Availability Of Cu Research Articles

Distribution of indium, germanium, gallium and other minor and trace elements in polymetallic ores from a porphyry system: The Morococha district, Peru

We report indium, germanium, gallium, and other minor and trace elements contents in sphalerite, chalcopyrite, galena, and tetrahedrite-tennantite occurring in skarn and skarn-free (“Cordilleran”) polymetallic mantos and vein ore bodies in the Miocene porphyry-related Morococha District, Central Peru. Among the investigated minerals, LA-ICP-MS measurements indicate that In and Ga concentrate mostly in sphalerite (Inter-Quartile Range [IQR] 217–2.7 ppm and up to 4608 ppm In; IQR 61–2.0 ppm and up to 2137 ppm Ga) and chalcopyrite (IQR 109–32 ppm and up to 1070 ppm In; IQR 62–1.5 ppm and up to 630 ppm Ga). In coeval generations of sphalerite and chalcopyrite, the contents of In and Ga in sphalerite are at least two times higher than in chalcopyrite. Germanium content is generally low in the four analyzed minerals (IQR 1.2–0.19 ppm), although late Fe-poor sphalerite may yield much higher values (IQR 129–74 ppm).Certain trace element contents appear to correlate with (i) the evolving characteristics of the hydrothermal fluids during individual mineralization events, and (ii) the location of the studied ore bodies relative to the hydrothermal feeders. The highest In values in sphalerite are found in high-sulfidation assemblages in Cordilleran polymetallic veins and, with lower amounts, in low-sulfidation assemblages in skarn bodies. In intermediate-sulfidation assemblages in Cordilleran mineralization, In content decreases from early to late generations of sphalerite, while that of Ge increases. Spatial trace-element trends in Cordilleran veins and replacement bodies formed during the so-called “Morococha district-scale polymetallic event” include, from porphyry-distal to porphyry-proximal locations: i) In and Cu, and to a lesser extent Ga, enrichment in sphalerite; ii) Se and Hg enrichment and Sn and Ag depletion in chalcopyrite; iii) In enrichment in galena; and iv) Ag depletion in tetrahedrite-tennantite.Our dataset suggests that In is incorporated in the sphalerite crystal lattice via coupled substitutions involving Cu and subordinately also Sn and Ag. Availability of Cu in the mineralizing fluids is therefore key to In enrichment in sphalerite. Progressive dilution of metal-rich magmatic-hydrothermal fluids and Cu precipitation probably account for the progressive In depletion in distal-to-porphyry Zn-Pb-Ag and Ag-Pb Cordilleran polymetallic mineralization and in late sphalerite generations in intermediate-sulfidation assemblages.

The Effect of Granular Activated Carbon and Biochar on the Availability of Cu and Zn to Hordeum sativum Distichum in Contaminated Soil.

The presence of heavy metals in the soil could impose serious problems on soil-plant systems due to the accumulation of heavy metals in plants. Even vital elements such as Cu and Zn have a toxic effect in the case of excessive intake by living organisms. The present work aimed to investigate the content of loosely bound (exchangeable, complexed, and specifically sorbed) compounds of Cu and Zn and their availability to spring barley (Hordeum sativum distichum) in contaminated Haplic Chernozem soil under the conditions of a model experiment (five approximate permissible concentrations (APC) and 10 APC of metal). Changes in the bioavailability of the metals upon application of carbon sorbents were observed. An increase in loosely bound metal compounds has been shown under conditions of soil contamination with metals (up to 57% of the total content). The increase in the availability of Cu in the soil was mainly due to the formation of complexed metal forms with organic matter (up to 17%). The availability of Zn was found to be associated with an increase in exchangeable (up to 21%) and specifically sorbed compounds (up to 27%). Granular activated carbon (GAC) and biochar have high sorption properties. A decrease in the content of loosely bound compounds of metals was established, especially in the most mobile forms such as exchangeable and complexed forms. The introduction of sorbents into the soil opened up a new venue for binding heavy metals in situ, eventually leading to a decrease in their bioavailability. The inactivation of Cu and Zn in the soil upon the application of sorbents led to a decrease in metal absorption by spring barley. The highest efficiency of biochar application was established at a dose of 2.5% and 5% in soil contaminations of 5 APC and 10 APC of Cu or Zn. The efficiency of the use of sorbents was more influenced by the dose of application than by the type of sorbent. There was no significant difference between biochar and GAC. Stabilization and inactivation of metals may improve soil fertility and plant growth.

