models put focus on the importance of copper recycling so that society can become more sustainable with respect to copper supply.