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.     

Heavy metal speciation and mobility assessment of arid soils in the vicinity of Al Ain landfill, United Arab Emirates

Sixty-four surface soil samples taken in the vicinity of Al Ain landfill were analysed for cadmium, chromium, copper, nickel, lead and zinc by inductively coupled plasma spectroscopy. Extraction techniques were used to establish the association of the total concentrations of the six metals in the soil samples with their contents in the exchangeable, carbonate, iron/manganese oxides, and residual fractions. In the investigated soils, the recorded concentrations were as follows: 0.043 mg kg^-1 for cadmium, 19.1 mg kg^-1 for chromium, 53.3 mg kg^-1 for copper, 60 mg kg^-1 for nickel, 13.7 mg kg^-1 for lead, and 117 mg kg^-1 for zinc. Cadmium, chromium, nickel, lead and zinc concentrations in the investigated soil samples reflect the natural background values in shale, whereas copper is slightly enriched. I-geo (geoaccumulation index) values of the metals in the soils under study indicate that they are uncontaminated with cadmium, chromium, nickel, lead and zinc, but contaminated to moderately contaminated with copper. Heavy metal contents in the sediments were found to be significantly influenced by different physico-chemical parameters. The effect of these parameters can be arranged in the following order: clay fraction > carbonate fraction > silt fraction > organic matter fractions. A sequential extraction procedure showed that the total concentrations of the heavy metals are largely bound to the residual phase (retained 71.4% of cadmium, 77.8% of chromium, 75% of copper, 47% of nickel, 62.8% of lead, and 75.8% of zinc). A likely sequence of mobility in the investigated soils is as follows: chromium > lead > nickel > cadmium > zinc > copper.     

Investigation of heavy metal accumulation in Polygonum thunbergii for phytoextraction

In this study, cadmium (II), lead (II), copper (II) and zinc (II) were determined in Polygonum thunbergii and soil from the Mankyung River watershed, Korea. Soil samples contained detectable lead (<17.5 g g(-1)), copper (<8.4 g g(-1)) and zinc (<24.5 g g(-1)), whereas cadmium was undetectable. Whole plants of P. thunbergii contained detectable lead (<320.8 g g(-1)), copper (<863.2 g g(-1)) and zinc (<2427.3 g g(-1)), whereas cadmium was detectable only in the stem (<7.4 g g(-1)) and root (<10.1 g g(-1)). Whole plant concentrations were very different for each metal, particularly in the case of zinc. The mean content of heavy metal in the whole plants increased in the order of cadmium (8.5 g g(-1))相似文献   

Contributions of heavy metals from municipal runoff to the sediments of Lake Pontchartrain, Louisiana

A study was conducted to determine the distribution and sources of heavy metal pollutants in the sediments of Lake Pontchartrain. Sediment samples were collected from the northern and southern shorelines and analyzed for heavy metals by atomic absorption spectrometry. The heavy metals of interest were barium, copper, nickel, lead, and zinc. The concentrations of these metals indicate that the principal source of heavy metal pollution is associated with urban stormwater runoff and municipal discharges.     

浮游球衣菌对Pb2+、Cu2+、Zn2+、Cd2+的吸附性能研究

研究了浮游球衣菌（Sphaerotilus natans）在不同吸附条件下对溶液中Pb^2＋、Cu^2＋、Zn^2＋、Cd^2＋的吸附规律。结果表明,Sphaerotilus natans对这4种重金属离子均有一定的吸附作用,并在20min内达到吸附平衡,pH对吸附过程影响较大,pH为5.5时Sphaerotilus natans对这4种金属离子的吸附效果最好,Sphaerotilus natans对它们的吸附选择性为Pb^2＋〉Cu^2＋〉Zn^2＋〉Cd^2＋,Pb^2＋、Cu^2＋能部分置换出已被菌体吸附的Zn^2＋、Cd^2＋。HCI和EDTA溶液可有效地将金属离子从菌体上解吸下来,解吸后的菌体可重复使用。     

