Bioaccumulation of metals and effects of a landfill in small mammals. Part II. The wood mouse, Apodemus sylvaticus

We assess the bioaccumulation of metals (Pb, Hg, Cd, Fe, Mg, Zn, Cu, Mn, Mo, Cr) and effects of landfill leachates on morphological (RI, relative weights), plasma (GPT, GOT, creatinine), and genotoxic (MNT) parameters in wood mice, Apodemus sylvaticus, inhabiting close the Garraf landfill site (NE Spain). Due to the high age- and sex-dependent variation in wild populations, we also studied the effect of these biotic factors on the parameters studied. Wood mice from the landfill site, sited in a partially protected area, showed more Cd, Fe, Zn, Cu, Mn, Mo, and Cr than specimens from the reference site. Moreover, mice near the landfill registered low RI and high relative renal weight, GPT, and MN frequency, which indicate that the landfill affects the health of wild mice. In contrast to sympatric shrews from a previous study, wood mice showed lower bioaccumulation of metals and lower variation caused by biotic factors. Moreover, the morphological and physiological alterations demonstrated that they were also more sensitive at environmental pollution. Given the contribution of small mammals to ecosystem function and the scarce ecotoxicological data on the effects of landfill pollution on wild terrestrial mammals, we consider that our study can be used to improve the management of this protected area.     

Metal bioaccumulation in the greater white-toothed shrew, Crocidura russula, inhabiting an abandoned pyrite mine site

Hepatic and renal concentrations of iron, magnesium, zinc, lead, copper, manganese, mercury, cadmium, molybdenum, chromium, and nickel were quantified in shrews (Crocidura russula) inhabiting a pyrite mine site in Portugal. Several morphological parameters (body weight, residual index, and relative weights) were also examined to clarify the physiological effects of pollution. Shrews from the mine showed increased bioavailability of Fe, Pb, Hg, Cd, Mo, and Ni in comparison with reference specimens. Adult shrews had the highest Cd levels while Cr and Ni concentrations diminished. Intersexual differences were found for Mo and Ni. As a consequence of metal pollution, the relative hepatic weight was higher in shrews from the mine site when compared with reference specimens. These data indicate that C. russula is a good bioindicator of metal pollution. We also evaluated the toxic effects of Pb, Hg, Cd, and Ni, because several shrews from the polluted site showed high concentrations of these metals. To approximate at the real biological impact of abandoned mines, after this first step it is necessary to associate the bioaccumulation levels and morphological effects with other physiological, ecological and genetical biomarkers.     

Heavy metals contents in agricultural topsoils in the Ebro basin (Spain). Application of the multivariate geoestatistical methods to study spatial variations

In this work the content of seven heavy metals (Cd, Cr, Cu, Hg, Ni, Pb and Zn) and other parameters (the pH, organic matter, carbonates and granulometric fraction) in agricultural topsoil in the Ebro basin are quantified, based on 624 samples collected according to an 8 by 8 km square mesh. The average concentrations (mg/kg) obtained were: Cd 0.415+/-0.163, Cr 20.27+/-13.21, Cu 17.33+/-14.97, Ni 20.50+/-22.71, Pb 17.54+/-10.41, Zn 17.53+/-24.19 and Hg 35.6+/-42.05 microg/kg. The concentration levels are relatively low in areas of high pH and low organic matter content concentration. The results of factor analysis group Cd, Cu, Hg, Pb and Zn in F1 and Cr y Ni in F2. The spatial heavy metals component maps based on geostatistical analysis, show definite association of these factors with the soil parent material. The local anomalies (found in Cu, Zn and Pb) are attributed to anthropogenic influence.     

