Determining the experimental leachability of copper, lead, and zinc in a harbor sediment and modeling

The potential leaching of pollutants present in harbor sediments has to be evaluated in order to choose the best practices for managing them. Little is known about the speciation and mobility of heavy metals in these specific solid materials. The objective of this paper is to determine and model the leachability of copper, lead, and zinc present in harbor sediments in order to obtain essential new data. The mobility of inorganic contaminants in a polluted harbor sediment collected in France was investigated as a function of physicochemical conditions. The investigation relied mainly on the use of leaching tests performed in combination with mineralogical analysis and thermodynamic modeling using PHREEQC. The modeling phase was dedicated to both confirm the hypothesis formulated to explain the experimental results and improve the determination of the main physico-chemical parameters governing mobility. The experimental results and modeling showed that the release of copper, lead, and zinc is very low with deionized water which is due to the stability of the associated solid phases (organic matter, carbonate minerals, and/or iron sulfides) at natural slightly basic conditions. However, increased mobilization is observed under pH values below 6.0 and above 10.0. This methodology helped to consistently obtain the geochemical parameters governing the mobility of the contaminants studied.     

Distribution of copper, lead, cadmium and zinc concentrations in soils around Kabwe town in Zambia

The extent of pollution of the environment as a result of mining activities in Kabwe, the provincial capital of Central province in Zambia has not yet been evaluated. Mining of lead and zinc were the core activities of Kabwe mine while cadmium and silver were produced as by-products. The smelting processes produced a significant amount of copper. The spatial distribution of four heavy metals in soils in the northern, eastern, southern and western directions of the mine was analyzed using atomic absorption spectrometry (AAS). Samples were collected up to 20 km in each direction from the mine. Results were consistent with the wind flow patterns in the town. Results ranged between 0.08 and 28 mg kg(-1) (Cd); 0.20 and 0.61 mg kg(-1) (Cu); 0.10 and 758 mg kg(-1) (Pb) and 0.40 and 234 mg kg(-1) (Zn) suggesting high precipitation of metals from the core mining activities. These concentrations were for only the fractions of metals extractable by 0.5M nitric acid and that could be available for plant uptake in the environment. The distribution of metals indicated a decrease of metal concentrations with distance from the mine, which confirmed that precipitation due to mining activities was the main cause of soil contamination.     

Chemical fractionation of copper, lead and zinc in ombrotrophic peat

Measurement of operationally defined chemical fractions in ombrotrophic peat samples provides information not obtained by total metal extractions. Examination of such sequential data permits interpretation of process dynamics. Results for copper, lead and zinc chemical fractionation of peat profiles from Ringinglow Bog, near Sheffield, Great Britain, are reported and discussed. Lead and zinc share similar patterns of partitioning. A considerable proportion of these records is in a form predisposed to transformation and mobilisation. In contrast, much of the copper is comparatively immobile, it being associated with the more chemically intractable fractions. The results suggest that peat copper deposition records may be used for reconstruction of pollution history. The use of lead and zinc records for these purposes is problematic.     

Levels of lead, cadmium and other elements in mink and otter from Ontario, Canada

Concentrations of Pb, Cd, Cu, Ni, Fe, Zn, Mn, Ca, P, Mg and S were measured in tissues of mink (Mustela vision) and river otter (Lutra canadensis) from five areas of Ontario, Canada. Bone Pb levels in both species were lowest in animals from the collection site most remote from industrial activity and atmospheric deposition of pollutants. Mean liver and kidney Cd levels were also different between collection sites and may reflect natural and/or anthropogenic sources. Copper levels in liver, but not kidney, were elevated in mink and otter from the heavily Cu-contaminated Sudbury region. However, tissue levels did not reflect environmental loading of other metals, such as Fe, Ni and Zn, in the Sudbury area. This may be a function of effective homeostatic regulation in mammals, or low potential for biomagnification of these elements.     

