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).     

Heavy metal concentrations in Mullus barbatus and Pagellus erythrinus in relation to body size,gender, and seasonality

Marine environments have been subjected to an increase in heavy metal pollution. Investigations were conducted in the bioaccumulation of heavy metals for both a benthic (Mullus barbatus) and a benthopelagic fish species (Pagellus erythrinus). The aim of this study was to examine the concentration levels of four metals in the body tissue of two fish species, in Pagasitikos Gulf in Greece, and to determine if metal concentration levels were affected by season, size, and species. Fish samples were collected monthly from September 2009 to August 2010. Chromium (Cr), Copper (Cu), Zinc (Zn), and Cadmium (Cd) concentrations were measured in muscle, gills, vertebral column, and in the “remaining fish sample.” Statistical analysis pinpointed substantial differences in metal concentration levels between some size classes. Significant differences were observed between two fish species’ tissues concerning Cu, Zn, and Cd concentrations. Cu and Zn concentrations varied amongst red mullet tissues as did Zn and Cd concentrations in common pandora. Ample variations were found seasonally in metal concentration levels; however, nonsignificant statistical differences were found among sexes.     

The influence of body size, condition index and tidal exposure on the variability in metal bioaccumulation in Mytilus edulis

Mussels are commonly used to monitor metal pollution despite high inter-individual variability in tissue concentrations. In this study, influences of body size, condition index and tidal height on concentrations of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were investigated. Body weight was inversely related to metal concentrations and for Cd, Mn, Pb and Zn the regression was affected by tidal height. Except for As, Fe and Mn metal concentrations were inversely related to physiological status though no differences between essential and non-essential metals were obvious. After correcting for body size, tidal height was related positively to As, Cd and Zn, negatively related to Cu, Fe and Mn while Co, Cr, Ni and Pb were independent of tidal height. The study recommends stringent measures during sampling for biomonitoring or metal concentrations at each location must be normalized to a common body size, CI and tidal height.     

Metal concentrations in edible mushrooms following municipal sludge application on forest land

In the context of biosolids utilisation in forestry, effects of sludge application on mushroom metal concentration were studied in six sites of maritime pine forests in the South-West of France. Municipal sludge were applied at a rate of 6 T dry matter per hectare. Edible mushrooms were collected two years after sludge application. As, Cd, Cu, Hg, Pb, Se and Zn concentrations were determined. Results showed a high variability for trace element concentrations in mushrooms collected from control areas. No significant correlation was found between soil parameters (pH and trace elements concentrations) and mushroom trace element concentrations. Even if the concentration of trace metals increased in the soils, sludge application did not affect As, Cu, Se and Zn concentrations in carpophores but slightly increased Cd, Pb and Hg concentrations on some sites. This effect is dependent on sludge type and sites.     

Bioaccumulation of heavy metals in terrestrial invertebrates.

In this literature study, accumulation data of metals in terrestrial invertebrates were collected and compared (Arthropoda and Lumbricidae). Based on total soil concentrations and body concentrations, regression equations were calculated for each metal (Cd, Cu, Pb and Zn) and each taxonomic group. We also tried to find out whether or not accumulation levels of metals in Lumbricidae are representative for all of the studied terrestrial invertebrates. Taxonomic groups could be ordered according to the extent of metal accumulation. Significant differences in accumulation levels of a factor 2-12 were found between taxonomic groups. Overall, metal concentrations were high in Isopoda and low in Coleoptera. The concentrations in Lumbricidae were in between. It should be kept in mind that the data for Lumbricidae were mainly derived from laboratory experiments, while the data for other groups were derived from field studies. The internal Pb, Cd and Cu concentration increased with the soil concentration for most taxonomic groups in the order Pb > Cd > Cu. Body concentrations of Zn were quite constant over a range of soil concentrations. The differences in accumulation level between taxonomic groups show the relevance of including detailed information on feeding behaviour in risk assessment for invertebrate-eating animals.     

Trends in airborne particulates in Stuttgart, Germany: 1972-2005

Since 1972, at the University of Hohenheim in Stuttgart, Germany, airborne particulate matter (PM12 and then PM10) was continuously collected on filters and analyzed for environmentally relevant elements by X-ray fluorescence analysis. The resulting long-term time series are suitable for the investigation of trends and of seasonal variation. For the period 1972-2005, monthly and annual concentration mean values of 13 elements (Br, Ca, Cr, Cu, Fe, K, Mn, Ni, Pb, S, Ti, V, and Zn) in the air are presented. Trend curves were fitted and the mean yearly variation of the concentration for these elements was calculated and represented graphically. All trend curves show a diminution of the air pollution during this period, but to different extents. Mean trends in percent per year were calculated for each element both for the entire investigation period and for three data subsets of 10-11 years. Possible explanations are discussed in detail.     

