The effect of temperature and salinity on copper body-burden and copper toxicity to Hediste (Nereis) diversicolor

Temperature from 12 to 22°C and salinity from 30.5 to 7.6 increased accumulation of copper in Hediste diversicolor. Copper accumulated ranged from 85.83 to 217.14 g g^-1. Sediments reduced accumulation of copper under temperature-salinity combinations. Accumulated copper ranged from 90.19 to 153.26 g g^-1.However, mortality of the worms was not solely dependent upon copper body-burden. It ranged from 34 to 45% and from 38 to 80% in the presence of sediment. A combination of osmoregulatory and thermal stresses increased the toxic effect of copper to the worms.     

Modelling and mapping of copper runoff for Europe

A predictive runoff rate model for copper has been refined and used to generate copper runoff maps for Europe. The new model is based on laboratory and field runoff data and expresses the runoff rate R (g m(-2) yr(-1)) through two contributions, both with a physical meaning: R = (0.37SO(0.5)(2) = 0.96 rain10(-0.62 pH) (cos(theta)/cos(45 degree)). Input parameters are the SO(2) concentration (microg m(-3)), pH, amount of rain (mm yr(-1)), and surface angle of inclination (theta). The first contribution originates from dry periods between rain events (the first-flush effect) and the second from the rain events. The dry term has been refined in comparison to the original model by assuming a mass balance between measured corrosion mass loss, calculated copper retention in the patina and predicted copper runoff. The refined model predicts 76% of all reported runoff rates, worldwide, within 35% from their measured value. This includes sites with low SO(2) concentration, where the original model erroneously predicted higher runoff rates than corrosion rates. Based on environmental data from the EMEP programme for the years 1980-2000, the new model has been used to derive runoff rate maps for Europe with 50 x 50 km grid resolution. The runoff mapping shows a substantial reduction in runoff rate over the investigated time period, and with copper runoff rates now generally less than 2 g m(-2) yr(-1).     

Continuous flow methods for evaluating the response of a copper ion selective electrode to total and free copper in seawater

This work describes the development of an instrument for measuring free and total copper in seawater by continuous flow analysis (CFA) with an Orion copper (II) ion selective electrode (CuISE). Sample analysis times are reduced considerably by using an extrapolation technique based on the fitting of an empirical mathematical expression to the electrode time-response curve enabling a prediction of the final equilibrium potential. CuISE measurements in seawater samples containing nanomolar levels of total copper can be very time consuming, and this predictive approach significantly reduces sample analysis time, and improves sample throughput. The time taken to measure pCu in seawater to a precision of +/- 0.1, using conventional potentiometry, varies considerably depending on the condition of the electrode membrane but can be reduced by a factor of 3-6 (typically from 60 to 10 min) by using the extrapolation technique in conjunction with CFA. Details are given of the protocols used for preconditioning the CuISE. The system can be used as a portable instrument for field measurements or for shipboard measurements of free copper in seawater. Extrapolated equilibrium potentials are within +/- 0.5 mV of true steady state values.     

Filtration of fullerene and copper oxide nanoparticles using surface-modified microfilters

This study evaluated the filtration of engineered nanoparticles of fullerene and copper oxide (CuO) from water by using surface-modified microsized filters. The surfaces of microsized filters of cellulose acetate and glass fibers were coated with cationic and anionic surfactants to give them positively and negatively charged surfaces, respectively. Uncoated microfilters removed 30 % of a fullerene suspension, while no nanosized CuO suspension was removed. Cationic surfactant-coated filters enhanced the removal efficiency up to 70 % for the fullerene suspension, while the anionic surfactant-coated filters could not remove fullerene at all. The positively charged filters with cationic surfactant coating could easily adsorb negatively charged fullerenes on their surfaces. However, none of the surfactant-coated filters removed the CuO nanoparticles because the nanoparticles were not affected by the electrical charge of the filtration medium. The Hamaker constants of nanoparticles interacting with the filter materials in water were calculated to study these interactions. The Hamaker constant of fullerene interacting with cellulose acetate in water, 4.68E???21 J, was higher than that of interacting with quartz in water, 2.59E???21 J. However, the Hamaker constants of CuO interacting with quartz and cellulose acetate in water were both negative values, implying repulsive van der Waals interactions. The curves of potential energy of interaction between nanoparticles and the various filter media implied that the nanoparticles were very stable in water, and so, natural deposition of nanoparticles on the filters would not occur. Therefore, electrical bonding and hydrophobic interactions were the forces dominating fullerene removal by positively charged filters.     