Mechanisms of lead, copper, and zinc retention by phosphate rock

The solid-liquid interface reaction between phosphate rock (PR) and metals (Pb, Cu, and Zn) was studied. Phosphate rock has the highest affinity for Pb, followed by Cu and Zn, with sorption capacities of 138, 114, and 83.2 mmol/kg PR, respectively. In the Pb-Cu-Zn ternary system, competitive metal sorption occurred with sorption capacity reduction of 15.2%, 48.3%, and 75.6% for Pb, Cu, and Zn, respectively compared to the mono-metal systems. A fractional factorial design showed the interfering effect in the order of Pb>Cu>Zn. Desorption of Cu and Zn was sensitive to pH change, increasing with pH decline, whereas Pb desorption was decreased with a strongly acidic TCLP extracting solution (pH = 2.93). The greatest stability of Pb retention by PR can be attributed to the formation of insoluble fluoropyromorphite [Pb(10)(PO(4))(6)F(2)], which was primarily responsible for Pb immobilization (up to 78.3%), with less contribution from the surface adsorption or complexation (21.7%), compared to 74.5% for Cu and 95.7% for Zn. Solution pH reduction during metal retention and flow calorimetry analysis both supported the hypothesis of retention of Pb, Cu, and Zn by surface adsorption or complexation. Flow calorimetry indicated that Pb and Cu adsorption onto PR was exothermic, while Zn sorption was endothermic. Our research demonstrated that PR can effectively remove Pb from solutions, even in the presence of other heavy metals (e.g. Cu, Zn).     

Solubility of lead, zinc and copper added to mineral soils

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.     

Sorption of copper, zinc and lead on soil mineral phases

Soil mineral phases play a significant role in controlling heavy metal mobility in soils. The effective study of their relation needs the integrated use of several analytical methods. In this study, analytical electron microscopy analyses were combined with sequential chemical extractions on soils spiked with Cu, Zn and Pb. Our aims were to study the metal sorption capacity of soil mineral phases and the effect of presence of iron oxide and carbonate on this property of soil minerals. Copper and Pb were found to be characterized by higher and stronger sorption on the studied samples than Zn. Only the former two metals showed significant differences in their immobilized metal amounts on the studied samples and soil mineral particles. Highest metal amounts were sorbed on the swelling clay mineral particles (smectites and vermiculites), but iron-oxide phases may also have similar lead sorption capacity. Alkaline conditions due to the carbonate content of soils resulted both in increased sorption on the mineral particles for Cu and in enhanced role of precipitation for all the studied metals. On the other hand, the intimate association of phyllosilicates and iron resulted in significant increase in metal sorption capacity of the given particle. The results of sequential extractions could be successfully completed by the analytical electron microscopy analyses for studying the sorption capacity of discrete mineral particles. Their integrated use helps us in better understanding the heavy metal-mineral interactions in soils.     

Reactions of compost-derived humic substances with lead, copper, cadmium, and zinc

Thermodynamic stability constants of the formation of complexes from the reactions of humic substances with various metals are usually used as parameters to judge the reactivities of both humic substances and metals. However, in calculating the thermodynamic stability constants, complicated processes for the acquisition of activities of components in reactions are absolutely inevitable. In this study, we investigated the average conditional concentration quotients of the complexes formed from the reaction of metals with humic substances and the relations of these quotients to thermodynamic stability constants. The characterized humic substances including HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) extracted from a swine compost were prepared to react with Pb, Cu, Cd, and Zn at 25 degrees C and at pH 4.00 and 6.50. Reactions of HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) with the four metals were carried out at 1:0.1, 1:0.5, 1:1, 1:5, and 1:10 ligand:metal stoichiometry. The concentrations of the free ions of Pb, Cu, Cd, and Zn in the reaction systems of metal-HA suspensions and metal-FA solutions were measured by anodic stripping voltammetry (ASV). The sequence of the average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals was FA(MW<1,000)>FA(MW>1,000)>HA(MW>1,000), showing the relative reactivities of the fractions of swine compost-derived humic substances. The sequence of reacting metals with humic substances was Pb>Cu>Cd>Zn, which is in good agreement with the sequence reported by judging the thermodynamic stability constants. The average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals were thus useful parameters that can be directly related to thermodynamic stability constants and other parameters.     