Size distribution of airborne particulate matter and associated heavy metals in the roadside environment

The size distributions of airborne particulate matter (PM) and associated heavy metals Pb, Cd, Ni, Cr, V, Mn, Cu and Fe in different inhalable fractions (< 0.8 microm, 0.8-1.3 microm, 1.3-2.7 microm, 2.7-6.7 microm and > 6.7 microm) were determined at a traffic-orientated urban site in the city of Thessaloniki, northern Greece. The airborne PM displayed a bimodal distribution with most of the mass (52%) contained in the submicron size range (< 0.8 microm) and an additional minor mode (20%) in the coarse size fraction (> 6.7 microm). Characteristic size distributions of heavy metals allowed identification of three main behavioral types: (a) metals whose mass was resided mainly within the accumulation mode (Pb,Cd), (b) those which were distributed between fine, intermediate and coarse modes (Ni,Cu,Mn), and (c) those which were mainly found within particles larger than 2.7 microm in diameter (Fe). The mean mass median aerodynamic diameter (MMAD) of PM was found at 0.85+/-0.71 microm, while the mean MMADs of heavy metals followed the order Pb (0.96 +/- 0.71 microm) < Cd (1.14 +/- 0.82 microm) < V (1.38 +/- 0.63 microm) < Ni (1.45 +/- 0.88 microm) < Cu (2.04 +/- 0.77 microm) < Mn (2.61 +/- 1.23 microm) < Cr (2.91 +/- 1.40 microm) < Fe (3.82 +/- 0.88 microm). The measured distributions are believed to result from a combination of processes including local anthropogenic and natural sources, such as traffic, industrial emissions and resuspension of road dust.     

Arrested municipal solid waste incinerator fly ash as a source of heavy metals to the UK environment

Arrested fly ash samples from most currently operating municipal solid waste (MSW) incinerators in the UK have been analysed for a range of elements. Some of the more important heavy metals ranged in concentration as follows: Cd, 21-4646 (median = 271) mg kg(-1); Cu, 296-1307 (642) mg kg(-1); Cr, 44-1328 (574) mg kg(-1); Ni, 45-2204 (74) mg kg(-1); Pb, 447-9704 (4337) mg kg(-1); and Zn, 2285-13,500 (9232) mg kg(-1). These concentrations represent considerable enrichments relative to median UK soil concentrations. Enrichment ratios (defined as median fly ash: median UK soil) were as follows: Mn 1.6; Co 2.6; Ni 3.3; Ba 11; Sr 11; Cr 15; Cu 35; Pb 108; Zn 113; Cd 387. It is estimated that MSW incinerator ash contributes c. 15 t Cd and 241 t Pb to UK landfill sites per annum. These figures compare with previous studies by Hutton & Symon (Hutton, M. & Symon, C. (1986). The quantities of cadmium, lead, mercury and arsenic entering the UK environment from human activities. Sci. Total Environ., 57, 129-50.) which estimated that annual inputs to UK landfills from coal fly ash are c. 60 t Cd and 1270 t Pb. However, it is argued that metals associated with MSW ashes are potentially of greater environmental significance than in coal ashes, because they are much more available and present at much higher concentrations.     

Partition and size distribution of heavy metals in the flue gas from municipal solid waste incinerators in Taiwan

This study investigates the partition of heavy metals in both solid and gas phases in the flue gas from municipal solid waste (MSW) incinerators. Six MSW incinerators in Taiwan were examined and heavy metals in the flue gas at the inlets and outlets of air pollution control devices (APCDs) were analyzed. Heavy metals including Hg, Pb, Cd, Zn, Cu and Cr were sampled by USEPA Method 29 and further analyzed using inductively coupled plasma-mass spectroscopy (ICP-MS) and cold vapor atomic absorption spectrometry (CVAAS). Experimental results revealed that the removal efficiencies of the APCDs for the heavy metals Pb, Cd, Zn, Cu and Cr greatly exceeded 90%, but that of Hg did not. Two groups of heavy metals upstream of APCDs were observed. Pb, Cd, Zn, Cu and Cr were present mainly in the solid phase with a solid to gas ratio (S/G) of over 12.3. However, in most cases, mercury appeared mainly in the gas phase with an S/G ratio from 0.15 to 1.04, because it has a low boiling point. Additionally, treatment with the APCDs increased the S/G ratio of mercury because gaseous mercury could be removed by injecting powdered activated carbon (PAC) into the flue gas. Moreover, the distribution of particle sizes in the solid phase was bimodal. Finer particles (d(p)2.5 microm) contained more Cr and Hg.     

