Toxicity of 2,4-dinitrotoluene to terrestrial plants in natural soils

The presence of energetic materials (used as explosives and propellants) at contaminated sites is a growing international issue, particularly with respect to military base closures and demilitarization policies. Improved understanding of the ecotoxicological effects of these materials is needed in order to accurately assess the potential exposure risks and impacts on the environment and its ecosystems. We studied the toxicity of the nitroaromatic energetic material 2,4-dinitrotoluene (2,4-DNT) on alfalfa (Medicago sativa L.), barnyard grass (Echinochloa crusgalli L. Beauv.), and perennial ryegrass (Lolium perenne L.) using four natural soils varying in properties (organic matter, clay content, and pH) that were hypothesized to affect chemical bioavailability and toxicity. Amended soils were subjected to natural light conditions, and wetting and drying cycles in a greenhouse for 13 weeks prior to toxicity testing to approximate field exposure conditions in terms of bioavailability, transformation, and degradation of 2,4-DNT. Definitive toxicity tests were performed according to standard protocols. The median effective concentration (EC₅₀) values for shoot dry mass ranged from 8 to 229 mg kg^− 1, depending on the plant species and soil type. Data indicated that 2,4-DNT was most toxic in the Sassafras (SSL) and Teller (TSL) sandy loam soils, with EC₅₀ values for shoot dry mass ranging between 8 to 44 mg kg^− 1, and least toxic in the Webster clay loam soil, with EC₅₀ values for shoot dry mass ranging between 40 to 229 mg kg^− 1. The toxicity of 2,4-DNT for each of the plant species was significantly (p ≤ 0.05) and inversely correlated with the soil organic matter content. Toxicity benchmark values determined in the present studies for 2,4-DNT weathered-and-aged in SSL or TSL soils will contribute to development of an Ecological Soil Screening Level for terrestrial plants that can be used for ecological risk assessment at contaminated sites.     

Comparison of toxicity and release rates of Cu and Zn from anti-fouling paints leached in natural and artificial brackish seawater

Biocide-containing anti-fouling paints are regulated and approved according to the added active ingredients, such as Cu. Biocide-free paints are considered to be less environmentally damaging and do not need an approval. Zn, a common ingredient in paints with the potential of causing adverse effects has received only minor attention. Laboratory experiments were conducted in artificial brackish seawater (ASW) and natural brackish seawater (NSW) to quantify release rates of Cu and Zn from biocide-containing and biocide-free labeled eroding anti-fouling paints used on commercial vessels as well as leisure boats. In addition, organisms from three trophic levels, the crustacean Nitocra spinipes, the macroalga Ceramium tenuicorne and the bacteria Vibrio fischeri, were exposed to Cu and Zn to determine the toxicity of these metals. The release rate of Cu in NSW was higher from the paints for professional use (3.2-3.6 µg cm⁻² d^− 1) than from the biocide leaching leisure boat paint (1.1 µg cm⁻² d^− 1). Biocide-free paints did leach considerably more Zn (4.4-8.2 µg cm⁻² d^− 1) than biocide-containing leisure boat paint (3.0 µg cm⁻² d^− 1) and ship paints (0.7-2.0 µg cm⁻² d^− 1). In ASW the release rates of both metals were notably higher than in NSW for most tested paints. The macroalga was the most sensitive species to both Cu (EC₅₀ = 6.4 µg l^− 1) and Zn (EC₅₀ = 25 µg l^− 1) compared to the crustacean (Cu, LC₅₀ = 2000 µg l^− 1 Zn, LC₅₀ = 890 µg l^− 1), and the bacteria (Cu, EC₅₀ = 800 µg l^− 1 and Zn, EC₅₀ = 2000 µg l^− 1). The results suggest that the amounts of Zn and Cu leached from anti-fouling paints may attain toxic concentrations in areas with high boat density. To fully account for potential ecological risk associated with anti-fouling paints, Zn as well as active ingredients should be considered in the regulatory process.     

Trace elements in home-produced eggs in Belgium: Levels and spatiotemporal distribution

The purpose of this study was to evaluate the levels of arsenic, cadmium, lead, copper and zinc in home-produced eggs, soils and kitchen waste samples of private chicken owners in Belgium, and to determine spatiotemporal differences in trace element contents in eggs. Eggs were sampled in all provinces of Belgium in autumn 2006 and spring 2007. A total number of 59 private chicken owners participated in the study. Trace elements were determined by inductively coupled plasma-mass spectrometry except for mercury, which was determined by atomic absorption of mercury vapour. The mean fresh weight concentrations in eggs in autumn and spring respectively were < 8.0 and < 8.0 µg/kg for arsenic, 0.5 and < 0.5 µg/kg for cadmium, 116 and 74 µg/kg for lead, 0.43 and 0.52 mg/kg for copper, 20.3 and 19.2 mg/kg for zinc, and 3.15 and 4.44 µg/kg for mercury. Analysis of variance determined significant differences in some trace element concentrations in eggs among seasons and regions in Belgium. Average concentrations of arsenic, cadmium and mercury corresponded well with values measured in other countries, while copper and zinc concentrations were within the same order of magnitude as in other countries. Average lead concentrations were high compared to concentrations in eggs from other countries and correlated well with lead concentrations in soil, indicating that the soil is an important source. Other sources of trace elements in eggs might be home-grown vegetables and forage (grass and herbs), and indirectly, air pollution.     

