Distribution of trace element pollutants in a contaminated ecosystem established on metalliferous fluorspar tailings. 3: fluoride

High total soil fluoride (10 000 microg g(-1)) in the metalliferous fluorspar tailings was reflected by elevated concentrations in standing live vegetation (300-1000 microg g(-1)); plant roots (c. 6000 microg g(-1)); plant litter (c. 4000 microg g(-1)); total body concentrations of invertebrates (400-4000 microg g(-1)) and the small mammals Microtus agrestis (120-360 microg g(-1)) and Sorex araneus (140-250 microg g(-1)). Seasonal changes in the standing live vegetation and the availability of soil fluoride to plants are discussed. Seasonal changes in total body concentrations of the small mammals were related to the age structure of the populations as well as dietary levels. In the small mammals, the concentration ratios were < 0.5 at the tailings dam and > 1.1 at the control site, indicating that both species were able to regulate fluoride accumulation at the higher levels of intake. Soft tissue concentrations were, as expected, very low compared to the hard tissues but, still, were generally significantly higher at the tailings dam compared to the control site. Evidence of dental fluorosis was found in Microtus agrestis, but not Sorex araneus.     

Response of a grassland ecosystem to air pollutants. IV. The chemical climate: concentrations of relevant non-criteria pollutants (trace gases and aerosols)

The concentrations of sulphur dioxide, nitric acid, nitrous acid, hydrogen chloride, ammonia and sulphate, nitrate, chloride and ammonium in aerosols were measured continuously for two years at the rural site of Rotenkamp near Braunschweig in south-east Lower Saxony. The level of air pollution registered is typical for rural areas near industrial areas in Central Europe. Long-range transport of polluted air masses from Saxony-Anhalt and Saxony affects air quality when high-pressure areas over Eastern Europe result in easterly winds and reduced vertical exchange due to low inversion layers.     

Distribution of antimony in contaminated grassland: 2--Small mammals and invertebrates

Concentrations of antimony in invertebrates and small mammals from grasslands in the vicinity of an antimony smelter were significantly elevated compared to a control site. Higher concentrations of antimony were recorded in liver, lung and kidney tissue of herbivorous and insectivorous mammals from the contaminated sites. However, there is little evidence of bioaccumulation of antimony in food chains represented by the soil-vegetation-invertebrate-insectivore pathway of the grasslands, and little indication of significant accumulation by herbivorous mammals despite marked contamination of their diet.     

Response of a grassland ecosystem to air pollutants. VI. The chemical climate: concentrations and potential flux densities of relevant criteria pollutants

Of the so-called criteria air pollutants, ozone (O3) and sulfur dioxide (SO2) are relevant to agriculture due to their known toxic (O3, SO2) and fertilizing (SO2) potentials. A proper entity to describe pollutant doses in dose-response relationships is the cumulative flux density absorbed by the respective receptor systems. For nutrient budgets the whole ecosystem acts as receptor; for toxicological considerations, stomatal uptake has to be considered primarily. In Central Europe, the atmospheric inputs of oxidized S (SO2, SO3(2-) and SO4(2-)) have declined from the past, and at present are generally below the nutrient requirements of agroecosystems. In contrast, the phytotoxic potential of O3 has increased during the last decade. Pollutant absorbed doses and weighted concentrations were used to describe the risk potential. It could be shown that these two differ significantly.     

Arsenic in the food chains of a revegetated metalliferous mine tailings pond.

The environmental distribution, transfer and ecotoxicological risk associated with arsenic in a grassland ecosystem established on metalliferous mine tailings has been determined. High levels of arsenic in the mine tailings (630 +/- 34 mg kg-1) were not reflected in live vegetation due to the physico-chemical nature of the tailings which mitigate against plant uptake. However, elevated levels of arsenic were associated with plant litter. Low concentrations of arsenic in herbivorous invertebrates mirrored those found in their food, although there was evidence of minor detrivoral food chain transfer. Dietary exposure of small mammals to arsenic was well below that demonstrated to induce a toxicological response, and tissue concentrations were consistently below analytical detection limits. There appears to be little ecotoxicological risk associated with arsenic residues at the mine site investigated.     