Computational spectroscopic study of copper, cadmium, lead and zinc interactions in the environment

Molecular modelling has been used to investigate the interactions of various heavy metals, in order to understand and possibly to control the nature and behaviour of metals, especially in the aquatic environment. The interactions of copper, cadmium, lead and zinc with organic acids were studied using density functional theory (DFT) calculations. Carboxylic acid was used as a model molecule. The structure of each metal carboxylate was optimized and the vibrational spectrum calculated. The results indicate that there is a shift in the calculated v_S(C=O) of metal carboxylates compared with that of carboxylic acid. It was also found that hexaaqua structures of both cadmium and zinc are stable whereas those of copper and lead are not. Furthermore, dipole moment calculations indicate that cadmium carboxylate dihydrate is more representative of cadmium interactions in the aquatic environment. Moreover, hexaaquo cadmium could further interact with surrounding molecules in the aquatic environment.     

Earthworms as biological monitors of cadmium, copper, lead and zinc in metalliferous soils

Earthworms (Lumbricus rebellus and Dendrodrilus rubidus) were sampled from one uncontaminated and fifteen metal-contaminated sites. Significant positive correlations were found between the earthworm and 'total' (conc. nitric acid-extractable) soil Cd, Cu, Pb and Zn concentrations (data log1) transformed). The relationships were linear, and the accumulation patterns for both species were similar when a single metal was considered, even though there were species difference in mean metal concentrations. Generally, the earthworm Cd concentration exceeded that of the soil; by contrast, the worm Pb concentration was lower than the soil Pb concentration in all but one (acidic, low soil Ca) site. Our observations suggest that Cu and Zn accumulation may be physiologically regulated by both species. Total-soil Cd explained 82-86% of the variability (V2) in earthworm Cd concentration; 52-58% of worm Pb and worm Zn concentrations were explained by the total-soil concentrations of the respective metals. Total-soil Cu explained only 11-32% of the worm Cu concentration. The effect of soil pH, total Ca concentration, cation-exchange capacity (CEC) and organic carbon on metal accumulation by L. rubellus and D. rubidus was investigated by multiple regression analysis. Soil pH (coupled with CEC) and soil Ca had a major influence on Pb accumulation (V2 of worm Pb increased to 77-83%), and there was some evidence that Cd accumulation may be suppressed in extremely organic soils. The edaphic factors investigated had no effect on Cu or Zn accumulation by earthworms. In the context of biomonitoring, it is proposed that earthworms have a potential in a dual role: (1) as 'quantitative' monitors of total-soil metal concentrations (as shown for Cd); and (2) as estimators of 'ecologically significant' soil metal, integrating the effects of edaphic factors (as shown for Pb).     

Concentrations of zinc and chromium in aquatic macrophytes from the sudbury and muskoka regions of Ontario, Canada

Root and shoot samples of Eriocaulon septangulare, Nuphar variegatum, Nymphaea odorata and Pontederia cordata were collected from 15 lakes in central Ontario during the summer of 1988 to investigate possible relationships between zinc and chromium levels in aquatic macrophytes and water and sediment variables. Although concentrations of zinc and chromium differed greatly among the four species, both metals were consistently higher in Eriocaulon. Generally, root and rhizome tissue contained higher zinc and chromium than shoot tissues of the same species and site. Zinc concentrations (dry weight) ranged from 6.3 microg g(-1) in Nuphar shoots to 87.7 microg g(-1) in whole Eriocaulon. Chromium ranged from 0.23 microg g(-1) in Pontederia shoots to 23.9 microg g(-1) in whole Eriocaulon. No significant trends were detected throughout the growing season in macrophyte or sediment concentrations of either metal. Results of multiple linear regression analyses of several water quality and environmental variables on Eriocaulon indicated that sediment zinc was the best predictor of plant zinc, and sediment chromium and calcium were the best predictors of plant chromium.     