Metal toxicity and natural antidotes: prevention is better than cure

Environmental Science and Pollution Research - Toxicity due to heavy metals (HM), specifically mercury (Hg), arsenic (As), lead (Pb), and cadmium (Cd) remains a challenge to scientists till date....     

Characteristics of leachate from pyrolysis residue of sewage sludge

The pyrolysis residue (SP) of sewage sludge (SS) produced at 500 degrees C was subjected to batch and column leaching tests to investigate the release of its organic and inorganic constituents and metals. For comparison, incineration ash (SI) obtained from a SS incinerator was also tested. Pyrolysis and incineration reduced organic matter of SS from 0.78 kg kg(-1)-dry SS to 0.16 and 0.01 kg kg(-1)-dry SS, respectively. Heavy metals remained in SP without being volatilized, although Cd and Pb were transferred into the off-gas during incineration. In the batch leaching test with the leaching liquid-to-solid mass ratio (L/S)=10, the pH of the SS, SP, and SI filtrates was 6.3, 7.9, and 11.0, respectively. The total organic carbon concentrations were in the order SS (877 l mg l(-1))>SP (99 mg l(-1))>SI (26 mg l(-1)). The SP and SI filtrates met the landfill standard for the Cd and Pb concentrations (<0.3 mg l(-1)). In the column tests, although the SP contained more organic matter than that of SI, its carbon discharge into the leachate under aerobic conditions was similar to that of SI under anaerobic conditions. The leaching of heavy metals, such as Cd, Cr, Pb, and Zn, was also suppressed in SP during the active decomposition of organic matter. We demonstrated that pyrolysis reduces the potential release of pollutants from sewage sludge in landfill, making it a promising method of treating sewage sludge before landfilling.     

Sources, distribution and variability of airborne trace metals in La Plata City area, Argentina

Airborne particulate trace metals have been measured bimonthly during day and night hours in four permanent stations located in residential, industrial and commercial sectors of La Plata City region, to characterize the sources and variability of atmospheric inputs. Airborne trace metal regional averages (Pb 64 +/- 62, Cu 30 +/- 27, Mn 26 +/- 20, Zn 273 +/- 227, Fe 1183 +/- 838, Ca 5343 +/- 3614, Mg 1472 +/- 967, Cr 4.3 +/- 2.4, Ni 3.2 +/- 3.5 and Cd 0.41 +/- 0.42 ng/m3) are comparable to the values reported for not grossly polluted cities and below the general trend described for urban particulates. Two- and three-way analysis of variance and variance components tests (P < 0.05) were performed to assess the contribution of the diurnal (day vs. night), spatial (inter-station) and temporal (inter-month) components of variability. Trace metal concentrations followed the behavior of total suspended particles with higher concentrations during the day and at the Downtown station and lower at the Residential site. In general, spatial and temporal variations prevailed over diurnal differences. Spatial differences were clearly most significant for Pb, which presented higher values at the Downtown site reflecting the importance of motor exhaust inputs. In contrast, diurnal differences were more important for Mn due to increased dust resuspension during day hours. A seasonal trend with concentrations usually increasing during winter months and decreasing in spring-summer was also detected. Enrichment factors (EF) were calculated to evaluate anthropogenic versus natural element sources. High EF (21-376) were obtained for Pb, Zn, Cd and Cu reflecting the importance of anthropic inputs. The comparison with EF calculated for high-emitting vehicle particle emissions indicated that motor exhausts are the most important source of these elements in La Plata region. In contrast, the EF calculated for Mn, Cr, Ni, Ca and Mg were low (1.3-7.5) suggesting chiefly natural sources, i.e. soil-derived dusts.     