Response of a grassland ecosystem to air pollutants: II--The chemical climate: Fluxes of sedimenting airborne matter

Measurement of the deposition of sedimenting particles requires a sampling device, which avoids simultaneous deposition of gases and aerosols to the collection surface. A sampler constructed for the purpose of collecting rain and sedimenting particles is described and characterized in detail, in particular with regard to its collection efficiency for rain. Its collection properties for gases and aerosols are shown to be negligible. From two years of sampling at different heights it was found that resuspension of particles and co-condensation of gases near the plant canopy may lead to a major overestimation of bulk deposition. As a consequence, the extension towards the canopy of the constant flux layer for sedimenting particles has to be determined experimentally. Bulk deposition of sodium, potassium, magnesium, calcium, lead, copper, cadmium, manganese, iron, ammonium, nitrate, phosphate, sulfate, total sulfur and chloride at Braunschweig-V?lkenrode, Southeast Lower Saxony, Germany, were recorded for six years. During this period a considerable decrease was observed in the deposition of lead, cadmium, nitrate, sulfate and total sulfur.     

Response of grassland ecosystem to air pollutants: I-Experimental concept and site of the Braunschweig grassland investigation program

Temporal changes in spatial distribution and population density of linyphiid spiders were studied in relation to physical factors and deltamethrin spraying in the field. The results of the study have been used to set the conditions necessary when plot size is reduced in field trials. The results showed independence of observations at 7 m from an unsprayed reservoir, with respect to migration, in the week following pesticide application. Soil moisture had a positive effect on trapping success, without having apparent effect on trapping success, without having was found for deltamethrin spraying on wet and dry soil. Shifts in the spatial distribution of spider activity showed a close correlation with crop microclimatic conditions. The effect of trapping on population density was shown to be limited. The results suggest that small plots surrounded by a border of 7 m are appropriate for assessing short term pesticide effects on adult linyphiid spiders in winter wheat.     

Soil amendments reduce trace element solubility in a contaminated soil and allow regrowth of natural vegetation

We tested the effects of three amendments (a biosolid compost, a sugar beet lime, and a combination of leonardite plus sugar beet lime) on trace element stabilisation and spontaneous revegetation of a trace element contaminated soil. Soil properties were analysed before and after amendment application. Spontaneous vegetation growing on the experimental plot was studied by three surveys in terms of number of taxa colonising, percentage vegetation cover and plant biomass. Macronutrients and trace element concentrations of the five most frequent species were analysed. The results showed a positive effect of the amendments both on soil chemical properties and vegetation. All amendments increased soil pH and TOC content and reduced CaCl(2)-soluble-trace element concentrations. Colonisation by wild plants was enhanced in all amended treatments. The nutritional status of the five species studied was improved in some cases, while a general reduction in trace element concentrations of the aboveground parts was observed in all treated plots. The results obtained show that natural assisted remediation has potential for success on a field scale reducing trace element entry in the food chain.     

Distribution and ecotoxicological concerns of persistent organic pollutants in sediment from creek ecosystem