Using vermiwash to enhance performance of small-scale vermifiltration for swine farm wastewater.

Pollution caused by swine wastewater is a growing concern in many countries. In the developing countries, swine wastewater is not properly collected and treated, the wastewater from swine farm pollutes the ecosystem. Especially for small swine farms, they could not afford to have wastewater treatment system. Therefore, farmers need cheap, sustainable technology for future mixed farming. Vermifiltration by earthworm has been introduced to be an answer for enhancing wastewater treatment. Vermiwash is the liquid gathered from vermicomposting that has high microbial activities and nutrients. This study was carried out on a small pilot scale to investigate swine wastewater treatment efficiency of vermifiltration system with and without vermiwash and compared with the geofiltration system. Vermiwash was incubated in vermifiltration and geofiltration systems for 1week before the treatment. The result showed improved efficiency of vermifiltration incubated with vermiwash in swine wastewater treatment for biological oxygen demand (BOD), chemical oxygen demand (COD) and total suspended solids (TSS) removal, which was highest followed by vermifiltration without incubated vermiwash, geofilter incubated with vermiwash and geofilter, respectively. Good performance of vermifiltration incubated with vermiwash compared with the geofilter treatment was demonstrated for removal of BOD (91.29 ± 9.89%, n = 10), COD (91.42 ± 6.34%, n = 10) and TSS (86.02 ± 10.45%, n = 10). Furthermore, the burrowing activity of the test earthworm (Eisenia fetida) promoted the aeration condition in vermifilter which led to more dissolved oxygen (DO) in effluent (61.28 ± 20.05%, n = 10). Moreover, the amount of copper (Cu) in effluent was decreased compared with influent by up to 88% in all treatment. After 10weeks of the experiment, the vermicompost that was incubated with vermiwash and produced from earthworm on the top layer was analyzed and showed that nutrients (nitrogen, phosphorus) and soil organic carbon were increased with vermifilter treatment (47.65, 81.61 and 31.79%, respectively) compared with geofilter treatment. In addition, bioavailability of Cu in soil in form of exchangeable Cu was decreased by increasing the bound to organic matter fraction. Transformation of Cu during vermifiltration happened and alleviated the mobility and availability of Cu. Copper in exchangeable form can change into non-toxic form. Therefore, vermifiltration process incubated with vermiwash could reduce the dispersion of copper in swine waste. In conclusion, vermiwash could enhance performance of vermifiltration for swine farm wastewater treatment. The available fraction of copper in vermicompost produced from vermifiltration decreased. Therefore, the farmer could produce vermicompost as the biofertilizer for agricultural production. Using vermifiltration for wastewater treatment in small swine farm could be the eco-solution for nutrient recovery, water resource recycles and minimize pollution.

Trace Metal Availability Affects Greenhouse Gas Emissions and Microbial Functional Group Abundance in Freshwater Wetland Sediments.

We investigated the effects of trace metal additions on microbial nitrogen (N) and carbon (C) cycling using freshwater wetland sediment microcosms amended with micromolar concentrations of copper (Cu), molybdenum (Mo), iron (Fe), and all combinations thereof. In addition to monitoring inorganic N transformations (NO3–, NO2–, N2O, NH4+) and carbon mineralization (CO2, CH4), we tracked changes in functional gene abundance associated with denitrification (nirS, nirK, nosZ), dissimilatory nitrate reduction to ammonium (DNRA; nrfA), and methanogenesis (mcrA). With regards to N cycling, greater availability of Cu led to more complete denitrification (i.e., less N2O accumulation) and a higher abundance of the nirK and nosZ genes, which encode for Cu-dependent reductases. In contrast, we found sparse biochemical evidence of DNRA activity and no consistent effect of the trace metal additions on nrfA gene abundance. With regards to C mineralization, CO2 production was unaffected, but the amendments stimulated net CH4 production and Mo additions led to increased mcrA gene abundance. These findings demonstrate that trace metal effects on sediment microbial physiology can impact community-level function. We observed direct and indirect effects on both N and C biogeochemistry that resulted in increased production of greenhouse gasses, which may have been mediated through the documented changes in microbial community composition and shifts in functional group abundance. Overall, this work supports a more nuanced consideration of metal effects on environmental microbial communities that recognizes the key role that metal limitation plays in microbial physiology.