Genotypic and environmental variation in chromium, cadmium and lead concentrations in rice

Genotypic and environmental variation in Cr, Cd and Pb concentrations of rice grains and the interaction between these metals were investigated by using 138 rice genotypes grown in three contaminated soils. There were significant genotypic differences in the three heavy metal concentrations of rice grains, with the absolute difference among 138 genotypes in grain Cr, Cd and Pb concentrations being 24.5-, 9.1- and 23.8-folds, respectively, under the slightly contaminated soil (containing 4.61mgkg(-1) Cr, 1.09mgkg(-1) Cd and Pb 28.28mgkg(-1), respectively). A highly significant interaction occurred between genotype and environment (soil type) in the heavy metal concentrations of rice grains. Cr concentration in rice grains was not correlated with Cd and Pb concentration. However, there was a significant correlation between Cd and Pb in slightly and highly contaminated soils. The results suggest the possibility to develop the rice cultivars with low Cd and Pb concentrations in grain.     

Speciation of heavy metals in marine sediments vs their bioaccumulation by mussels.

Total contents and speciation of selected heavy metals, including Al, Fe, Co, Ni, Pb, Zn, Cu, Cr, were measured in sediment samples and mussels Mya arenaria and Astarte borealis collected in the Horsund Fjord off Spitsbergen (Norwegian Sea) and the Bay of Gdansk (Baltic Sea). The investigation aimed at revealing differences in the accumulation pattern of heavy metals in mussels inhabiting sediments characterized by varying metal bioavailability. The contents of metals adsorbed to sediments and associated with iron and manganese hydroxides, which were obtained by sequential extraction, were utilized as a measure of metal bioavailability. The contents of Cd, Pb, Zn, Cu and Cr in mussels collected off Spitsbergen were generally lower than those in mussels from the Baltic Sea. In sediments collected off Spitsbergen the bioavailable fraction represented a small proportion (0-3.7% adsorbed metals and 0-11% associated with metals hydroxides) of total heavy metal contents. In sediments from the Baltic Sea the percentages of metals adsorbed and bound to hydroxides were 1-46% and 1-13%, respectively. The differences in bioavailable metal contents measured in sediments were utilized to explain the different contents of metals in mussels collected in the corresponding sites.     

Use of zebra mussel (Dreissena polymorpha) to assess trace metal contamination in the largest Italian subalpine lakes.

Trace metal (Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn) contamination was evaluated in zebra mussels from the lakes Maggiore, Lugano, Como, Iseo and Garda, which are located in the most highly populated and industrialised area in Italy. Zebra mussels from Lake Maggiore contained the highest concentrations (3.44, 1.51, 4.97, 0.158, 5.87, 346 microg g(-1) for Cd, Co, Cr, Hg, Pb, Zn, respectively) of all metals analysed except Cu and Ni. The lowest levels of most metals were in animals from Garda and Lugano (0.78 and 0.60 microg g(-1) for Cd, 2.87 and 2.03 microg g(-1) for Cr, 0.065 and 0.049 microg g(-1) for Hg, 12.1 and 11.9 microg g(-1) for Ni, 1.96 and 2.46 microg g(-1) for Pb, 158 and 163 microg g(-1) for Zn). The most contaminated sites and possible local sources of metals were identified for each lake, and the lakes classified into quality classes concerning metal pollution.     

Heavy metals mobility in full-scale bioreactor landfill: initial stage

Selected heavy metals (HMs) including Cd, Cr, Cu, Ni, Pb and Zn initially released from a full-scale bioreactor landfill were monitored over the first 20 months of operation. At the initial landfill stage, the leachate exhibited high HMs release, high organic matter content (27000-43000gl(-1) of TOC) and low pH (5-6). By the fifth month of landfilling, the methanogenic stage had been established, and HMs release was reduced below the Chinese National Standards. Total released HMs accounted for less than 1% of landfill deposited during the investigated period. Most landfill HMs were inorganic. Fourier-transform infrared (FT-IR) spectra data and model calculations using Visual MINTEQ indicated that humic substances strongly affected the mobility of organic fractions of HMs in the methanogenic landfill. The initial rates of HMs release could be enhanced by recycling the leachate back to bioreactor landfill, but the total quantity released may be reduced by early establishment of methanogenic stage in bioreactor landfill.     

Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China

Guiyu, China is infamous for its involvement in primitive e-waste processing and recycling activities. Freshwater samples were collected in and outside of Guiyu for dissolved metal analysis. It was found that dissolved metal concentrations were higher in Lianjiang and Nanyang River within Guiyu than the reservoir outside of Guiyu. Lianjiang was enriched with dissolved As, Cr, Li, Mo, Sb and Se, while Nanyang River had elevated dissolved Ag, Be, Cd, Co, Cu, Ni, Pb and Zn. Temporal distributions of the metals suggested recent discharges of metals attributable to a strong acid leaching operation of e-waste, where dissolved Ag, Cd, Cu and Ni (0.344+/-0.014, 0.547+/-0.074, 87.6+/-3.0 and 93.0+/-1.4 microg/L, respectively) were significantly elevated. Pb isotopic composition of dissolved Pb confirmed that more than one non-indigenous Pb were present in Lianjiang and Nanyang River. In summary, it was evident that the riverine environment of Guiyu was heavily impacted by e-waste related activities.     

Assessment of heavy metals (Cd, Cr and Pb) in water, sediment and seaweed (Ulva lactuca) in the Pulicat Lake, South East India

The concentrations of three heavy metals chromium (Cr), cadmium (Cd) and lead (Pb) were examined in water, sediment and green algae (Ulva lactuca); collected from six different stations at Pulicat Lake, which receives effluents from industries located in North Chennai Coastal region. Concentrations of Cd (64.21 microg g(-1)) and Cr (28.51 microg g(-1)) were found to be high in sediment, whereas in green algae concentration of Pb (8.32 microg g(-1)) was higher than water and sediment samples. The relative abundance of these heavy metals in U. lactuca and sediment were found to be in the order Cd>Cr>Pb, whereas in water the ratio was found to be Cr>Pb>Cd. The seasonal variations in Cd and Pb followed a similar pattern in both seaweeds and sediments, but not in water samples. Spearman correlation coefficient study showed no significant correlation in the concentration of metals in U. lactuca, water and sediment samples.     

Heavy metal levels and solid phase speciation in street dusts of Delhi,India

Street dust samples were collected from three different localities (industrial, heavy traffic and rural) situated in the greater Delhi area of India. The samples analyzed for Cd, Zn, Pb, Ni, Cu, and Cr indicated remarkably high levels of Cr, Ni, and Cu in the industrial area, whilst Pb and Cd did not show any discernible variations between the three localities. A multivariate statistical approach (Principal Component Analysis) was used to define the possible origin of metals in dusts. The street dusts were sequentially extracted so that the solid pools of Cd, Zn, Pb, Ni, Cu, Cr could be partitioned into five operationally defined fractions viz. exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. Metal recoveries in sequential extractions were +/- 10% of the independently measured total metal concentrations. Cd was the only metal present appreciably (27.16%) in the exchangeable fraction and Cu was the only metal predominantly associated (44.26%) with organic fraction. Zn (45.64%) and Pb (28.26%) were present mainly in the Fe-Mn oxide fraction and the residual fraction was the most dominant solid phase pool of Cr (88.12%) and Ni (70.94%). Assuming that the mobility and bioavailability are related to the solubility of geochemical forms of the metals and decrease in order of extraction, the apparent mobility and potential metal bioavailability for these highly contaminated street dust samples is: Cd>Zn approximately equal Pb>Ni>Cu>Cr.     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Geochemical evidences of the anthropogenic alteration of trace metal composition of the sediments of Chiricahueto marsh (SE Gulf of California)