In order to study the distribution and ecotoxicological concerns of persistent organic pollutants, grab sediment samples were collected from different locations across Thane creek, India. Analyses of samples were carried out using gas chromatography (GC)–electron capture detector and GC–mass spectrometry techniques. In organochlorine pesticides (OCPs), DDT (1,1,1,-trichloro-2,2-bis(p-chlorophenyl) ethane), DDE (1,1-dichloro-2,2-bis(p-chlorophenyl) ethylene), DDD (1-chloro-4-(2,2-dichloro-1-(4-chlorophenyl)ethyl) benzene) and α, β, and γ conformer of hexachlorocyclohexane (HCH), and 9 polychlorinated biphenyls (PCBs) congeners were analyzed in surface sediment samples. Concentrations of these pollutants in grab sediment samples may indicate their current use and impact on marine ecosystem. Average concentrations of total DDT (including DDD and DDE), HCH, and Σ₉PCBs were found to be 4.9, 12.5, and 2.9 µg kg^?1(dry weight) respectively. High concentrations of OCPs and PCBs were found at discharge locations in creek compared to other locations. Location-wise distribution of OCPs and PCBs indicates their high concentrations at the waste water receiving point. Data were compared for ecotoxicological impacts based on the levels specified in the sediment quality standards of the US Environmental Protection Agency and the Canadian Council of Ministers of the Environment. γ-HCH was found to have maximum potential to induce ecotoxicological impacts.     

Response of a grassland ecosystem to air pollutants: III--The chemical climate: Vertical flux densities of gaseous species in the atmosphere near the ground

The establishment of element balances for ecosystems presupposes a knowledge of the amounts of the respective element exchanged between the ecosystem and the atmosphere near the ground by determining their vertical flux densities. Any adequate approach to calculate flux densities of gaseous species in the atmosphere has to use micrometeorological techniques. The authors applied the ratiometric method, which is described in detail. Results of flux density calculations for sulfur dioxide, nitrogen dioxide, nitric oxide and ammonia obtained during two years of measurement are discussed with regard to their role in element balances. Flux densities and deposition velocities of ozone are interpreted as functions of meteorological parameters as well as of the biological activity of the canopy. The latter is characterized by the flux density and flux-to-concentration ratio of carbon dioxide.     

Impact of earthworms on trace element solubility in contaminated mine soils amended with green waste compost

The common practice of remediating metal contaminated mine soils with compost can reduce metal mobility and promote revegetation, but the effect of introduced or colonising earthworms on metal solubility is largely unknown. We amended soils from an As/Cu (1150 mgAs kg⁻¹ and 362 mgCu kg⁻¹) and Pb/Zn mine (4550 mgPb kg⁻¹ and 908 mgZn kg⁻¹) with 0, 5, 10, 15 and 20% compost and then introduced Lumbricus terrestris. Porewater was sampled and soil extracted with water to determine trace element solubility, pH and soluble organic carbon. Compost reduced Cu, Pb and Zn, but increased As solubility. Earthworms decreased water soluble Cu and As but increased Pb and Zn in porewater. The effect of the earthworms decreased with increasing compost amendment. The impact of the compost and the earthworms on metal solubility is explained by their effect on pH and soluble organic carbon and the environmental chemistry of each element.     

Factors affecting accumulation of thallium and other trace elements in two wild Brassicaceae spontaneously growing on soils contaminated by tailings dam waste

Thallium is a scarce, highly toxic element. There are several investigations that report Tl accumulation in plants of the family Brassicaceae. These plants could pose a risk in areas where Tl is present at higher concentrations than normal soils. The present study reports analyses of two wild Brassicaceae, Hirschfeldia incana and Diplotaxis catholica, growing spontaneously at five sampling sites moderately polluted with Tl and other trace elements in the Green Corridor of the Guadiamar river, Seville, S. Spain. In general, trace element content was unremarkable in all part plants, despite the concentrations present in soil. Thallium was the only element whose concentration in both plant species was above normal for plants (maximum values of 5.00 mgkg(-1) in H. incana flowers). There were significant positive correlations between total Tl in soil and Tl in both plant species. Transfer Coefficients (TC) for all elements were, in general, <1 for both species, except for Tl in flowers and fruits at some sites. The highest Enrichment Factor (EF) was found for Tl in H. incana fruits (EF = 607) and D. catholica flowers (EF = 321). H. incana was studied in a previous growing season (2004) in the same area, although the rainfall was 3 times more than in the year of the present study (2005), giving a maximum Tl content of 46.5 mgkg(-1) in H. incana flowers. The data presented here show that Tl content of plants growing in semi-arid conditions can be significantly influenced by precipitation. In dry years, plant Tl accumulation may be significantly reduced.     

