The effect of emergent macrophytes on the dynamics of sulfur species and trace metals in wetland sediments

This study focuses on the effect of plants on the biogeochemistry of sulfur species and the mobility of heavy metals in wetland sediments. Results showed that, in the presence of plants, sediments had elevated sulfate concentrations in the rhizosphere during the growing season, ranging from 0.2 to 6.20 mmol L(-1), whereas only a small difference in the sulfate profiles between vegetated and non-vegetated sediments was observed during senescence. Based on the sulfate concentration increase, the oxygen release rate from the roots to achieve the corresponding oxidation of sulfide was estimated as 0.85 g m(-2) day(-1). Evapotranspiration-induced advection is a major contributor to the transport of sulfate from the water column into the sediments, and also allows dissolved trace metals (i.e. Cd, Pb, and Zn) to be transported into the sediments and react with the acid volatile sulfide pool, resulting in the immobilization of trace metals in these sediments.     

Influence of hydrology on heavy metal speciation and mobility in a Pb-Zn mine tailing

Among the inorganic toxicants of greatest concern in mine tailings, Pb, Zn, Cu, Cd and As figure prominently due to their abundance and potential toxicity. Here we report on their biolability and solid-phase speciation in two sediment cores subject to variable hydrological regimes at an abandoned pyritic mine tailing. The oxic conditions of well-drained sediments induced pyrite oxidation and the subsequent liberation of H+, SO4(2-) and considerable quantities of Fe(III), which precipitated as goethite. Solubility of Pb, Zn, Cu and Cd was closely coupled to pH and goethite presence. Metal lability was particularly low in zones of neutralization, formed by the accumulation of calcite, first carried then deposited by percolating waters in both saturated and unsaturated cores. We conclude that differential hydrology induces variable heavy metal speciation and biolability in Pb-Zn mine tailings, and suggest that site-specific risk assessments must account for past and present hydrological regimes.     

Non-destructive pollution exposure assessment in the European hedgehog (Erinaceus europaeus): II. Hair and spines as indicators of endogenous metal and As concentrations

The role of hair and spines of the European hedgehog as non-destructive monitoring tools of metal (Ag, Al, Cd, Co, Cr, Cu, Fe, Ni, Pb, Zn) and As pollution in terrestrial ecosystems was investigated. Our results showed that mean pollution levels of a random sample of hedgehogs in Flanders are low to moderate. Yet, individual hedgehogs may be at risk for metal toxicity. Tissue distribution analyses (hair, spines, liver, kidney, muscle and fat tissue) indicated that metals and As may reach considerable concentrations in external tissues, such as hair and spines. Positive relationships were observed between concentrations in hair and those in liver, kidney and muscle for Al, Co, Cr, Cu, and Pb (0.43 < r < 0.85). Spine concentrations were positively related to liver, kidney and muscle concentrations for Cd, Co, Cr, Cu and Pb (0.37 < r < 0.62). Hair Ag, As, Fe and Zn and spine Ag, Al, As and Fe were related to metal concentrations in one or two of the investigated internal tissues (0.31 < r < 0.45). The regression models presented here may be used to predict metal and As concentrations in internal tissues of hedgehogs when concentrations in hair or spines are available. The present study demonstrated the possibility of using hair and spines for non-destructive monitoring of metal and As pollution in hedgehogs.     

Cosorption study of organic pollutants and dissolved organic matter in a soil

In this study we have evaluated the effects of dissolved organic matter (DOM) on sorption of imidacloprid, 3,4-dichloroaniline (3,4-DCA) and 4-bromoaniline (4-BA) on a typical calcareous soil (Luvic Xerosol) from south-eastern Spain. Two different types of DOM were used, that is to say, dissolved natural organic matter extracts from a commercial peat (DNOM) and a high-purity tannic acid (TA) solution. The experiments were carried out in a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results indicated that the presence of both DNOM and TA, over a concentration range of 15-100 mg L(-1), produced an increase in the amount of 3,4-DCA and 4-BA sorbed and a decrease in the amount of imidacloprid retained on the soil studied. A modified distribution coefficient, K(doc), has been proposed as a safer parameter for soil sorption predictions of organic pollutants and it could be of help to model the fate of these in the environment.     

Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.     