Restoration of properties of cultivated soils polluted by copper and nickel

The long-term observations of the restoration of chemical and biological properties of cultivated podzol soil polluted by airborne emissions from a copper-nickel smelter located in the western Arctic of Russia were carried out. After 8 years, the total content of copper in soil decreased to a third (from 6230 to 2080 mg kg(-1)) and nickel to a sixth (from 3500 to 580 mg kg(-1)). Based on these observations, the removal time for heavy metals to reach permissible levels was calculated. The estimate was 100 years for copper and 108 years for nickel. Soil remained toxic to wheat seedlings, especially to their roots, for the whole observation period. A restoration of the number and activity of soil microorganisms was associated with the reduction in soil metal-toxicity. The number of non-sporeforming saprophytic bacteria was quickly restored concurrently with the removal of metals from the soil; fungal biomass also increased.     

Multi-component assessment of worker exposures in a copper refinery. Part 2. Biological exposure indices for copper, nickel and cobalt

Urinary copper (Cu), nickel (Ni) and cobalt (Co) concentrations were determined for 127 Cu refinery workers (40 females, 87 males), with values of the 95% upper confidence interval of the geometric mean in nmol per mmol creatinine of 89 (Ni), 42 (Cu) and 3.4 (Co) for electrorefinery workers. In the pyrometallurgical departments, the corresponding concentrations were 37 (Ni), 99 (Cu) and 11 (Co). Female workers had higher Co urinary concentrations than males (p< or = 0.05) while no gender difference was observed for Cu and Ni. Inter-elemental correlations were moderate to weak. Based on the inhalable aerosol levels reported previously for the same workers, the observed urinary Cu concentrations were considerably lower than expected, relative to Co and Ni. This is interpreted in terms of the current understanding of Cu homeostasis.     

Effects of soil copper and nickel on survival and growth of Scots pine

The contribution of soil Cu and Ni pollution to the poor vitality and growth rate of Scots pine growing in the vicinity of a Cu-Ni smelter was investigated in two manipulation experiments. In the first manipulation, Cu-Ni smelter-polluted soil cores were transported from a smelter-pollution gradient to unpolluted greenhouse conditions. A 4-year-old pine seedling was planted in each core and cultivated for a 17-month period. In the second manipulation, pine seedlings from the same lot were cultivated for the same 17-month period in a quartz sand medium containing increasing doses of copper sulfate, nickel sulfate, and a combination of both. The variation in the biomass growth of the seedlings grown in the smelter-polluted soil cores was very similar to that of mature pine stands growing along the same smelter-pollution gradient in the field. In addition, the rate of Cu and Ni exposure explained a high proportion of the biomass growth variation, and had an effect on the Ca, K, and Mg status of the seedlings. According to the lethal threshold values determined on the basis of the metal sulfate exposure experiments, both the Cu and Ni content of the 0.5 km smelter-polluted soil cores were high enough to cause the death of most of the seedlings. The presence of Cu seemed to increase Ni toxicity.     

Derivative spectrophotometric method for copper determination

A simple, sensitive and selective method by solvent extraction-first derivative spectrophotometry is described for the determination of microamounts of copper in water by means of its reaction and extraction at pH 8.0 with 3-(4-phenyl-2-pyridinyl-5-phenyl-1,2,4-triazine) (PPT) and picrate (2,4,6-trinitro-phenol) into 1,2-dichloroethane. Copper was thus determined in the range 7.5–350 ng/ml with a detection limits (3) of 2.3 ng/ml. The relative standard deviations were in all instances less than 2.0%. The proposed method was successfully applied for the determination of copper in several kinds of water.     

Predictive models of copper runoff from external structures

A general model for annual runoff rate predictions of total copper from naturally patinated copper on buildings at specific urban or rural sites of low chloride influence has been deduced from laboratory and field data. All parameters within the model have a physical meaning and include the average annual rain acidity (pH), the annual rain quantity and the geometry of a building in terms of surface inclination. In 70% of all reported annual runoff rates, the predicted values are within 30% from the observed values. The individual and interactive effect of rain composition in terms of pH, sulfate, chloride and nitrate concentration was investigated in immersion experiments in artificial rain water representative of urban and rural sites of Europe. The results show pH to have a dominating effect on patina dissolution, nitrate to have a small inhibiting effect, whereas no significant effect was seen for chloride and sulfate. In case pH data are not available, a model has been statistically deduced from field data by considering SO2 as influencing parameter, rather than pH. The predictability with the SO2 model is not as good as with the pH model i.e. the pH model should preferentially be used since it is a better predictor and all parameters within the model can be physically explained.     

