Enhanced-electrokinetic remediation of copper–pyrene co-contaminated soil with different oxidants and pH control

Electrokinetic (EK) remediation has potential to simultaneously remove heavy metals and organic compounds from soil, but the removal percent of these pollutants is very low in general if no enhancing treatment is applied. This study developed a new enhanced-EK remediation technology to decontaminate a heavy metal–organic compound co-contaminated soil by applying different oxidants and pH control. A red soil was used as a model clayed soil, and was spiked with pyrene and Cu at about 500 mg kg^?1 for both to simulate real situation. Bench-scale EK experiments were performed using four oxidants (H₂O₂, NaClO, KMnO₄, and Na₂S₂O₈) and controlling electrolyte pH at 3.5 or 10. After the treatments with 1.0 V cm^?1 of voltage gradient for 335 h, soil pH, electrical conductivity, and the concentrations and chemical fractionations of soil pyrene and Cu were analyzed. The results showed that there was significant migration of pyrene and Cu from the soil, and the removal percent of soil pyrene and Cu varied in the range of 30–52% and 8–94%, respectively. Low pH favoured the migration of soil Cu, while KMnO₄ was the best one for the degradation of pyrene among the tested oxidants, although it unfortunately prevented the migration of soil Cu by forming Cu oxide. Application of Na₂S₂O₈ and to control the catholyte pH at 3.5 were found to be the best operation conditions for decontaminating the Cu-pyrene co-contaminated soil.     

Superior photodecomposition of pyrene by metal ion-loaded TiO₂ catalyst under UV light irradiation

BACKGROUND: The photocatalytic degradation of pyrene under UV (125 W Hg-Arc, 10.4 mW/cm2) irradiation of TiO2 aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu2+, Fe3+, Ag+, and Au3+, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1 eV) of TiO2, the photoexcited electron transfer occurs more readily and reduces electron–hole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO2 because of rapid Fermi energy equilibrium between the CB of TiO2 and its surface adsorbed metal ions. RESULTS AND DISCUSSION: The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni2+ having more negative reduction potential (?0.25 eV) than the CB of TiO2 imparts negligible co-catalytic activity to TiO2 photoreaction. It also revealed that loading of Au3+ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe+3 and Au3+ ions gradually increases from 0.1 to 2 wt.%, the pyrene photodecomposition rate also become faster.     

An oxygenated metabolite of benzo[a]pyrene increases hepatic β-oxidation of fatty acids in chick embryos

Polycyclic aromatic hydrocarbons (PAHs) are well-known carcinogens to humans and ecotoxicological effects have been shown in several studies. However, PAHs can also be oxidized into more water soluble-oxygenated metabolites (Oxy-PAHs). The first purpose of the present project was to (1) assess the effects of a mixture containing three parent PAHs: anthracene, benz[a]anthracene, and benzo[a]pyrene versus a mixture of their oxygenated metabolites, namely: anthracene-9,10-dione, benz[a]anthracene-7,12-dione, and 9,10-dihydrobenzo[a]pyrene-7-(8H)-one on the hepatic fatty acid β-oxidation in chicken embryos (Gallus gallus domesticus) exposed in ovo. The second and also main purpose of the project was to (2) assess the effects of the parent PAHs versus their oxy-PAHs analogues when injected individually, followed by (3) additional testing of the individual oxy-PAHs. The hepatic β-oxidation was measured using a tritium release assay with [9,10-³H]-palmitic acid (16:0) as substrate. The result from the first part (1) showed reduced hepatic β-oxidation after exposure in ovo to a mixture of three PAHs, however, increased after exposure to the mixture of three oxy-PAHs compared to control. The result from the second part (2) and also the follow-up experiment (3) showed that 9,10-dihydrobenzo[a]pyrene-7-(8H)-one was the causative oxy-PAH. The implication of this finding on the risk assessment of PAH metabolite exposure in avian wildlife remains to be determined. To the best of our knowledge, no similar studies have been reported.     

Integrated bioleaching of copper metal from waste printed circuit board—a comprehensive review of approaches and challenges

Waste electrical and electronic equipment (e-waste) is the most rapidly growing waste stream in the world, and the majority of the residues are openly disposed of in developing countries. Waste printed circuit boards (WPCBs) make up the major portion of e-waste, and their informal recycling can cause environmental pollution and health risks. Furthermore, the conventional disposal and recycling techniques—mechanical treatments used to recover valuable metals, including copper—are not sustainable in the long term. Chemical leaching is rapid and efficient but causes secondary pollution. Bioleaching is a promising approach, eco-friendly and economically feasible, but it is slower process. This review considers the recycling potential of microbes and suggests an integrated bioleaching approach for Cu extraction and recovery from WPCBs. The proposed recycling system should be more effective, efficient and both technically and economically feasible.     