Aquatic risk assessment of the new rice herbicide profoxydim

A tiered protocol for assessing ecological risks has been applied to the rice pesticide profoxydim. The initial assessment (Tier I) was based on toxicity exposure ratio (TER) calculations based on laboratory data using a worst-case rice scenario. The first refinement (Tier II) was based on direct toxicity assessment (DTA) of water samples collected during a field-mesocosm study. Finally, a higher-tier assessment on the in situ assessment of paddy community responses (field-mesocosm-Tier III) was performed. A successive application of three pesticides, the herbicides azimsulfuron, propanil and the insecticide malathion, was used as reference controls. The refined assessments indicated a lower risk than that predicted from TER estimations. DTA-based Tier II showed toxicity effects only for concentrations above the recommended dose of profoxydim. Effects for reference controls were observed in DTA which were not expected from Tier I. The field-mesocosm study confirmed these effects but also showed that they were transient and of low relevance.     

Biodegradation studies of selected priority acidic pesticides and diclofenac in different bioreactors

The biodegradation of selected priority acidic pesticides MCPP, MCPA, 2,4-D, 2,4-DP and bentazone and the acidic pharmaceutical diclofenac was investigated using a membrane bioreactor (MBR) and a fixed-bed bioreactor (FBBR). A pilot plant MBR was fed with raw water spiked with the selected compounds. The experiment was repeated every week during four weeks to enhance the adaptation of microorganisms. In order to further study the biodegradability of these compounds, degradation studies in a FBBR were carried out. All the samples were analysed by solid phase extraction-gas chromatography-mass spectrometry (SPE-GC-MS). The results indicate that in the MBR compounds except for bentazone were eliminated within the first day of the experiment at rates ranging from 44% to 85%. Comparing these results with the degradation rates in the FBBR showed that in the latter only MCPP, MCPA 2,4-D and 2,4-DP were degraded after a much longer adaptation phase of microorganisms.     

Passive air sampler as a tool for long-term air pollution monitoring: Part 1. Performance assessment for seasonal and spatial variations

The potential of passive air sampling devices (polyurethane foam disks) to assess the influence of local sources on the quality of the surrounding environment was investigated. DEZA Valasske Mezirici, a coal tar and mixed tar oils processing plant, and Spolana Neratovice, a chemical factory with the history of high production of organochlorinated pesticides (OCPs), were selected as the point sources of PAHs, and OCPs, respectively. Levels of PCBs, OCPs and PAHs were determined for all sampling sites and sampling periods. The study brought useful data about the air concentrations of POPs in the investigated regions. More important, it provided information on the transport and fate of POPs in the vicinity of local sources of contamination useful for the estimation of their influence. Very good capability of passive samplers to reflect temporal and spatial fluctuation in concentrations of persistent organic pollutants in the ambient air was confirmed which makes them applicable for monitoring on the local scale.     

Passive air sampler as a tool for long-term air pollution monitoring: Part 2. Air genotoxic potency screening assessment

The capability of passive air sampling to be employed in the evaluation of direct genotoxicity of ambient air samples was assessed. Genotoxic effects of the total extracts from the polyurethane foam filters exposed for 28 days during a regional passive air sampling campaign were investigated. Twenty sampling sites were selected in Brno city on the area of approximately 20x20 km in October and November 2004. Brno is the second largest city of the Czech Republic, highly industrialized with approximately 370,000 of permanent inhabitants. The levels of PAHs, PCBs, and chlorinated pesticides were determined in all samples. Fraction of each extract was also assayed in the bacterial genotoxicity test using Escherichia coli sulA::lacZ. Complete dose-response relationships of the air extracts were determined. The statistical analysis showed significant correlation between observed biological effects and PAHs concentrations in samples.     

Bioassay for determining sensitivity to sulfosulfuron on seven plant species

This study presents a bioassay procedure, based on the root and shoot growth parameters, for the determination of the herbicide sulfosulfuron (1-(4,6 dimethoxypyrimidin-2-yl)-3-(2-ethylsulfonylimidazo[1,2-a]pyridin-3-ylsulfonil)urea) sensitivity on seven vegetal species. Plant response to sulfosulfuron was calculated with the equations fitted to the root growth data as a function of the logarithm of the herbicide concentration by non-linear regression and was used to calculate the doses for 10, 30 and 50% inhibition of root growth (EC10, EC30 and EC50). The results indicate that the phytotoxic effect of sulfosulfuron in all the species assayed followed the order: flax > maize > onion > vetch > lepidium sativum > tomato > barley. These species showed phytotoxicity at low levels of sulfosulfuron and flax appeared to be the most susceptible species to sulfosulfuron (0.001 mg/L).