Effect of shore position and environmental metal levels on body metal burdens in the barnacle, Elminius modestus

Body (thorax and prosoma) weight, shell growth, and Zn, Cu, Fe, Mn and Ca levels were measured in artificially settled Elminius modestus over a 14-month period following transfer to high, mid and low tide positions in the uncontaminated Menai Strait and two mid tide sites within a Zn and Cu polluted bay on the North West coast of Anglesey. Barnacles showed higher mortality and slower growth at the upper shore position than at any other site. There was no evidence of Zn and Cu regulation by the bodies or shells, and both seemed to reflect environmental levels. Body metal levels were lowest in early winter and the highest second year values were found in January (Zn), March (Cu, Fe) or May (Ca). Higher shore barnacles contained larger concentrations of Zn than mid or low tide animals. Differences in feeding activity and the amount of testes may account for these variations. Reciprocal transplants between polluted and 'clean' sites indicate that body Cu and Zn accumulation and loss was very rapid. Spatial and temporal changes in shell metal levels closely mirror that of the body.     

The distribution and intracellular compartmentation of metals in the endogeic earthworm Aporrectodea caliginosa sampled from an unpolluted and a metal-contaminated site

The tissue distribution of Cd, Cu, Pb, Zn and Ca in the endogeic earthworm Aporrectodea caliginosa living in a non-polluted and a heavy metal polluted soil was investigated. The tissues of animals from the contaminated soil contained greater concentrations of Cd, Pb and Zn than the corresponding tissues of animals from the unpolluted soil. The greatest concentrations of Cd, Pb, Zn, and Ca were primarily accumulated within the posterior alimentary canal (PAC), a tissue fraction which contained the greatest proportion of the whole-worm burdens of the respective metals. Cu was distributed fairly evenly in the tissue fractions investigated. The pattern of accumulation for the 'heavy' metals is broadly similar to that for epigeic earthworms; in contrast, a different pattern of tissue accumulation was found for Ca. In animals from the uncontaminated site, the major elemental constituents of the chloragosomes were P, Ca, Zn and S. A significant positive correlation exists between P and Ca within the chloragosomal matrix. These intracellular vesicles are major foci for Pb and Zn accumulation within the PAC, with 'excess' metals associated with P ligands within the chloragosome matrix. The incorporation of Pb and Zn appears to involve the cationic displacement of Ca. Such compartmentation appears to prevent dissemination of large concentrations of these metals into other earthworm tissues, and may thus represent a detoxification strategy based on accumulative immobilization. No intracellular localization of Cd was identified in the study, although the Cd concentration in the metalliferous soils examined was not exceptionally high. The observations are discussed in the context of a contribution to enhanced understanding of metal ecotoxicology in earthworms by providing baseline data on a little investigated ecophysiological group of earthworms. Comparisons of metal distribution and mechanisms of metal sequestration are made with other ecophysiological groups of earthworms, and the significance of the findings to biomonitoring and toxicity-testing programmes is considered.     

A comparison of (Pb, Cd and Zn) accumulation in terrestrial slugs maintained in microcosms: evidence for metal tolerance

The relative tissue accumulation of Pb, Cd and Zn were compared in two populations each of two species of slugs (Arion subfuscus and Deroceras reticulatum). One population was resident at a contaminated Pb/Zn mine site, and the other population was from an uncontaminated site and was transferred for 20 days to microcosms established at the mine site. It was found that when the experiment was conducted during late spring (May), but not in late winter (February), that the Pb and Zn concentrations in the tissues of the 'transplants', were significantly higher than in the tissues of 'residents'; the Cd concentrations in the transplants, although significantly higher in the May sample than in February, did not exceed those of their 'resident' counterparts. It was postulated that: (a) Pb and Zn tolerance in slugs is phenotypically expressed by a reduction in metal accumulation; (b) Cd tolerance, if present, may be characterized by enhanced storage capacity; and (c) the presence of local metal-tolerant ecotypes is a biotic variable that may confound the relationship between dry tissue and environmental metal concentrations that forms a basis of pollution biomonitoring.     