Response of microcystis to copper stress: do phenotypes of microcystis make a difference in stress tolerance?

To elucidate the role of phenotype in stress-tolerant bloom-forming cyanobacterium Microcystis, two phenotypes of M. aeruginosa - unicellular and colonial strains were selected to investigate how they responded to copper stress. Flow cytometry (FCM) examination indicated that the percents of viable cells in unicellular and colonial Microcystis were 1.92-2.83% and 72.3-97.51%, respectively, under 0.25 mgl(-1) copper sulfate treatment for 24h. Upon exposure to 0.25 mgl(-1) copper sulfate, the activities of antioxidative enzyme, such as superoxide dismutase (SOD) and catalase (CAT), were significantly increased in colonial Microcystis compared to unicellular Microcystis. Meanwhile, the values of the photosynthetic parameters (F(v)/F(m), ETR(max), and oxygen evolution rate) decreased more rapidly in unicellular Microcystis than in colonial Microcystis. The results indicate that colonial Microcystis has a higher endurance to copper than unicellular Microcystis. This suggests that the efficient treatment concentration of copper sulfate as algaecides will be dependent on the phenotypes of Microcystis.     

Do DOM optical parameters improve the prediction of copper availability in vineyard soils?

Environmental Science and Pollution Research - Accumulation of copper (Cu) in soils due to the application of fungicides may be toxic for organisms and hence affect winegrowing sustainability. Soil...     

The effects of 3,3′,4,4′-tetrabromobiphenyl on rats fed diets containing a constant level of copper and varying levels of molybdenum

Copper (Cu) metabolism is altered in rats fed diets high in molybdenum (Mo) and low in Cu. This 10-week study was carried out to examine the effects of supplemental Mo (7.5–240 μg/g diet) on male Sprague–Dawley rats fed diets adequate in Cu (5 μg/g diet) and to determine the susceptibility of Mo-treated animals to the environmental pollutant 3,3′,4,4′-tetrabromobiphenyl (TBB). After 7 weeks of dietary treatment, half of the rats in each group received a single IP injection of TBB (150 μM/kg bw), while the other half received the corn oil vehicle. Rats sacrificed at 10 weeks showed no effects of Mo on growth, feed efficiency, or selected organ or tissue weights. Dose-dependent effects on plasma Mo (0–5.1 μg/mL), plasma Cu (0.95–0.20 μg/mL), and bone Cu (3.4–10 μg/g) in control through the high dose were found. Cu sequestration in the bone of Mo-treated rats is a new finding. TBB treatment resulted in dramatic weight loss and loss of absolute organ mass. Relative organ weights were increased, except for the thymus. TBB altered the concentrations of certain amino acids. Compared to control rats, this polybrominated biphenyl congener significantly decreased plasma Cu and ceruloplasmin at higher concentrations of dietary Mo and promoted the process of plasma Cu decrease by Mo, suggesting a combined effect.     

Effects of a copper smelter on a grassland community in the Puchuncaví Valley, Chile

A grassland formation has been subjected to pollution generated by the Ventanas copper smelter since 1964 (Puchuncaví Valley, central zone of Chile) with extensive damage to local vegetation and important changes in soil characteristics. The aims of the study were (1) to detect soil parameters that best explain changes observed in plant species richness and abundance and (2) to determine if pollution-derived stresses have also affected regeneration capabilities of plant communities from the soil seed bank. The grassland was quantitatively analysed in terms of physicochemical soil characteristics, plant species diversity and abundance, and soil seed bank species composition and abundance. Results showed that a decrease in total soil nitrogen explained 13% of the changes detected in plant abundance while soil pH and 0.05 M EDTA extractable copper explained 10% and 7%, respectively, of the vegetation change. It was also found that the pollution has already affected plant species regeneration capabilities from the soil seed bank and the microsite distribution of the seeds in soils.     

Green sol–gel synthesis of novel nanoporous copper aluminosilicate for the eradication of pathogenic microbes in drinking water and wastewater treatment

Environmental Science and Pollution Research - We used a green sol–gel synthesis method to fabricate a novel nanoporous copper aluminosilicate (CAS) material. Nanoporous CAS was characterized...     

Removal of copper from water by electrocoagulation process—effect of alternating current (AC) and direct current (DC)

Purpose and aim

In general, direct current (DC) is used in an electrocoagulation processes. In this case, an impermeable oxide layer may form on the cathode as well as corrosion formation on the anode due to oxidation. This prevents the effective current transfer between the anode and cathode, so the efficiency of electrocoagulation processes declines. These disadvantages of DC have been diminished by adopting alternating current (AC) in electrocoagulation processes. The main objective of this study is to investigate the effects of AC and DC on the removal of copper from water using magnesium alloy as anode and cathode.