Response of soil fertility and Cu and Cd availability to biochar application on paddy soils with different acidification levels

The activation of toxic heavy metals caused by soil acidification has shown detrimental effect on rice safety and quality in paddy soil of southern China. Previous reports have shown that biochar had great potential in controlling heavy metal pollution in soil, but the effect of biochar on soil fertility and heavy metal availability in different soil acidity levels remains unknown. In our study, rice straw (RSBC) and rice husk (RHBC) were selected to produce biochar. An incubation experiment with three biochar application rates, namely 0 (CK), 20 g kg−1 (C1), and 50 g kg−1 (C2) combined with four soil acidification levels, pH value 4.09 (L1), 4.48 (L2), 4.68 (L3), and 5.04 (L4), was conducted in this study. The soil pH, total nitrogen (N), soil organic matter (SOM), available phosphorus (P), available potassium (K), available Cu and Cd concentrations were determined after incubation for 60 days. Results showed that the RSBC is greater in improving the pH and nutrients in acidified soil than RHBC, and the increase depends on biochar dosage. Compared with RHBC, the RSBC showed greater performance in decreasing the availability of Cu and Cd in four soil acidity levels (L1, L2, L3, and L4); the available Cu reduced by 41.32, 25.09, 21.42, and 5.80%, and available Cd by 15.69, 13.73, 17.65, and 17.65%, respectively. In addition, higher soil acidification degree induced smaller increase range of soil pH and available P concentration by biochar. We suggest that biochar can be applied in acidified paddy field to remediate heavy metal pollution in Southern China rice production. At the same time, we need to further ascertain the impact of these two biochars on the bioavailability of heavy metals in different soil acidity levels.

The Availability and Accumulation of Heavy Metals in Greenhouse Soils Associated with Intensive Fertilizer Application.

In China, greenhouse agriculture, which provides abundant vegetable products for human consumption, has been rapidly developed in recent decades. Heavy metal accumulation in greenhouse soil and products obtained have received increasing attention. Therefore, the availability and accumulation of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) and their association with soil pH, soil organic matter (SOM), inorganic nitrogen (IN), total nitrogen (TN), available phosphorus (AP), and planting year (PY) in greenhouse soils were analyzed. The results showed that the mean concentrations of available Cd, Cu, Ni, Pb, and Zn were 17.25 μg/kg, 2.89, 0.18, 0.36, and 5.33 mg/kg, respectively, while their suggested levels in China are 0.6, 100, 100, 120, and 250 mg/kg. Cd, Cu, and Zn might be mainly originated from fertilizer application. A lower soil pH significantly increased the available Cu, Ni, and Zn concentrations and reduced Cd, Cu, Ni, and Zn accumulation. A higher AP significantly increased the proportions of available Cu, Ni, and Zn and elevated Cd, Cu, and Zn accumulation. There was a strong positive correlation between Cd, Pb, and Zn availability and TN, while IN was negatively related to the availability and accumulation of Cu and Zn. It was concluded that chemical fertilizer application increased the availability of Cu, Ni, Pb, and Zn and the accumulation of Cd, Cu, and Zn. Manure application clearly elevated the accumulation and availability of Cd and Zn in greenhouse soil.

Influence of mycorrhiza and fly ash on the survival, growth and heavy metal accumulation in three Acacia species grown in Cu-Ni mine soil.