Trace metal residues in finfish from Maryland waters, 1978-1979

Levels of seven heavy metal residues, arsenic, cadmium, chromium, copper, lead, mercury and zinc were monitored in samples of various species of finfish harvested from the Maryland section of the Chesapeake Bay and its tributaries over a two year period (1978-79). Results of the analysis of the edible portions of these finfish are presented along with the species of finfish, date and location of harvest. A number of samples of finfish gonad and liver tissue were analyzed to study the relative level of preconcentration of heavy metals in these tissues compared to the edible (flesh) portion. Results of this study are consistent with other available data for Atlantic Coast finfish. Gonad tissue, when compared to flesh, show enrichment of copper and zinc and decreased mercury and cadmium levels. Liver tissue shows enrichment in copper, zinc and cadmium and generally lower levels of mercury compared to flesh.     

Effects of pH on the toxicity of cadmium, copper, lead and zinc to Folsomia candida Willem, 1902 (Collembola) in a standard laboratory test system

EC₅₀s for cadmium, copper, lead and zinc were determined for juvenile production of Folsomia candida at pH6.0, 5.0 and 4.5 in a standard laboratory test system. In contrast to most previous studies where metal toxicity was increased at low pHs, in our experiments there was no clear relationship between soil acidity and EC_{50-reproduction} in this species. The EC_{50-reproduction} values (μg g⁻¹) for cadmium and zinc were similar at all three pHs (pH6.0: Cd 590, Zn 900; pH5.0: Cd 780, Zn 600; pH4.5: Cd 480, Zn 590). In contaminated field sites adjacent to primary zinc smelters, zinc is invariably present in soils at concentrations of at least 50 times that of cadmium Thus deleterious effects of mixtures of these metals on populations of Collembola in such sites can be attributed to zinc rather than cadmium.     

Consequences and implication of heavy metal spatial variations in sediments of the Keelung River drainage basin, Taiwan

A great deal of effort was enforced to reduce the pollution of the Keelung River in the past 20 years. A set of sediments covering most of the Keelung River drainage basin was analyzed for bulk sediment heavy metal concentrations, grain size content and Pb-210 dating in order to understand the spatial variations of sediment heavy metal contents as well as to evaluate the effectiveness of pollution control. The results showed that anthropogenic pollution and grain size are two of the most important factors in controlling spatial variations of metals in the Keelung River sediments. In addition, little reduction of sediment heavy metal concentrations was observed in the Keelung River drainage basin. Large spatial variations of metals and grain size were observed. High concentrations of zinc, copper, lead and cadmium were found in sediments near the main outlets of the adjacent Da-Wu-Lun Industrial Park and municipal waste drainage systems. Anthropogenic sources of heavy metal have altered the natural sediment heavy metal distributions. Positive linear relationships between aluminum, iron and fine-grained sediments showed that spatial grain size variations controlled the natural aluminum and iron concentrations in sediments. Zinc, copper, lead and cadmium contents were much higher than those measured 15 years ago. The unusually high concentrations of heavy metals, high enrichment factors and their rapid increases with time in Pb-210 dated core showed that the efforts in heavy metal reduction were futile. A proper regulation to prevent further heavy metals from entering into the river is urgently needed.     

Oribatid mite communities and metal bioaccumulation in oribatid species (Acari, Oribatida) along the heavy metal gradient in forest ecosystems

The responses of oribatid communities to heavy metal contamination were studied. Concentration of cadmium, copper and zinc in nine oribatid species along a gradient of heavy metal pollution was measured. Oribatid mites were sampled seasonally during two years in five forests located at different distances from the zinc smelter in the Olkusz District, southern Poland. The most numerous and diverse oribatid communities were found in the forest with moderate concentrations of heavy metals. Analysis by atomic absorption spectrophotometry revealed large differences in metal body burdens among species. All studied oribatid species appeared to be accumulators of copper with Oppiella nova, Nothrus silvestris and Adoristes ovatus characterized by the highest bioaccumulation factors. Most species poorly accumulate cadmium and zinc. The accumulation of heavy metals in the body of oribatids was not strictly determined by their body size or the trophic level at which they operate.     