Seven sediment cores (60-80 cm) were collected at Chiricahueto marsh, a salt marsh influenced by agrochemical, domestic and industrial effluents. The concentrations of Ag, Al, Cd, Co, Cu, Fe, Li, Mn, Pb, V and Zn were studied in the solid phase at each 1-cm section. The profiles of Ag, Cd, Cu, Mn, Ni, Pb and Zn showed a slight recent pollution in the site with enrichment and anthropogenic factors higher than unity; and correlation analysis indicated a direct association with organic carbon. Al, Co, Cr, Fe, Li, and V concentration profiles displayed a negative correlation with organic C and positive with mud content and no consistent enrichment at surface. Based on the principal component analysis and correlation analysis, two principal groups of metals were identified. The first group includes Al, Co, Cr, Fe and Li, that are derived predominantly from the weathering of parent materials in the local bedrock; and the second group include most of the metals, which were relatively enriched at surficial sediments, that are produced mainly by anthropogenic activities such as agriculture (Cd, Cu and Zn), sewage effluents (Ag, Cd, Cu, Ni, Pb and Zn) and in lesser extent atmospheric deposition (Cd and Pb).     

Heavy metals in water, sediment and tissues of Leuciscus cephalus from a stream in southwestern Turkey

Concentrations of heavy metals (Cd, Cr, Cu, Pb and Zn) were measured in water, bottom sediment and tissues (muscle and gills) of Leuciscus cephalus from the Dipsiz stream in the Yatagan basin (southwestern Turkey), the site of a thermal power plant. Results for levels in water were compared with national and international water quality guidelines, as well as literature values were reported for streams and rivers. Comparisons were made of metal concentrations in water and sediment with those in the muscle and gills of L. cephalus caught from the Dipsiz stream. We found that there was metal accumulation in the gills compared to the muscle. Concentrations of Cd, Pb, Zn and Cr in the gills were higher than that in the muscle; however, Cu levels were higher in muscle than that in gills. Concentrations of heavy metals in L. cephalus muscle were below the legal limits for human consumption, although Cr, Pb and Zn levels in the gills were above the limits in the fish taken from the Dipsiz stream. On the other hand, no correlation was found between metal concentrations in water and sediment or between metal concentrations in water and muscle and gills of L. cephalus. A positive correlation was found between concentrations of Cu and Zn in the sediment and in fish tissue, whereas there was no relationship between other metal concentrations in the sediment and water, and muscle and gills of L. cephalus. As with water, Pb and Cd concentrations in particular were higher in sediment than that in background levels. The results show that the pollutants from the thermal power plant may be a source of these elements.     

Cadmium in soil solutions from a transect of soils away from a fertiliser bin

The effects of high inputs of phosphate fertiliser on Cd concentrations were studied in soil solutions extracted from topsoils. Soils were sampled along a transect at distances of 1-100 m away from a fertiliser bin. The transect was sampled four times during 1 year. Soil solutions were analysed for Cd, pH, major cations and anions, and other heavy metals (As, Cr, Cu, Pb). For one of the transect samplings, soil total Cd, Cr, Cu, Pb and P were also measured. Cd speciation in the soil solutions was calculated by the GEO-CHEM-PC computer program. Chemical composition varied substantially along the transect, and also between samplings, indicative of seasonal effects and the influence of a fresh application of superphosphate fertiliser during the year. Application of fertiliser decreased soil solution pH and increased the levels of heavy metals in soil solution. Generally, soil total Cd, Cr, Cu, Pb, and P decreased with increasing distance from the fertiliser bin. Correlations between P and the four heavy metals were: P and Cd (R2 = 0.978), P and Cr (R2 = 0.712), P and Pb (R2 = 0.538), P and Cu (R2 = 0.267). Less than 1% of the total Cd in the soil samples was found in the soil solution. The free metal ion Cd2+ accounted for 55-90% of solution Cd. Of the complexed species of Cd, the chloride and sulphate complexes were usually the most important, even when nitrate and phosphate concentrations were relatively high. The presence of As, Cr, Cu and Pb had no effect on Cd speciation.