Materials and methods

Magnesium alloy of size 2.0 dm² was used as anode and as cathode. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and effect of current density were studied. Copper adsorbed magnesium hydroxide coagulant was characterized by SEM, EDAX, XRD, and FTIR.

Results

The results showed that the optimum removal efficiency of copper is 97.8 and 97.2 % with an energy consumption of 0.634 and 0.996 kWh/m³ at a current density of 0.025 A/dm², pH of 7.0 for AC and DC, respectively. The adsorption of copper is preferably fitting the Langmuir adsorption isotherm for both AC and DC respectively. The adsorption process follows the second-order kinetics model with good correlation. Temperature studies showed that adsorption was endothermic and spontaneous in nature.

Conclusions

The magnesium hydroxide generated in the cell removes the copper present in the water, reducing the copper concentration to less than 1 mg/L, making it safe for drinking. The results of the scale-up study show that the process was technologically feasible.     

Metal contamination in the lichen Alectoria sarmentosa near the copper smelter of Murdochville, Québec

Lichens were used to evaluate the metal pollution in a forest ecosystem around the smelter of Murdochville, Canada. As reached values 5.8 times higher in the smelter vicinity than in the 'background' sites. This enrichment was 2 times higher for 3 metals (Cu, Cd and Pb). The highest As, Ba, Cd, Cu, and Pb concentrations in lichens were 4, 112, 1, 23, 50 and 952mg/kg respectively. Contamination declined exponentially with increasing distance from the smelter and was related to elevation and slope exposition to the smelter flux. (206)Pb/(207)Pb and (206)Pb/(204)Pb ratios were low close to the smelter (1.16 and 18), but increased with distance to constant values (1.19 and 18.7) and showed an inverse correlation with lead concentrations. Forest contamination was detectable up to 30km from the smelter.     

Aerial application of copper for dothistroma control in New Zealand’s planted forests—effect on stream environments

Environmental Science and Pollution Research - Limited information is available on the risk to aquatic environments from the aerial application of copper fungicides to treat dothistroma needle...     

Use of benzo[a]pyrene relative abundance ratios to assess exposure to polycyclic aromatic hydrocarbons in the ambient atmosphere in the vicinity of a Söderberg aluminum smelter

The purpose of this study was to investigate the use of benzo[a]pyrene (B[a]P) relative abundance ratios (RARs) to assess exposure to polycyclic aromatic hydrocarbons (PAHs) in the urban atmospheric air in the vicinity of a horizontal stud S?derberg aluminum reduction facility. The B[a]P RARs refer to the concentration of individual PAHs measured in a given sample divided by the concentration of B[a]P found in the same sample. This study compared the B[a]P RARs calculated for the facility stack and three sites near the S?derberg aluminum smelter for three different sampling periods. Interperiod differences were significant for many of the PAHs, and the differences between the stations proved insignificant at p < 0.05. The differences between each individual station and the facility stack were significant for all PAHs. B[a]P RARs increased in value at the stations compared with the stack, indicating that B[a]P may be degraded or removed from the atmosphere at a rate greater than that of the majority of the measured PAHs. It is concluded that B[a]P and B[a]P RARs may be poor markers of exposure to PAHs in the vicinity of this S?derberg aluminum refinery for the entire mixture of PAHs present in the ambient atmosphere.     

Benzo[b]fluoranthene,a Potential Alternative to Benzo[a]pyrene as an Indicator of Exposure to Airborne PAHs in the Vicinity of Söderberg Aluminum Smelters

ABSTRACT

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two Söderberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Benzo[b]fluoranthene, a potential alternative to benzo[a]pyrene as an indicator of exposure to airborne PAHs in the vicinity of Söderberg aluminum smelters

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two S?derberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Do trace metals (chromium, copper, and nickel) influence toxicity of diesel fuel for free-living marine nematodes?

The objective of this study was to test the hypotheses that (1) free-living marine nematodes respond in a differential way to diesel fuel if it is combined with three trace metals (chromium, copper, and nickel) used as smoke suppressants and that (2) the magnitude of toxicity of diesel fuel differs according to the level of trace metal mixture added. Nematodes from Sidi Salem beach (Tunisia) were subjected separately for 30 days to three doses of diesel fuel and three others of a trace metals mixture. Simultaneously, low-dose diesel was combined with three amounts of a trace metal mixture. Results from univariate and multivariate methods of data evaluation generally support our initial hypothesis that nematode assemblages exhibit various characteristic changes when exposed to different types of disturbances; the low dose of diesel fuel, discernibly non-toxic alone, became toxic when trace metals were added. For all types of treatments, biological disturbance caused severe specific changes in assemblage structure. For diesel fuel-treated microcosms, Marylynnia bellula and Chromaspirinia pontica were the best positive indicative species; their remarkable presence in given ecosystem may predict unsafe seafood. The powerful toxicity of the combination between diesel fuel and trace metals was expressed with only negative bioindicators, namely Trichotheristus mirabilis, Pomponema multipapillatum, Ditlevsenella murmanica, Desmodora longiseta, and Bathylaimus capacosus. Assemblages with high abundances of these species should be an index of healthy seafood. When nematodes were exposed to only trace metals, their response looks special with a distinction of a different list of indicative species; the high presence of seven species (T. mirabilis, P. multipapillatum, Leptonemella aphanothecae, D. murmanica, Viscosia cobbi, Gammanema conicauda, and Viscosia glabra) could indicate a good quality of seafood and that of another species (Oncholaimellus mediterraneus) appeared an index of the opposite situation.     