Acacia albida, Acacia luederitzii, and Acacia tortilis are dominant acacia species in Botswana and have the potential to rehabilitate the heavy metal degraded environment. To establish this claim, experiments to assess the influence of mycorrhizal inoculation and fly ash amendments on the survival, growth and heavy metal accumulation of these species in mine tailings were conducted. A two-factor (AM inoculation × fly ash) in CRD was done on each of the three Acacia species consisting of four treatments: control (no mycorrhizal, no fly ash coded as - AM/- FA), with mycorrhizal but no fly ash (+ AM/- FA), no mycorrhizal but with fly ash (- AM/+ FA), and with mycorrhizal and with fly ash (+ AM/+ FA). After 24weeks, results showed that the survival and dry matter yield of all Acacia species were enhanced by 10% with fly ash amendments. However, mycorrhiza inoculation alone improved the survival of A. albida and A. luederitzii but reduced that of the A. tortilis in mine tailings. Fly ash amendments increased the pH of the mine tailings, reduced the availability of Cu, Ni, Pb, Mn and Zn and consequently reduced the concentration of these metals in shoots. On the other hand, it increased the availability of As in the mine tailings. In addition, mycorrhizal inoculation reduced the concentration of these metals in shoots regardless of fly ash amendments. Overall, combined mycorrhizal inoculation and fly ash amendment enhanced the establishment of A. luederitzii in heavy metal-contaminated soils by reducing the heavy metal availability and metal uptake, thus increasing the survival and dry matter yield of plants.

Solubility and availability of micronutrients extracted from silicate agrominerals

Abstract: The objective of this work was to evaluate the solubility of the micronutrients copper, nickel, and zinc, chemically extracted from silicate agrominerals, as alternative sources of potassium for lettuce (Lactuca sativa) and rice (Oryza sativa) cultures, as well as their availability to the plants. The micronutrient contents of five agrominerals (alkaline ultramafic, biotite schist, volcanic breccia, phlogopite schist, and mining by-product from Chapada) were evaluated, after being extracted by the citric acid, hydrochloric acid, diethylenetriaminepentaacetic acid, 3051A, neutral ammonium citrate, and Mehlich-3 methods. The agrominerals, at the doses of 0 (control), 200, 400, and 600 kg ha-1 K, were mixed to soil where lettuce and rice were cultivated. The agrominerals presented a low solubility of Ni, Cu, and Zn, with lower contents in lettuce shoots and rice grains than the corresponding soluble standards in sulfate form. The availability of micronutrients to the plants increased with the use of agrominerals, in comparison with the control. Similarities were observed in micronutrient solubility and availability between the different groups of agrominerals. The solubility and availability of Cu, Ni, and Zn depend on the solubility of the minerals that compose the agrominerals.

Effects of Parent Material and Land Use on the Variability of Available Cu in a Wetland Soil under Long-Term Farming System

The study was carried out in the dry season to evaluate the variation in available Cu in wetland soil under long-term farming systems. Twenty four surface (0-20 cm) composite soil samples of acidic nature were obtained and analyzed for available Cu in the soils using five extractants (0.01M HCl, Coca-cola, 0.05M EDTA, 0.05M DTPA, and 1N NH4OAc) respectively. Some important soil char- acteristics like soil texture, pH, SOM, and ECEC were also determined and corre- lated with the extractable Cu. The result shows that the content of available Cu varied significantly from 1.72-10.76 mg kg-1 by DTPA and Coca-cola methods, and these were rated from low to moderate, respectively. The study further shows that, the comparative extraction capacity of these extractants followed the order: Coca-Cola > O.1N HCl > 0.05M EDTA > NH4OAc > 0.005M DTPA. The wide variability of the available Cu in the wetland soils under long-term farming sug- gests that the availability of Cu in the soil are haply influenced by the agricultural locations, type of land use systems and soil parent materials, respectively. Corre- lation data also indicated that the fractions of Cu by different extractants were in a state of dynamic equilibrium and dependent were on pH, organic matter, ECEC, and clay content. The marginally Cu content of the wetland soils suggests that the use of integrated organo-mineral fertilizer with copper sulphate com- pound (CuSO4.5H2O) is required to boost the soil Cu and hence increased crop production.