Loading estimates of lead, copper, cadmium, and zinc in urban runoff from specific sources

Urban stormwater runoff is being recognized as a substantial source of pollutants to receiving waters. A number of investigators have found significant levels of metals in runoff from urban areas, especially in highway runoff. As an initiatory study, this work estimates lead, copper, cadmium, and zinc loadings from various sources in a developed area utilizing information available in the literature, in conjunction with controlled experimental and sampling investigations. Specific sources examined include building siding and roofs; automobile brakes, tires, and oil leakage; and wet and dry atmospheric deposition. Important sources identified are building siding for all four metals, vehicle brake emissions for copper and tire wear for zinc. Atmospheric deposition is an important source for cadmium, copper, and lead. Loadings and source distributions depend on building and automobile density assumptions and the type of materials present in the area examined. Identified important sources are targeted for future comprehensive mechanistic studies. Improved information on the metal release and distributions from the specific sources, along with detailed characterization of watershed areas will allow refinements in the predictions.     

Multi-generation toxicity of zinc, cadmium, copper and lead to the potworm Enchytraeus albidus

In standard chronic terrestrial toxicity tests with invertebrates, adult organisms are exposed to the contaminants and the number of offspring is quantified. These procedures do not allow the assessment of possible effects on all life stages of the organism, which may lead to an underestimation of the toxicity of the test substance. To evaluate the importance of this issue, the potworm Enchytraeus albidus was exposed to zinc, cadmium, copper and lead for two subsequent generations. Juvenile production was assessed for both generations. Considering the variability of metal toxicity data reported in the literature, it is concluded that the two generation assay did not markedly increase the sensitivity of the standard E. albidus test for the tested metals. Therefore, toxicity data obtained with the proposed test guideline with E. albidus are protective for all life stages.     

Distribution of chromium, cadmium, nickel and lead in agricultural soils collected from Kazanli-Mersin, Turkey

This study reports total levels of chromium, cadmium, nickel and lead in the agricultural land adjacent a factory producing chromate compounds in Kazanli-Mersin. Surface soil samples were collected from fields around the factory as well as from fields farther away to measure contamination due to aerial transportation and deposition of dust produced in the industrial process. Heavy metals in soil were extracted using wet digestion, and concentrations were measured by atomic absorption spectrophotometry. The concentrations were compared with Turkish maximum allowable concentration values. The metal concentrations averaged 80, 0.14, 228 and 431mg1kg^-1 for chromium, cadmium, nickel and lead, respectively. Soil samples contaminated with chromium were mainly found 500–20001m from the factory and decreased with increasing distance from the factory. Elevated chromium and nickel concentrations were determined in the soils around the factory, especially to the northwest (prevailing wind) and west. Lead concentrations exceeded the limit in only roadside soils (4000 and 50001m to the west), but tended to increase in the vicinity of industrial activity (especially in the west, the northwest and the north). The cadmium concentration did not exceed the limit and was within the normal range for soils.     

Environmental and economic evaluation of bioenergy in Ontario, Canada

We examined life cycle environmental and economic implications of two near-term scenarios for converting cellulosic biomass to energy, generating electricity from cofiring biomass in existing coal power plants, and producing ethanol from biomass in stand-alone facilities in Ontario, Canada. The study inventories near-term biomass supply in the province, quantifies environmental metrics associated with the use of agricultural residues for producing electricity and ethanol, determines the incremental costs of switching from fossil fuels to biomass, and compares the cost-effectiveness of greenhouse gas (GHG) and air pollutant emissions abatement achieved through the use of the bioenergy. Implementing a biomass cofiring rate of 10% in existing coal-fired power plants would reduce annual GHG emissions by 2.3 million metric tons (t) of CO2 equivalent (7% of the province's coal power plant emissions). The substitution of gasoline with ethanol/gasoline blends would reduce annual provincial lightduty vehicle fleet emissions between 1.3 and 2.5 million t of CO2 equivalent (3.5-7% of fleet emissions). If biomass sources other than agricultural residues were used, additional emissions reductions could be realized. At current crude oil prices ($70/barrel) and levels of technology development of the bioenergy alternatives, the biomass electricity cofiring scenario analyzed is more cost-effective for mitigating GHG emissions ($22/t of CO2 equivalent for a 10% cofiring rate) than the stand-alone ethanol production scenario ($92/t of CO2 equivalent). The economics of biomass cofiring benefits from existing capital, whereas the cellulosic ethanol scenario does not. Notwithstanding this result, there are several factors that increase the attractiveness of ethanol. These include uncertainty in crude oil prices, potential for marked improvements in cellulosic ethanol technology and economics, the province's commitment to 5% ethanol content in gasoline, the possibility of ethanol production benefiting from existing capital, and there being few alternatives for moderate-to-large-scale GHG emissions reductions in the transportation sector.     