Prolonged toxicity characteristic leaching procedure for nickel and copper aluminates

The toxicity characteristic leaching procedure (TCLP) is a regulatory testing method widely employed to evaluate the environmental friendliness of waste materials. TCLP analysis provides a fast, easy and economical way to determine the mobility of waste pollutants under simulated landfill conditions. Recent studies on metal stabilization have reported the potential for nickel and copper aluminates to form in thermal treatment conditions, and suggested a more reliable method of stabilizing hazardous metals, particularly when products are to be reused. There is thus an urgent need for a convenient and effective method of quantifying metal leachability and identifying the metal leaching behavior of sparingly soluble materials. In this study, standard TCLP analysis was modified into a prolonged leaching experiment to investigate the leaching behavior of nickel and copper oxides (NiO and CuO) and their aluminates (NiAl(2)O(4), CuAl(2)O(4) and CuAlO(2)). The results demonstrate the difficulty of differentiating the leachability of highly insoluble phases, such as NiO and NiAl(2)O(4), using the standard TCLP. The prolonged TCLP method, however, confirmed NiAl(2)O(4) to have a lower degree of intrinsic leachability than NiO and that it could be expected to undergo congruent dissolution under landfill conditions. For the more soluble copper system, the aluminates were still found to possess a much lower degree of leachability, and their leaching behavior to follow an incongruent dissolution pattern. The results of this study prove prolonged TCLP analysis to be a convenient and effective way to evaluate the environmental friendliness of metal waste and to identify the leaching behavior of waste materials.     

Dye removal using modified copper ferrite nanoparticle and RSM analysis

In this paper, copper ferrite nanoparticle (CFN) was synthesized, modified by cetyl trimethylammonium bromide, and characterized. Dye removal ability of the surface modified copper ferrite nanoparticle (SMCFN) from single system was investigated. The physical characteristics of SMCFN were studied using Fourier transform infrared, scanning electron microscopy, and X-ray diffraction. Acid Blue 92, Direct Green 6, Direct Red 23, and Direct Red 80 were used as model compounds. The effect of operational parameters (surfactant concentration, adsorbent dosage, dye concentration, and pH) on dye removal was evaluated. Response surface methodology (RSM) was used for the analysis of the dye removal data. The experimental checking in these optimal conditions confirms good agreements with RSM results. The results showed that the SMCFN being a magnetic adsorbent might be a suitable alternative to remove dyes from colored aqueous solutions.     

Effects of roof and rainwater characteristics on copper concentrations in roof runoff

Copper sheeting is a common roofing material used in many parts of the world. However, copper dissolved from roof sheeting represents a source of copper ions to watersheds. Researchers have studied and recently developed a simple and efficient model to predict copper runoff rates. Important input parameters include precipitation amount, rain pH, and roof angle. We hypothesized that the length of a roof also positively correlates with copper concentration (thus, runoff rates) on the basis that runoff concentrations should positively correlate with contact time between acidic rain and the copper sheet. In this study, a novel system was designed to test and model the effects of roof length (length of roof from crown to the drip edge) on runoff copper concentrations relative to rain pH and roof angle. The system consisted of a flat-bottom copper trough mounted on an apparatus that allowed run length and slope to be varied. Water of known chemistry was trickled down the trough at a constant rate and sampled at the bottom. Consistent with other studies, as pH of the synthetic rainwater decreased, runoff copper concentrations increased. At all pH values tested, these results indicated that run length was more important in explaining variability in copper concentrations than was the roof slope. The regression equation with log-transformed data (R ² = 0.873) accounted for slightly more variability than the equation with untransformed data (R ² = 0.834). In log-transformed data, roof angle was not significant in predicting copper concentrations.     

Bioaccumulation and glutathione-mediated detoxification of copper and cadmium in Sphagnum squarrosum Crome Samml.

Physiological and biochemical responses, metal bioaccumulation and tolerance potential of Sphagnum squarrosum Crome Samml. to Cu and Cd were studied to determine its bioindication and bioremediation potential. Results suggest that glutathione treatment increases the metal accumulation potential and plays a definite role in heavy metal scavenging. High abundance of Sphagnum in metal-rich sites strongly suggests its high metal tolerance capabilities. This experiment demonstrates that S. squarrosum is able to accumulate and tolerate a high amount of metals and feasibility of its application as bioindicator and remediator test species of metal-contaminated environment.     