Influence of initial pH on bioleaching of heavy metals from contaminated soil employing indigenous Acidithiobacillus thiooxidans

Bioleaching of heavy metals from contaminated soil was carried out employing indigenous sulfur oxidizing bacterium Acidithiobacillus thiooxidans. Experiments were carried out to assess the influence of initial pH of the system on bioleaching of chromium, zinc, copper, lead and cadmium from metal contaminated soil. pH at the end of four weeks of bioleaching at different initial pH of 3-7 was between 0.9 and 1.3, ORP between 567 and 617mV and sulfate production was in the range of 6090-8418mgl(-1). Chromium, zinc, copper, lead and cadmium solubilization ranged from "59% to 98%" at different initial pH. A. thiooxidans was not affected by the increasing pH of the bioleaching system towards neutral and it was able to utilize elemental sulfur. The results of the present study are encouraging to develop the bioleaching process for decontamination of heavy metal contaminated soil.     

公路周边土壤重金属污染及植物修复

随着中国公路建设迅猛发展,公路周边土壤重金属污染也日趋严重。文中结合近年来国内外的研究情况,以公路土壤污染中的铅、镉、锌、铜、铬等元素为重点,对土壤重金属污染的危害、分布特征及其影响因素,以及相应的植物修复技术等相关研究进行综述。     

Effects of heavy metals on sea urchin embryo development. Part 2. Interactive toxic effects of heavy metals in synthetic mine effluents

Interactive toxic effects between heavy metals were investigated using a sea urchin (Anthocidaris crassispina) bioassay. An effluent from an abandoned mine showed significant inhibitory effects on embryo development as well as producing specific malformations. The effects on the embryos were reproduced by synthetic polluted seawater consisting of eight metals (manganese, lead, cadmium, nickel, zinc, chromium, iron, and copper) at the concentrations detected in the mine effluent. This indicated that the heavy metals were responsible for the effects observed. Five heavy metals were ranked in decreasing order of toxicity as follows: Cu>Zn>Pb>Fe>Mn. Among these, zinc and manganese could cause malformation of the embryos. From bioassay results using 27 combinations of heavy metals, 16 combinations including zinc could produce specific malformations, such as radialized, exo-gastrulal, and spaceship Apollo-like gastrulal embryos. Zinc was one of the elements responsible for causing malformations and its effects were intensified by the presence of the other metals, such as manganese, lead, iron, and copper.     

Metal accumulation in the earthworm Lumbricus rubellus. Model predictions compared to field data

The mechanistic bioaccumulation model OMEGA (Optimal Modeling for Ecotoxicological Applications) is used to estimate accumulation of zinc (Zn), copper (Cu), cadmium (Cd) and lead (Pb) in the earthworm Lumbricus rubellus. Our validation to field accumulation data shows that the model accurately predicts internal cadmium concentrations. In addition, our results show that internal metal concentrations in the earthworm are less than linearly (slope<1) related to the total concentration in soil, while risk assessment procedures often assume the biota-soil accumulation factor (BSAF) to be constant. Although predicted internal concentrations of all metals are generally within a factor 5 compared to field data, incorporation of regulation in the model is necessary to improve predictability of the essential metals such as zinc and copper.     