Variation in the mineral composition of eggs of the snail, Helix aspersa between populations exposed to different levels of metal contamination

The eggs of terrestrial gastropods represent a major investment of resources by the parent, not least in the provision of essential metals. In this experiment 11 populations of Helix aspersa were collected from habitats with different histories of lead exposure and allowed to reproduce in the laboratory. After 4 months on a low metal diet, five four-egg samples were taken from a single clutch of each population and analysed for their metal content. Within-clutch and between population variation in the eggs were measured. No Pb or Cd was detected in any of the eggs. Both trace and essential metals show considerable variation between eggs within the same clutch. Cu levels were consistent across populations while egg Zn was closely correlated with soil Zn. Median Ca and Mg levels show little relation to soil concentrations. However, Ca provision declines with soil Pb across the populations. While the metal content of the eggs appears to be closely regulated, an interaction between Pb and Ca in the parental tissues may mediate the supply of Ca to the eggs.     

Accumulation of Al, Mn, Fe, Cu, Zn, Cd and Pb by the bryophyte Scapania undulata in three upland waters of different pH.

Measurements were made of the contents of Al, Mn, Fe, Cu, Zn, Cd and Pb in Scapania undulata in three streams (D2, D5, D11) in the English Lake District. The stream waters had average pH values of 5.35 (D2), 5.81 (D5) and 7.26 (D11), the main differences in other major chemical components being in Mg, Al, Ca and alkalinity. There was generally more metal accumulation in the older parts of the plants, but this was not significant in all cases. Extents of accumulation varied with stream pH and dissolved metal concentration. For Al, accumulation was greatest in streams D2 and D5. Mn accumulated most in D5 and Fe was without preference. Cu, Zn and Cd accumulated mostly in the plants in stream D11 and Pb accumulated more in D5 and D11. In terms of enrichment factors (amount of metal in the plants divided by stream water concentration) the sequence was Zn < Cd < Cu < Mn < Pb < Al < Fe. Laboratory experiments supported the findings of the field data, providing evidence that uptake increases with pH at constant total metal concentration. The results are interpreted qualitatively in terms of the chemical speciation of the metals in the stream water and competition between metal ions and protons at the plant-water interface. It is suggested that Al, Cu, Zn, Cd and Pb behave according to chemical complexation, whereas redox processes and/or colloidal interactions may be significant for Mn and Fe.     

Reconstructing temporal trends in heavy metal deposition: assessing the value of herbarium moss samples

The use of the herbarium moss archive for investigating past atmospheric deposition of Ni, Cu, Zn, As, Cd and Pb was evaluated. Moss samples from five UK regions collected over 150 years were analysed for 26 elements using ICP-MS. Principal components analysis identified soil as a significant source of Ni and As and atmospheric deposition as the main source of Pb and Cu. Sources of Zn and Cd concentrations were identified to be at least partly atmospheric, but require further investigation. Temporal and spatial trends in metal concentrations in herbarium mosses showed that the highest Pb and Cu levels are found in Northern England in the late 19th century. Metal concentrations in herbarium moss samples were consistently higher than those in mosses collected from the field in 2000. Herbarium moss samples are concluded to be a useful resource to contribute to reconstructing trends in Pb and Cu deposition, but not, without further analysis, for Cd, Zn, As and Ni.     

Metal accumulation in arthropods near a lead/zinc smelter in Arnoldstein, Austria. II. Formicidae

Ants are of considerable importance in the cycling of pollutant metals in contaminated terrestrial ecosystems. However, little is known about their ecophysiological response to chronic (and acute) metal stress, either at the individual or the population level. In the present study, the concentrations of Pb, Cd, Cu, and Zn were compared in 13 species of Formicidae from different sites in the vicinity of a lead/zinc smelter in Arnoldstein, Austria. Results indicate species- and metal-dependent differences in site-specific accumulation patterns. A generalized ranking of metal levels in higher taxa, in decreasing order, is: Formicinae-Dolichoderinae-Myrmicinae. Lead, Cd and Zn body burdens decreased with increasing distance from the emission source, at least in some species, whereas Cu levels appeared to be site-independent in most cases. In general, metal body burdens were higher in summer than in spring, irrespective of site, species or metal. Measured lead levels in Formicidae exceeded previously reported field data by 1 to 2 orders of magnitude, stressing the enormous impact of lead on the Arnoldstein area. A decrease of Cd, Cu and Zn concentrations was recorded in ants collected two years after closure of the smelting complex, but lead levels remained constant. The metal levels were lower in pupae than in workers. The present results indicate differentiated metal regulatory capabilities and strategies in the investigated species, but the inherent bionomics of ants render interpretations of field data difficult and more emphasis should be laid on the ecophysiology of metals in Formicidae.     