Study on the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chloro-phenoxyacetic sodium (MCPA sodium) in natural agriculture-soils of Fuzhou, China using capillary electrophoresis

A new method of analyzing trace 2,4-Dichlorophenoxyacetic acid (2,4-D) and 2-methy-4-chloro-lphenoxyacetic sodium (MCPA sodium) in soils by capillary electrophoresis (CE) has been developed in this study. The optimum analytical conditions including chemical component and concentration of buffer solution, pH, separation voltage and sample injection time were studied in detail. Under the optimum conditions, 2,4-D and MCPA sodium in soils can be speedy separated and determined within 20 min with detection limits of 0.15 µg/g (2,4-D) and 0.25 µg/g (MCPA sodium) , a RSD (n = 6) < 5% and a recovery > 89%.With the help of analytical method developed in this study, the degradations of 2,4-D and MCPA sodium in natural agriculture-soils of Fuzhou were studied. The experimental results indicated that the degradations of 2,4-D and MCPA sodium follow first-order kinetics with degradation constants of 0.1509 day^-1 (2,4-D) and 0.2722 day^-1 (MCPA sodium) respectively. The degradation half-life were calculated to be 4.6 days (2,4-D) and 2.6 days (MCPA sodium) at 27 °C, implied that 2,4-D and MCPA sodium can be speedy degraded in natural agriculture-soils of Fuzhou, China.     

Effect of cadmium, lead and arsenic on the oviposition, hatching and embryonic survival of Biomphalaria glabrata

Biomphalaria glabrata is a widespread freshwater gastropod mollusc. The easy aquaculture of these organisms allow its use as an accessible tool for contamination bioassays. B. glabrata showed marked metabolic responses when exposed to cadmium, lead and arsenic. Those responses could also affect the reproduction of the snails. Taking into account this hypothesis, B. glabrata were exposed for 96 h (acute laboratory bioassays) to different concentrations of cadmium (0.1, 0.05 and 0 mg/L), lead (0.5, 0.1, 0.05 and 0 mg/L) and arsenic (0.5, 0.1, 0.05 and 0 mg/L). Snails were removed from the aquaria while eggs were left in the same contaminant concentrations. The effect of the assayed toxicants on snail reproduction was registered as the alterations of the total number of laid eggs (TNLE), hatching time and embryonic survival.At 0.10 mg/L cadmium significantly decreased the TNLE (p < 0.05) and no embryos survived. The lowest assayed level (0.05 mg/L) of cadmium, delayed the hatching time twice when it was compared with the control group (p < 0.01).Lead decreased the TNLE at 0.5 mg/L level (p < 0.01). The other assayed doses (0.05 and 0.10 mg/L) also decreased embryonic survival significantly (p < 0.05 and p < 0.01 respectively) and extended twice the time to hatching (p < 0.01). The 0.50 mg/L level killed all embryos.Arsenic at all studied concentrations decreased the TNLE (p < 0.05) while the hatching time was increased by 50%. Embryo survival only decreased at the highest level (0.5 mg/L) of arsenic assayed.In summary, the acute exposure (96 h) to cadmium lead and arsenic, altered the reproduction of B. glabrata, modifying the TNLE, hatching time and embryonic survival.     

Anaerobic biotransformation of 2,4-dinitrotoluene with ethanol as primary substrate: Mutual effect of the substrates on their biotransformation

The effect of the initial concentration of 2,4-dinitrotoluene (DNT) on its biotransformation and on the microbial utilization of ethanol was investigated. The culture used in this study was acclimated in a continuous flow laboratory fermentor with 2,4-DNT and ethanol as substrates under strict anaerobic conditions at 35°C. Biochemical Methane Potential (BMP) tests were conducted in an anaerobic respirometer, and the acclimated culture from the fermentor served as the inoculum. 2,4-DNT was completely transformed to 2,4-diaminotoluene (DAT) under anaerobic conditions. Two intermediates, 2-amino-4-nitrotoluene (2-A-4-NT) and 4-amino-2-nitrotoluene (4-A-2-NT), were found during the biotransformation. 2,4-DNT inhibited its own biotransformation as well as the acetogenesis of ethanol. The extent of the inhibition increased with the increase of the initial concentration of 2,4-DNT. Propionate was formed during the fermentation of ethanol without 2,4-DNT or with low initial concentrations of 2,4-DNT. Higher initial concentrations of 2,4-DNT caused a decrease in the extent of formation of propionate with acetate production being favored.     