Competitive sorption and availability of coexisting heavy metals in mining-contaminated soil: Contrasting effects of mesquite and fishbone biochars

Mesquite and fishbone were pyrolyzed to produce biochar (MBC and FBC, respectively) at different temperatures. The effects of the MBC and FBC on the removal of single and competitive metals (Cd, Pb, Zn, and Cu) from aqueous solutions were evaluated. A greenhouse pot experiment was also conducted using wheat plants with the mining-contaminated soils. In the presence of MBC or FBC (dosages of 15 and 30 g kg−1), the bioavailability of co-existing Cd, Pb, Zn, Cu, Mn, and Fe were assessed. The results clearly indicated competitive adsorption among metals with the highest adsorption preference toward Pb. The removal efficiency and partition coefficient (PC) values of heavy metals for FBCs were higher than those for MBCs. These two values increased with MBC pyrolysis temperature under both single- and multi-metals adsorption conditions. Applying FBC to mining soil resulted in the highest reduction in most NH4NO3-extractable heavy metals, reducing their availability to wheat plants. At the highest application dosage of 30 g kg−1, the highest metal immobilization, which accounted for 40.0% and 43.0% for Pb, 61.7% and 66.2% for Cu, 48.3% and 55.6% for Zn, and 32.7% and 33.8% for Cd, was achieved following the application of FBC400 and FBC600, respectively. However, applying MBC lead to a significant reduction in the availability of Cu and Pb but not that of Zn and Cd. FBC is thus more effective in removing heavy metal from aqueous solutions, as well as in immobilizing co-existing heavy metals in contaminated mining soil. It could, therefore, be an effective sorbent and immobilizing agent.

Indium Mineralization in the Volcanic Dome-Hosted Ánimas–Chocaya–Siete Suyos Polymetallic Deposit, Potosí, Bolivia

A volcanic dome complex of Miocene age hosts the In-bearing Ánimas–Chocaya–Siete Suyos district in SW Bolivia. Ore mineralization occurs as banded and massive infillings in sub-vertical, NE-SW striking veins. In this article, a detailed petrographic study is combined with in situ mineral geochemistry determinations in ore from the Arturo, Chorro and Diez veins in the Siete Suyos mine, the Ánimas, Burton, Colorada, and Rosario veins in the Ánimas mine and the Nueva vein in the Chocaya mine. A three-stage paragenetic sequence is roughly determined for all of them, and includes (1) an early low-sulfidation stage that is dominated by cassiterite, pyrrhotite, arsenopyrite, and high-Fe sphalerite (FeS > 21 mol. %); (2) a second intermediate-sulfidation stage dominated by pyrite + marcasite ± intermediate product, sphalerite (FeS < 21 mol. %), stannite, and local famatinite; and, (3) a late intermediate-sulfidation stage dominated by galena and Ag-Pb-Sn sulfosalts. Electron-probe microanalyses reveal high indium enrichment in stage-2 sphalerite (up to 9.66 wt.% In) and stannite (up to 4.11 wt.% In), and a moderate enrichment in rare wurtzite (up to 1.61 wt.% In), stage-1 sphalerite (0.35 wt.% In), cassiterite (up to 0.25 wt.% In2O3), and ramdohrite (up to 0.24 wt.% In). Therefore, the main indium mineralization in the district can be associated to the second, intermediate-sulfidation stage, chiefly in those veins in which sphalerite and stannite are more abundant. Atomic concentrations of In and Cu in sphalerite yield a positive correlation at Cu/In = 1 that agrees with a (Cu+ + In3+) 2Zn2+ coupled substitution. The availability of Cu in the mineralizing fluids during the crystallization of sphalerite is, in consequence, essential for the incorporation of indium in its crystal lattice and would control the distribution of indium enrichment at different scales. The highest concentrations of indium in sphalerite, which is found in the Diez vein in the Siete Suyos mine, occur in crustiform bands of sphalerite with local “chalcopyrite disease” texture, which has not been observed in the other studied veins. In stannite, the atomic concentrations of In are negatively correlated with those of Cu and Sn at Cu + In = 2 and Sn + In = 1. Thus, atomic proportions and correlations suggest the contextualization of the main indium mineralization in the sphalerite–stannite–roquesite pseudoternary system.