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.     

Habitat type-based bioaccumulation and risk assessment of metal and As contamination in earthworms, beetles and woodlice

The present study investigated the contribution of environmental factors to the accumulation of As, Cd, Cu, Pb and Zn in earthworms, beetles and woodlice, and framed within an exposure assessment of the European hedgehog. Soil and invertebrate samples were collected in three distinct habitat types. Results showed habitat-specific differences in soil and invertebrate metal concentrations and bioaccumulation factors when normalized to soil metal concentration. Further multiple regression analysis showed residual variability (habitat differences) in bioaccumulation that could not be fully explained by differences in soil metal contamination, pH or organic carbon (OC). Therefore, the study demonstrated that in bioaccumulation studies involving terrestrial invertebrates or in risk assessment of metals, it is not sufficient to differentiate habitat types on general soil characteristics such as pH and/or OC alone. Furthermore, simple generic soil risk assessments for Cd and Cu showed that risk characterization was more accurate when performed in a habitat-specific way.     

Assessment of heavy metal pollution in surface soils of urban parks in Beijing, China

Assessing the concentration of potentially harmful heavy metals in the soil of urban parks is imperative in order to evaluate the potential risks to residents and tourists. To date, little research on soil pollution in China's urban parks has been conducted. To identify the concentrations and sources of heavy metals, and to assess the soil environmental quality, samples were collected from 30 urban parks located in the city of Beijing. Subsequently, the concentrations of Cu, Ni, Pb and Zn in the samples were analyzed. The investigation revealed that the accumulations of Cu and Pb were readily apparent in the soils. The integrated pollution index (IPI) of these four metals ranged from 0.97 to 9.21, with the highest IPI in the densely populated historic center district (HCD). Using multivariate statistic approaches (principal components analysis and hierarchical cluster analysis), two factors controlling the heavy metal variability were obtained, which accounted for nearly 80% of the total variance. Nickel and Zn levels were controlled by parent material in the soils, whereas Cu, Pb and, in part, Zn were accounted for mainly by anthropogenic activities. The findings presented here indicate that the location and the age of the park are important factors in determining the extent of heavy metal, particularly Cu and Pb, pollution. In addition, the accumulation of Zn did not appear to reach pollution levels, and no obvious pollution by Ni was observed in the soils of the parks in Beijing.     

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.     

Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

Soluble and insoluble fractions of heavy metals in wet and dry atmospheric depositions in Bologna,Italy

Atmospheric depositions were collected monthly using a modified wet and dry sampler (dry deposition was collected on a water surface) located in Bologna, a northern Italian urban area, to evaluate the impact of airborne heavy metals on the local pollution load. Wet deposition samples were filtered and heavy metal contents in soluble and insoluble fractions were determined. The same procedure was applied to the water samples which collected dry deposition. The entire procedure was tested using a certified reference material (CRM), which provided satisfying recovery results. The percentage of heavy metal soluble fraction in dry deposition was generally lower than in wet one; Cd, V, Cu and Zn showed a higher average solubility than Cr, Ni and Pb both in wet and dry deposition. Factor analysis, after a varimax rotation of principal components, suggested possible anthropogenic sources which explain different metal deposition patterns. This data analysis also allowed to distinguish different clusters formed by monthly fluxes of heavy metals.     

Copper, zinc and lead speciation in salt marsh sediments colonised by Halimione portulacoides and Spartina maritima

Total concentrations and fractionation of Cu, Zn and Pb in seven operationally defined phases (exchangeable, carbonates, manganese oxides, organic complexes, amorphous iron oxides, crystalline iron oxides and residual) were determined in sediments colonised by the halophyte species Halimione portulacoides and Spartina maritima in a Tagus estuary salt marsh (Portugal). We aimed to determine whether the speciation of these metals was different in areas colonised by each halophyte. Higher concentrations of Cu, Zn and, in particular Pb, were found in the rhizosphere of S. maritima than in the root sediments of H. portulacoides. Geochemical fractionation of Cu, Zn and Pb in sediments of the salt marsh depended upon the metal, and for Zn and Pb clearly varied with depth and with the colonising species. The higher redox potential observed in sediments colonised by H. portulacoides may in part explain the observed differences in the speciation of Cu, Zn and Pb.