Sediment quality guidelines for copper and zinc for filter-feeding estuarine oysters?

Sediment quality guidelines (SQGs) assess the ability of bottom sediment to sustain healthy infauna and water quality guidelines (WQGs) provide protection for a designated percentage of aquatic species. Filter-feeding marine species, e.g. oysters and mussels, acquire food from particles in the water column and protection of these animals is not provided by SQGs or WQGs. The current work investigated the relationship between metal (Cu, Zn) concentrations in total and fine-fraction (<62.5 μm) surficial sediment digested in a range of acids and chelating agents and oyster tissue metal concentrations. A strong correlation between oyster tissue Cu and Zn concentrations and fine-fraction surficial sediment digested in 1 M HCl provided a sedimentary guideline which predicted tissue metal concentrations in oysters and established a level (<45 μg g⁻¹ and <1000 μg g⁻¹, respectively) for protecting oysters from exceeding human consumption levels (70 μg g⁻¹ and 1000 μg g⁻¹, respectively).     

Emissions from the copper–nickel industry on the Kola Peninsula and at Noril'sk,Russia

Published estimates for base metal emissions from the copper–nickel industry on the Kola Peninsula are re-examined in the light of (a) chemical data on the composition of the ores; (b) official emission figures for 1994; and (c) modelled emissions based on dry and wet deposition estimates derived from data for snow and rain samples collected in 1994. The modelled emissions, official emission figures and chemical data are mutually compatible for Ni, Cu and Co and show that previously published figures underestimated the emissions of the major elements, Ni and Cu (though within the same order of magnitude) and overestimated the emissions of As, Pb, Sb and Zn by up to several orders of magnitude, in some cases exceeding the calculated total input to the plants. Published estimates have neglected information on the nature and chemistry of the ores processed in metallurgical industries in the Noril'sk area of Siberia and the Urals. Revised emission estimates for 1994, using knowledge of the chemistry of the ores, are proposed: taken with published information on total emissions up to 2000 these data give an indication of emission levels in more recent years.     

Gene expression of heat shock protein 70, interleukin-1β and tumor necrosis factor α as tools to identify immunotoxic effects on Xenopus laevis: a dose-response study with benzo[a]pyrene and its degradation products

The exposure to benzo[a]pyrene (B[a]P) results in an alteration of immune function in mammals and fish, and the analysis of cytokine mRNA levels has been suggested for predicting the immunomodulatory potential of chemicals. To obtain evidence of the innate immune responses to B[a]P in Xenopus laevis, the present study monitored the mRNA expression of interleukin 1-β (IL-1β), tumor necrosis factor α (TNF-α) and heat shock protein 70 (HSP70) in a laboratorial exposure. Tadpoles exposed to 8.36, 14.64, 89.06 and 309.47 μg/L of B[a]P,were used for detecting hsp70, IL-1β and TNF-α mRNA induction. A dose-response increase in the expression of hsp70 and IL-1β mRNA was found. The results of this study confirmed the use of hsp70 and IL-1β, but not TNF-α, as sensitive indicators of immunotoxic effect of B[a]P in X. laevis. Further research would be required for the validation of these endpoints.     

Analysis of a population of magnetotactic bacteria of the Gulf of Gabès,Tunisia

The occurrence of magnetotactic bacteria (MTB) on a Tunisian marine coast exposed to heavy metals pollution (Sfax, Gulf of Gabès, Mediterranean Sea) was investigated. The MTB population of this Southern Mediterranean coast was compared to the MTB populations previously investigated on the French Northern Mediterranean coast. A dominant MTB coccus morphotype was observed by microscopy analysis. By pyrosequencing technology, the analysis of the 16S ribosomal RNA (rDNA) revealed as much as 33 operational taxonomic sequence units (OTUs) close to sequences of MTB accessible in the databases. The majority were close to MTB sequences of the “Med group” of α-Proteobacteria. Among them, a dominant OTU_001 (99 % of the MTB sequences) affiliated within the Magnetococcales order was highlighted. Investigating the capacities of this novel bacterium to be used in bioremediation and/or depollution processes could be envisaged.