Complementary assessment of As, Cu and Zn environmental availability in a stabilised contaminated soil using large-bore column leaching, automatic microcolumn extraction and DGT analysis

Soil pollution with trace elements is a concerning issue worldwide. Monitoring of soil pollution and remediation protocols need still from valid complementary analytical approaches able to detect changes in speciation and lability of metals in soils (e.g. stabilization or mobility). In this work, we compare three different analytical approaches to assess potential changes in environmental availability of Cu, As and Zn in a Mediterranean polluted soil that was amended with different combinations of iron sulphate and alkaline paper sludge waste. The studied methods were: (i) a standard large-bore flow-through column system (macrocolumn), (ii) an automatic dynamic flow-through microcolumn extraction system, and (iii) the diffusive gradients in thin gels technique (DGT). The three analytical approaches tested showed immobilization of Zn and Cu in contaminated mine soils after co-application of paper sludge and iron sulphate, but they differ quantitatively in terms of As mobility. Interconversion between oxidation states of inorganic As is observed to occur to a larger extent in macrocolumn. Because this may only occur in very specific Mediterranean scenarios (i.e. organic matter application to intermittently flooded mine soils), macrocolumn extraction procedures might not appropriately mimic the environmental availability of As in soils with organic amendments (e.g., paper sludge waste). Microcolumn leaching is the fastest screening tool to ascertain the efficiency of chemical amendments, but DGT is a good alternative with less technical demands.

Biochar improves the morphological, physiological and biochemical properties of white willow seedlings in heavy metal-contaminated soil

Biochar is an efficient soil amendment used for promoting plant resistance to heavy metal (HM)-contaminated soils. There is a need for further investigation of its impacts on plants and soil. This study was undertaken as a pot experiment to assess the effect of biochar (0, 2.5, and 5% mass fractions) on the morphological, physiological and biochemical responses of white willow seedlings (Salix alba L.) cultured in uncontaminated soil and mixed soil contaminated with HM (Cu, Pb, and Cd). Additionally, some chemical properties and HM bioavailability were evaluated. Biochar increased height and diameter, root elongation, leaf area and dry biomass of the seedlings in both soils. Its addition to the contaminated soil reduced electrolyte leakage, the malondialdehyde and proline contents but increased the chlorophyll content, net photosynthesis rate, intercellular CO2 concentration and transpiration rate in the leaf. Use of biochar (especially at 5% rate) in both soils, increased soil pH, total nitrogen, soil organic carbon and available P and K, while in the contaminated soil the availability of Cu, Pb, and Cd decreased. The results showed that biochar is a suitable amendment to contaminated soils that improves plant properties by improving soil chemical features and immobilizing HMs.

Growth, biochemical response and nutritional status of Angico-Vermelho (Parapiptadenia rigida (Bentham) Brenan) under the application of soil amendment in Cu-contaminated soil

Forest species Angico-Vermelho (Parapiptadenia rigida (Bentham) Brenan) is an alternative for the revegetation of areas contaminated with high levels of heavy metals such as copper (Cu). However, excess Cu may cause toxicity to plants, which is why the use of soil amendments can facilitate cultivation by reducing the availability of Cu in the soil. The aim of this study was to assess how the use of amendment can contribute to growth and nutritional status as well as reduce oxidative stress in Angico-Vermelho grown in Cu-contaminated soil. Samples of a Typic Hapludalf soil containing high Cu content were used for the application of four amendments (limestone, organic compost, Ca silicate and zeolite), in addition to a control treatment. The treatments were arranged in a completely randomized design, with four replicates. The use of amendments decreased Cu content available in soil and contributed to improve both plant nutritional status and its antioxidant response expressed by enzymatic activity. The application of the amendments, especially zeolite and Ca silicate, increased dry matter yield of Angico-Vermelho. Thus, the results presented here suggest that the use of amendments contributes to improving Cu-contaminated soils and favors revegetation with Angico-Vermelho.