Long-term effects of heavy metals on aouatic plants

In long-term experiments lasting up to 73 days the effect of rather low levels of zinc, copper, lead and cadmium on the growth and metal uptake was studied by investigating four aquatic plant species: Elodea nuttallii, Callitriche plataycarpa, Spirodela polyrhiza and Lemma gibba. Except Elodea, which was already very sensitive to 5 μmol Cu 1^?1, no differentiation in growth or mortality could be detected depending on species or elements. There was a clear differentiation between the uptake levels of the heavy metals with regard to the plant species, resulting in a higher heavy metal content in de submerged species in comparison to the floating ones. For zinc, lead and cadmium, an equal ratio was detected between the concentration in the medium and in the plant tissue independent of the plant species. The involvement of roots in element absorption by aquatic plants and the possibility of using aquatic plants as indicators of heavy metal pollution in Dutch waters are discussed.     

Mayfly larvae (Baetis rhodani and B. vernus) as biomonitors of trace metal pollution in streams of a catchment draining a zinc and lead mining area of Upper Silesia,Poland

Larvae of two Baetis species were used to investigate spatial and temporal variability in the bioavailabilities of cadmium, copper, lead, zinc and iron in the river Biala Przemsza and its tributaries draining an area of lead and zinc mining in Upper Silesia, Poland. Accumulated metal concentrations were measured in April, May, August and November 2000. Both species indicated significant local geographical variability in availabilities of zinc, iron, lead and cadmium, but not copper. Accumulated concentrations of lead, zinc and cadmium confirmed the high general contamination of the Biala Przemsza system by these three trace metals. Larvae showed little seasonal variation in concentrations of cadmium, copper, lead and iron. Accumulated zinc concentrations were low in Baetis rhodani in August, perhaps as a result of insufficient time for high concentrations to accumulate since hatching of the larvae. Samples collected in August most nearly matched criteria of the greatest availability of larvae for collection and their size homogeneity, minimising the possibilities of any effect of differential larval size and/or age on accumulated metal concentrations. Mayfly larvae are members of a suite of potential stream biomonitors in Central Europe, which together can provide information on the different sources of bioavailable trace metals present in aquatic ecosystems.     

Palygorskite as a feasible amendment to stabilize heavy metal polluted soils

The sorption behaviour of palygorskite has been studied with respect to lead, copper, zinc and cadmium in order to consider its application to remediate soils polluted with these metals. The Langmuir model was found to describe well the sorption processes offering maximum sorption values of 37.2 mg/g for lead, 17.4 mg/g for copper, 7.11 mg/g for zinc and 5.83 mg/g for cadmium at pH 5-6. In addition the effect of palygorskite amendment in a highly polluted mining soil has been studied by means batch extractions and leaching column studies. The soluble metal concentrations as well as the readily-extractable metal concentrations were substantially decreased at any concentration of palygorskite applied to soil (1, 2, 4%), although the highest decrease is obtained at the 4% dose. The column studies also showed a high reduction in the metal leaching (50% for lead, 59% for copper, 52% for zinc and 66% for cadmium) when a palygorskite dose of 4% was applied.     

Metal accumulation in soil arthropods in relation to micro-nutrients

Nine species of soil arthropod collected at two sites of different pollution levels were compared for concentrations of seven different elements (Ca, Cd, Cu, Fe, Mn, Pb, Zn) and correlations between the different elements were calculated. Significant effects of site on element concentrations of the animals were found for cadmium, iron, manganese and zinc, whereas calcium, copper and lead concentrations showed no significant difference between the sites. Significant differences between the species were found for all metal. The pattern of accumulation was comparable for some of the metals. Correlations were found between calcium, iron, manganese and lead concentrations and between zinc and cadmium concentrations of the species. No significant correlations were found for copper. The study showed that species can not be easily categorised as accumulators or non-accumulators; the pattern depends on the metal.     