Comparison of the adsorption of lead,cadmium, copper,zinc and barium to freshwater surface coatings

Measurements were made regarding the adsorption of lead, cadmium, copper, zinc and barium to freshwater surface coatings (biofilms and associated minerals), which were collected in Nanhu Lake in Jilin Province, PR China, in order to investigate the variability of adsorption capacities of these heavy metals mentioned in the above surface coatings. The adsorption of lead and other heavy metals to the biofilms was observed to decrease in the following order: copper, lead, zinc, cadmium, and barium. Generally, the values of Gamma(max) (the maximum adsorption, micromol/m(2)) increased with the standard electrode potential of metal elements used and were recorded as 166.7, 40.0, 29.4, 10.8, and 1.8 for copper, lead, zinc, cadmium and barium, respectively. The values of 1/Gamma(max) increased linearly with the decrease in values of the standard electrode potential of metal elements with a significant correlation (n=5, p=0.01) and increased linearly with the increase in values of covalent radius of metal elements with a significant correlation (n=5, p=0.05). This indicates that standard electrode potential and covalent radius were two of the principal characteristics of metals employed, causing the variation of lead and other heavy metal adsorption to the surface coatings.     

Difference of lead,copper and zinc concentrations between interiors and exteriors of peds in some contaminated soils

Solute transport of elements in soils depends on the soil structural and hydraulic properties, and it is controlled by sorption and diffusion, which both limit the mobility and distribution of elements in soils. This study was conducted to compare lead (Pb), copper (Cu) and zinc (Zn) concentrations between ped exteriors and interiors of some contaminated soils. The results show that the differences of the heavy metals between exteriors and interiors decreased in the order clayey soil, clayey loam soil, loam soil. For same soils, the differences decreased from Pb to Cu to Zn. The differences in readily extractable concentrations of the three metals between ped exteriors and interiors were much larger than the differences in their total metals, this may indicate that extractable metals were more recently deposited. The higher Pb and Cu concentrations in the ped exteriors than interiors may additionally be explained by anthropogenic input, movement and downward through preferential flow.     

Sources of phenolic compounds in two catchments of southern Portugal - effect of season, land use and soil type

Water quality monitoring in reservoirs used for human water consumption, carried out by the Alentejo Regional Authorities of the Environment (south Portugal), revealed seasonal peaks of phenolic compounds above the water-quality legislation. The main objectives of this work were to identify the main phenolic compounds present in water and soil leachates, and to determine the sources of the seasonal concentrations of phenolic compounds in two catchments with different land use patterns: Roxo and Santa Clara catchments. The main phenolic compound detected was 2,4-dinitrophenol (2,4-DNP), both in stream water and soil leachates, with concentrations higher in Roxo catchment. Roxo catchment represents a larger agricultural area than Santa Clara, and it is likely that the origin of the 2,4-DNP is associated with the use of pesticides. A peak of 2,4-DNP concentrations was observed in stream water of both catchments during February, when farmers plough their fields and apply pesticides. The 2,4-DNP peak was probably caused by a precipitation event shortly after the application of pesticides, increasing their transfer from land surfaces to adjacent streams. The leaching behaviour of 2,4-DNP was strongly dependent on the type of soil and pH. In soils with high clay content and low pH, 2,4-DNP was easily adsorbed, and its runoff from the soil to adjacent streams was reduced. Ribeira de Santa Vitória, from Roxo catchment, was the only stream showing a high abundance of vegetation, and the lowest concentrations of 2,4-DNP in water. Plants may play a role in removing contaminants from stream water.