Geospatial Distribution of Copper in the Intensively Rice Growing Soils of Madurai District, Tamil Nadu

The present study was undertaken to assess the status of available copper (Cu) in the intensively rice growing soils of Madurai district, Tamil Nadu. A total of 235 geo referenced surface soil samples were collected and analysed for plant available Cu and simple correlation was worked out to ascertain the degree of relationship between soil properties and available Cu content of soils of the study area. Plant available Cu in the entire rice growing soils ranged from 0.08 to 9.50 mg kg-1. Out of two hundred and thirty five locations of rice growing soils of Madurai district collected for the purpose of delineation of copper, 29.78 per cent of the soils were deficient in Cu status while 31.91 and 38.29 per cent areas were medium and high in available Cu. Among the soil properties, clay, silt and CEC had a positive influence on the availability of Cu whereas, sand, pH, OC and CaCO3 content had negative influence on available copper. The step-wise multiple regression equation in general indicated that the pH, CEC, OC and sand accounted for 54.50 per cent variation in available Cu in the soils of study area.

Availability and vertical distribution of Cu, Cd, Ca, and P in soil as influenced by lime and apatite with different dosages: a 7-year field study.

It is well known that alkaline amendments could effectively decrease the bioavailability of heavy metals in soils. However, the vertical distribution of heavy metals and the nutrients enriching in amendments are little concerned during long-term field remediation. Thus, the objective of the present study was to investigate the vertical distribution and availability of Cu, Cd, Ca, and P after a 7-year field experiment. In this study, a single application of lime and apatite was conducted with the rates of 1.71-6.84 and 6.84-19.8tons/ha, respectively. Soil pH and immobilization efficiency of Cu and Cd were both increased with increasing dosages of lime and apatite (0-50cm). Applications of lime and apatite decreased the mobility of Cu and Cd although soil Cu and Cd in the surface soil were increased due to the input by atmospheric dry and wet deposition. Moreover, concentrations of Cu and Cd in lime- and apatite-amended soils (0-13cm) were higher than those in the control group. However, applications of lime and apatite decreased the downward eluviations of heavy metals in soils (13-50cm). For soil nutrients, the Ca concentrations at 0-13 and 13-30cm were both enhanced with increasing amendment dosages, while only soil P concentration at 0-13cm was increased in apatite-treated soils and majority of them presented in stable-P. In addition, resin-P was increased with increasing dosages of the apatite, which suggested that high eutrophication risk was induced by excessive P loss. Thus, more attention should be paid to the nutrients (phosphorus) and pollutants enriching in the amendments during in-situ remediation of heavy metal-contaminated soils.

Study of potential availability of heavy metals to phytoremediation to use of ash from biomass combustion

<p>Ashes, formed as a result of combustion of biomass are a new class of by-products of combustion and due to the large variety of these materials their chemical composition has not been fully determined. Their use is limited, despite the fact that their production has increased. This work presents the results of studies on the possibility of limiting the potential availability of Cu, Mn, Pb and Zn for plants by use of an inorganic stabilizer - ash from biomass combustion. In this study the usefulness of ash from biomass for binding mobile fractions of heavy metals (Cu, Mn, Pb and Zn) was evaluated. The investigations were executed using three extraction tests with the use of the following extraction solutions: 1 M HNO3 – acid soluble forms (As), 0.05 M EDTA – bioavailable forms (Bio), 2.5% CH3COOH – exchangeable forms (Ex). The values of the following parameters: Mobility Index (MI), Contamination Factor (CF), Pollution Load Index (PLI), Geo – accumulation Index (Igeo) and Ecological Risk Index (RI) were defined and determined for their suitability as a test soil stabilizer. Furthermore, a multivariate statistical analysis was carried out. It was found, that a phytoremediation process using investigated ash from biomass combustion can be applied to soil contaminated by heavy metals.</p>

Optimization and Validation of an Extraction Method for Evaluating the Availability of Cu, Zn, Mn, Ni, Cr and Cd in Soil with the Use of the Mehlich-1 Extractor