Effect of mixed cadmium,copper, nickel and zinc at different pHs upon alfalfa growth and heavy metal uptake

Alfalfa plants were grown in soil-pots contaminated with a mixture of Cd(II), Cu(II), Ni(II), and Zn(II), (at 50 mg/kg each) at pHs of 4.5, 5.8, and 7.1. The plants were fertilized using a nutrient solution, which was adjusted appropriately to the same pH. Plants in the control treatment were grown in the absence of the heavy metals mixture. The growth of the control plants was the same at the three pHs studied and the heavy metal stressed plants also showed similar behavior at each pHs. There were statistically significant differences (P<0.05) between the shoot length of the control treatment plants and the length of plants grown in the presence of the heavy metal mixture. Under the effects of the heavy metal mixture, nickel was the most accumulated element in the shoot tissue, with 437, 333, and 308 ppm at pH 7.1, 5.8, and 4.5, respectively. Cadmium was found to be second in accumulated concentrations with 202 ppm, 124 ppm, and 132 ppm at pH 7.1, 5.8, and 4.5, respectively, while zinc was third, followed by copper. The maximum relative uptakes (element in plant/element in soil-water-solution) were found to be 26 times for nickel, 23 times for cadmium, 12 times for zinc. and 6 times for copper. We considered these relations as indicative of the ability of alfalfa plants to take up elements from a soil matrix contaminated with a mixture of cadmium, copper, nickel, and zinc.     

Effects of cadmium, copper, lead and zinc on growth, reproduction and survival of the earthworm Eisenia fetida (Savigny): Assessing the environmental impact of point-source metal contamination in terrestrial ecosystems

The earthworm Eisenia fetida (Annelida: Oligochaeta) was exposed to a geometric series of concentrations of cadmium, copper, lead and zinc in artificial soil using the OECD recommended protocol. Mortality, growth and cocoon production were measured over 56 days to determine LC50 and EC50 values. No observed effect concentrations (NOECs) were also estimated. Furthermore, the percentage of viable cocoons and number of juveniles emerging per cocoon was recorded. Cocoon production was more sensitive than mortality for all the metals, particularly cadmium and copper for which NOEC reproduction values were an order of magnitude lower than those for NOEC mortality. However, there was no significant effect of metals on the viability of cocoons. The weights of earthworms declined in all treatments (including the controls) during the experiment. This was probably due to the lack of suitable food in the OECD standard soil medium used. It was concluded that future experiments should include animal manure in the test medium. The LC50, EC50 and NOEC values determined in this study were compared with concentrations of metals in soils in the vicinity of a smelting works at Avonmouth, southwest England. The 14-day LC50 for zinc in Eisenia fetida was exceeded in soils covering an area of 75 km2 around the works, compared to 4.2 km2 for copper and 4.7 km2 for lead. Soil values for cadmium did not exceed the LC50 value anywhere in the region. Similar estimates of relative effects on reproduction confirmed that zinc is most likely to be responsible for the absence of earthworms from sites close to the Avonmouth works. However, the OECD standard test overestimated the potential effects of metals on populations, since earthworms can be found as close as 1 km from the smelting works. The discrepancy between test and field observations was probably due to the greater availability of the metals in the artificial soil.     

Trace metal residues in shellfish from Maryland waters, 1976-1980

Levels of seven heavy metal residues, arsenic, cadmium, chromium, copper, lead, mercury and zinc were monitored in samples of the American oyster (Crassostrea virginica), the soft shell clam (Mya arenaria), the hard shell clam (Mercinaria mercinaria) and the blue crab (Callinectes sapidus). Samples were taken from the Maryland section of the Chesapeake Bay and its tributaries over a five year period (1976-80). This study was undertaken to provide an estimate of a baseline for values of trace heavy metals. Also, the oyster, being a non-mobile filter feeder, provides information regarding the level of metal residues in its environment (water and sediment), because heavy metal uptake is related to the surrounding metal concentrations. Additionally, this type of monitoring program is essential to ensure that shellfish sold for human consumption are within safe limits established for toxic substances by the United States Food and Drug Administration. Results of the study are consistent with data from previous years and no statistically significant year-to-year trends were observed over the period of the investigation.