The interaction between concrete pavement and corrosion-induced copper runoff from buildings

Changes in chemical speciation of copper and the capacity of concrete pavement to retain copper in runoff water from external buildings have been investigated at urban field conditions, and in parallel laboratory experiments simulating outdoor scenarios. The research study showed the concrete surface to form a copper rich surface layer (≈50 μm thick) upon exposure, and a high capacity to significantly reduce the bioavailable fraction of released copper (20–95%). The retention capacity of copper varied between 5 and 20% during single runoff events in the laboratory, and between 10 and 40% of the total copper release during single natural runoff events. The capacity to retain and reduce the bioavailable fraction of non-retained copper increased with increasing wetness of the concrete surfaces, increasing pH of the runoff water and decreasing flow rates. Bioassay testing with bacterial and yeast bioreporters showed the bioavailable fraction of non-retained copper to be significantly lower than the total copper concentration in the runoff water, between 22 and 40% for bacteria and between 8 and 31% for yeast. The application of generated data to simulate a fictive outdoor scenario, suggests a significant reduction of bioavailable and total copper to background values during environmental entry as a result of dilution, and the interaction with solid surfaces, organic matter and complexing agents already in the drainage system.     

Interlaboratory comparability of copper complexation capacity determination in natural waters

The results of a test of interlaboratory comparability for the determination of copper complexation capacity and copper-ligand complex formation constant are presented. Eight water samples comprising, six natural waters, a synthetic ligand solution and a blank solution were analysed by seven laboratories using their own methods of complexation titration. Given the wide variation that might have been possible, relatively good comparability was demonstrated amongst the variety of methods for determining copper complexation capacity. The complexation capacity data largely satisfied the predefined criterion of agreement to within 50%. This provides support for the use of metal speciation criteria in the regulation of copper in the environment. Data for the determination of complex formation constants were of poorer comparability, ranging between 10(7) and 10(12) for the same water.     

Physicochemical factors affecting the sensitivity of Ceriodaphnia dubia to copper

The effects of physicochemical conditions, such as pH, water hardness, flow rates and natural organic substances on the sensitivity of Ceriodaphnia dubia to the toxic effects of copper were investigated using static bioassay cups and specially designed flow-through bioassay chambers. We found that C.dubia was very sensitive to pH changes and the total copper LC50 values of C. dubia neonates increased by 15-fold as the pH increased from pH 7 to 10. It was also observed that the LC50 values increased sharply upon increasing the water hardness value to 2.4 meq. In addition, increasing flow rates from zeroto 50 mL hr^-1 also increased its sensitivity to copper, which was possibly due to hydrodynamic stress.The presence of natural organic substances (humic acid and dissolved organic matter) and suspended particles decreased thetoxic effect of copper. This significant decrease in the toxicity of copper in the presence of natural organic materialscan be explained by a reduction in the free ion concentration due to complexation. Furthermore, we observed that the kinetics of copper interactions with natural organic materials are a significant factor in the toxic effect of copper and that the acute LC50 values increased with increasing reaction time betweensolubilized copper and water-borne organics.     

Ultra-sensitive quantification of copper in food and water samples by electrochemical adsorptive stripping voltammetry

A new electrochemical adsorptive stripping voltammetry method was developed for the determination of trace amounts of copper in food and water samples. The study of electrochemical behavior of Cu ion indicated that Cu(II) and Schiff base formed a complex in H₃BO₄–NaOH buffer solution (pH?=?7.25). An accumulation potential of ?100 mV (vs Ag/AgCl) was applied while the solution was stirred for 60 s. The response curve was recorded by scanning the potential, and the peak current of ?0.31 V (vs Ag/AgCl) was recorded. The peak current and concentration of copper accorded with linear relationship in the range of 0.04–120 ng mL^?1. The relative standard deviation (for 12 ng mL^?1 of copper) was 1.73 %, and the detection limit was 0.007 ng mL^?1. The possible interference of some common ions was studied. The proposed method was applied to the determination of copper in water, rice, wheat, tea, milk, and tomato with satisfactory results.     

Determination of lead, cadmium and copper in roadside soil and plants in Elazig, Turkey

The concentrations of lead, cadmium and copper in roadside soil and plants in Elazig, Turkey were investigated. Soil samples were collected at distances of 0, 25 and 50 m from the roadside. The concentrations of lead, cadmium and copper were measured by Flame Atomic Absorption Spectrophotometry (FAAS). A slotted tube atom trap (STAT) was used to increase the sensitivity of lead and cadmium in FAAS. Lead concentrations in soil samples varied from 1.3 to 45 mg kg⁻¹ while mean lead levels in plants ranged from120 ng g⁻¹ for grape in point-4 to 866 ng g⁻¹ for apple leaves in point-2. Lead analyses showed that there was a considerable contamination in both soil and plants affected from traffic intensity. Overall level of Cd in soil samples lies between 78 and 527 ng/g while cadmium concentration in different vegetations varied in the range of 0.8–98.0 ng g⁻¹. Concentrations of copper in soil and plant samples were found in the range of 11.1–27.9 mg kg⁻¹ for soil and 0.8–5.6 mg kg⁻¹ for plants. Standard reference material (SRM) was used to find the accuracy of the results of soil analyses.