The Mehlich-1 extractor is routinely used to evaluate the bioavailability of metals in soil since it has a high closeness between the amount of these elements absorbed by the plants and those available in soil, as well as being simple and practical to use. Thus, the aim of this work was to improve (optimize) a Mehlich-1 extraction method for evaluating the availability of Cu, Zn, Mn, Ni, Cr and Cd in soil using Box-Behnken type response surface method (RSM). After optimizing the soil amount, Mehlich-1 extractor volume and stirring time, the validation of the newly developed method was performed by evaluating the following parameters: matrix adjustment, linearity, linear range, limits of detection (LOD) and of quantification (LOQ), precision and accuracy. The analytical method proposed by this study can be routinely employed for the evaluation of soil toxicity since it presented advantages such as simplicity, speed and efficacy, as well as being precise and accurate.

Green synthesis of a plant-derived protein protected copper quantum cluster for intrauterine device application.

Fluorescent copper quantum clusters (CuQCs) have received great interest in recent times due to their attractive features, such as water solubility, low cost, wide availability of Cu and good biocompatibility. Recently, considerable efforts have been devoted to the preparation and applications of CuQCs. Herein, we report a simple one-pot green method for the preparation of fluorescent CuQCs using a plant-derived protein, gluten, as a stabilizing agent. Gluten, a naturally abundant, low-cost and sustainable plant-protein derived from wheat, was employed both as a reducing and stabilizing agent to produce blue emitting CuQCs. The CuQCs were characterized by UV-Vis absorption, fluorescence, FT-IR, TEM, and XPS. We further incorporated CuQCs into a polymer to study the release rate of Cu2+ ions from a CuQC-polymer composite, since copper ions are well known for their fungicidal properties and contraceptive action in copper-T (CuT). The CuQCs were incorporated into a model polymer, polyurethane (PU), by melt compounding, and the mixtures were extruded in the form of a wire. It was observed that the CuQCs were uniformly dispersed within the polymer matrix. An in vitro experiment was carried out to quantify the potential release of Cu(ii) ions for contraceptive applications. The developed nanocomposite releases Cu(ii) ions for 90 days, which suggests the potential application of the CuQCs in the medical field like the development of short-term intrauterine devices (IUDs). Compared to conventional IUDs, here the CuQC-PU nanocomposite reduces the burst release of the Cu2+, and the release rates can be tuned by changing the composition of the materials. These results suggest that the CuQC-PU nanocomposites have great potential to replace current commercial intrauterine devices.

Indium-bearing sulfides from the Hämmerlein skarn deposit, Erzgebirge, Germany: evidence for late-stage diffusion of indium into sphalerite

At the Hammerlein skarn deposit, located in the western Erzgebirge (Germany), a major cassiterite-dominated Sn mineralization stage is spatially associated with a younger Zn-Cu-In sulfide mineralization stage. In this contribution, we provide the first detailed description of the Zn-Cu-In sulfide mineralization stage, based on field geological observations combined with detailed petrographic studies and electron probe microanalysis data. Indium-rich sulfide mineralization occurs as irregular, semi-massive lenses or as infill of short, discontinuous veinlets that crosscut the cassiterite-bearing skarn assemblage. Indium- and Cu-rich sphalerite and roquesite are found to be closely associated with In-bearing chalcopyrite. The highest In concentrations in sphalerite occur at the rims and along cracks of sphalerite grains. The distribution resembles diffusion profiles, suggesting that the In enrichment is due to an hydrothermal overprint that postdates the initial formation of both sphalerite and chalcopyrite. Textural relations illustrate that the diffusion fronts in sphalerite grains are thicker where they are in contact to anhedral masses of hematite and magnetite. Our observations suggest that In enrichment in sphalerite at the Hammerlein skarn deposit is due to the decomposition of In-bearing chalcopyrite. The resultant release of Fe led to the formation of hematite and magnetite, whereas Cu and In were incorporated into sphalerite along grain boundaries and micro fractures. Incorporation into the sphalerite lattice took place by coupled substitution of Cu+ + In3+ ↔ 2Zn2+, suggesting that the concurrent availability of Cu and In may be an essential factor to enrich In in sphalerite in hydrothermal ore-forming environments.