Mobility of heavy metals from tailings to stream waters in a mining activity contaminated site

In this paper the results of a recent characterization of Rio Piscinas (SW of Sardinia, Italy) hydrological basin are reported. In such area (about 50 km2), previous mining activities caused a serious heavy metal contamination of surface waters, groundwater, soils and biota. Acid mine drainage phenomena were observed in the area. The main sources of contamination are the tailings stored in mine tunnels and abandoned along fluvial banks. A methodological approach was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments samples were collected. XRD analyses were performed for mineralogical characterization, while acid digestion was carried out for determining metal contents. Batch sequential leaching tests were performed in order to assess metal mobility. Also groundwater and stream water were sampled in specific locations and suitably characterized. All information collected allowed the understanding of the effect of tailings on water contamination, thus contributing to the qualitative prediction of pollution evolution on the basis of metal mobility. Finally, a potential remediation strategy of stream water is proposed.     

Use of the modified BCR three-step sequential extraction procedure for the study of trace element dynamics in contaminated soils

The modified BCR three-step sequential extraction procedure was used to examine the temporal dynamics of trace elements in soils contaminated by an accidental spill from an opencast mine in south-west Spain. Soils were mainly contaminated with pyritic sludge and acidic wastewater, whereas some soils were affected only by acidic wastewater. The distributions obtained for both some major (Ca, Fe and Mn) and trace elements (As, Cd, Cu, Pb and Zn) in the sludge and soil samples taken at different times after the accident, 1-3 months and 21 months, were compared. Sequential extractions were useful in identifying different sources of contamination, and in obtaining additional information on the solubility of secondary minerals formed by pyrite oxidation. Thus, the effectiveness of the BCR procedure has proved to be a useful tool for predicting short- and long-term mobility of trace elements, even in complex environmental scenarios.     

Impact of river overflowing on trace element contamination of volcanic soils in south Italy: part II. Soil biological and biochemical properties in relation to trace element speciation

The effect of heavy metal contamination on biological and biochemical properties of Italian volcanic soils was evaluated in a multidisciplinary study, involving pedoenvironmental, micromorphological, physical, chemical, biological and biochemical analyses. Soils affected by recurring river overflowing, with Cr(III)-contaminated water and sediments, and a non-flooded control soil were analysed for microbial biomass, total and active fungal mycelium, enzyme activities (i.e., FDA hydrolase, dehydrogenase, beta-glucosidase, urease, arylsulphatase, acid phosphatase) and bacterial diversity (DGGE characterisation). Biological and biochemical data were related with both total and selected fractions of Cr and Cu (the latter deriving from agricultural chemical products) as well as with total and extractable organic C. The growth and activity of soil microbial community were influenced by soil organic C content rather than Cu or Cr contents. In fact, positive correlations between all studied parameters and organic C content were found. On the contrary, negative correlations were observed only between total fungal mycelium, dehydrogenase, arylsulphatase and acid phosphatase activities and only one Cr fraction (the soluble, exchangeable and carbonate bound). However, total Cr content negatively affected the eubacterial diversity but it did not determine changes in soil activity, probably because of the redundancy of functions within species of soil microbial community. On the other hand, expressing biological and biochemical parameters per unit of total organic C, Cu pollution negatively influenced microbial biomass, fungal mycelium and several enzyme activities, confirming soil organic matter is able to mask the negative effects of Cu on microbial community.     

Effects of incubation on solubility and mobility of trace metals in two contaminated soils

Much research has focused on changes in solubility and mobility of trace metals in soils under incubation. In this experiment, changes in solubility and mobility of trace metals (Pb, Cu and As) and Fe in two contaminated soils from Tampa, Florida and Montreal, Canada were examined. Soils of 30 g were packed in columns and were incubated for 3-80 days under water-flooding incubation. Following incubation, metal concentrations in pore water (water soluble) and in 0.01 M CaCl2 leachates (exchangeable+water soluble) were determined. While both soils were contaminated with Pb (1600-2500 mg kg(-1)), Tampa soil was also contaminated with As (230 mg kg(-1)). Contrast to the low pH (3.8) of Tampa soil, Montreal soil had an alkaline pH of 7.7 and high Ca of 1.6%. Concentrations of Fe(II) increased with incubation time in the Tampa soil mainly due to reductive Fe dissolution, but decreased in the Montreal soil possibly due to formation of FeCO3. The inverse relationship between concentrations of Pb and Fe(II) in pore water coupled with the fact that Fe(II) concentrations were much greater than those of Pb in pore water may suggest the importance of Fe(II) in controlling Pb solubility in soils. However, changes in concentrations of Fe(II), Pb, Cu and As in pore water with incubation time were similar to those in leachate, i.e. water soluble metals were positively related to exchangeable metals in the two contaminated soils. This research suggests the importance of Fe in controlling metal solubility and mobility in soils under water-flooded incubation.     

Impact of river overflowing on trace element contamination of volcanic soils in south Italy: part I. Trace element speciation in relation to soil properties

Volcanic soils affected by different numbers of polluted river flooding events were investigated. Chromium and Cu were the major soil contaminants. Nickel, Fe, Zn and Mn total content never exceeded the Italian mandatory limits. The distribution of Cr and Cu total contents among studied soils indicated that only Cr contamination was related to overflowing events. In polluted soils, sequential chemical extractions revealed a preferential association of Cr and Cu with organic forms. A progressive Cr insolubilization with ageing was observed. Significant amounts of Cr and Cu were extracted by NH(4)-oxalate, suggesting metals association with short-range-order aluminosilicates and organo-mineral complexes. Possible methodological drawbacks in the use of the EU-BCR chemical speciation protocol on volcanic soils are discussed. Micromorphology and SEM/WDS analyses revealed Cr and Cu enriched silt and clay coatings in surface and subsurface soil horizons, suggesting a transfer of metal-rich sediments along the soil pore network with water movement.     

Field effects of pollutants in dynamic environments. A case study on earthworm populations in river floodplains contaminated with heavy metals

In industrialized countries river floodplains can be strongly polluted with heavy metals. Published studies on effects of heavy metal pollution on soil invertebrates in floodplains, however, are inconclusive. This is unexpected since studies in other less dynamic environments reported clear effects at even lower levels of pollution. Flooding induces extra variation in invertebrate biomass and abundance which may reduce the probability to detect heavy metal effects. In this paper we combine reported data from studies on river floodplains in The Netherlands and Belgium and statistically analyze the effect of heavy metals on species composition, biomass, density and individual weight of earthworms. Interaction effects of heavy metal stress and flooding are also considered. The results suggest clear effects of zinc and copper on all variables and interaction of heavy metals and flooding for individual weight.     

Distribution and mobility of metals in contaminated sites. chemometric investigation of pollutant profiles

The distribution and mobility of heavy metals in the soils of two contaminated sites in Piedmont (Italy) was investigated, evaluating the horizontal and vertical profiles of 15 metals, namely Al, Cd, Cu, Cr, Fe. La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr. The concentrations in the most polluted areas of the sites were higher than the acceptable limits reported in Italian and Dutch legislations for soil reclamation. Chemometric elaboration of the results by pattern recognition techniques allowed us to identify groups of samples with similar characteristics and to find correlations among the variables. The pollutant mobility was studied by extraction with water, dilute acetic acid and EDTA and by applying Tessier's procedure. The fraction of mobile species, which potentially is the most harmful for the environment, was found to be higher than the one normally present in unpolluted soils, where heavy metals are, to a higher extent, strongly bound to the matrix.