Maternal levels of organochlorines in two communities in southern Vietnam

Some pesticides and PCBs continue to be reported as environmental problems in some areas of Vietnam. In 2005, a study among delivering women took place in two communities in south-central Vietnam (Khanh Hoa Province), namely the coastal city of Nha Trang and the rural district of Dien Khanh located about 10 km inland. The main findings in plasma (n = 189) were relatively high mean concentrations of p,p′-DDE (12.2 µg/l in Nha Trang and 11.4 µg/l in Dien Khanh) and p,p′-DDT (1.2 µg/l in Nha Trang and 1.1 µg/l in Dien Khanh) with no significant community differences. The ratio of p,p′-DDE/p,p′-DDT (11.5 in Nha Trang/12.7 in Dien Khanh) suggests, as in other Vietnamese OCs studies, a relatively recent use of this pesticide. Mean concentrations of PCB 153 (0.15 µg/l in Nha Trang and 0.10 µg/l in Dien Khanh) and other congeners were low in both communities. Age and parity (all compounds), as well as community of residence for PCB 153, were the most important predictors of plasma OCs concentrations.     

Evaluation of the acute, chronic and teratogenic effects of a mixture of eleven pharmaceuticals on the cnidarian, Hydra attenuata

Pharmaceuticals have recently emerged as novel pollutants of potential concern in the aquatic environment where they are commonly introduced as complex mixtures via municipal effluent. In the present experiment, the freshwater cnidarian Hydra attenuata was exposed to a mixture of 11 pharmaceuticals (ibuprofen, naproxen, gemfibrozil, bezafibrate, carbamazepine, sulfapyridine, oxytetracycline, novobiocin, trimethoprim, sulfamethoxazole and caffeine) up to 10 000 times (×) the concentration found in municipal effluent. Hydra regeneration and teratogenicity was measured, having an IC₅₀ of 781× and was found to be non teratogenic with an A/D value of ∼ 1. Toxicity was investigated using both lethal (based on morphology) and sub-lethal (based on morphology, feeding behaviour, hydranth number and attachment) endpoints. The pharmaceutical mixture incurred a significant decrease in morphology at 0.1, 10 and 100× but a significant increase at 1000×. All parameters were significantly reduced at 10 000×. An EC₅₀ of 425× and 65× based on morphology and feeding respectively and a toxicity threshold (TT) of 3.2× were calculated. When compared to the toxicity of each pharmaceutical exposed individually as previously reported [Quinn B, Gagné F, Blaise C. An investigation into the acute and chronic toxicity of eleven pharmaceuticals found in wastewater effluent on the cnidarian, H. attenuata. Sci Total Environ 2008a; 389: 306-314], the compounds in the mixture were present at concentrations 2 to 3 orders of magnitude lower for the equivalent toxicity (EC₅₀ and TT). These results indicate that pharmaceuticals act additively in a mixture, having sub-lethal effects at environmentally relevant (µg/L-ng/L) concentrations and that their combined concentrations could potentially prove significantly ecotoxic to Hydra and possibly to other aquatic taxa.     

Perfluorinated contaminants in fur seal pups and penguin eggs from South Shetland, Antarctica

Perfluorinated compounds (PFCs) have emerged as a new class of global environmental pollutants. In this study, the presence of perfluorochemicals (PFCs) in penguin eggs and Antarctic fur seals was reported for the first time. Tissue samples from Antarctic fur seal pups and penguin eggs were collected during the 2003/04 breeding season. Ten PFC contaminants were determined in seal and penguin samples. The PFC concentrations in seal liver were in the decreasing order, PFOS > PFNA > PFHpA > PFUnDA while in Adélie penguin eggs were PFHpA > PFUnDA > PFDA > PFDoDA, and in Gentoo penguin eggs were PFUnDA > PFOS > PFDoDA > PFHpA. The PFC concentrations differed significantly between seals and penguins (p < 0.005) and a species-specific difference was found between the two species of penguins (p < 0.005). In our study we found a mean concentration of PFOS in seal muscle and liver samples of 1.3 ng/g and 9.4 ng/g wet wt, respectively, and a mean concentration in Gentoo and Adélie penguin eggs of 0.3 ng/g and 0.38 ng/g wet wt, respectively. PFCs detected in penguin eggs and seal pups suggested oviparous and viviparous transfer of PFOS to eggs and off-springs.     

Short-term exposure to the environmentally relevant estrogenic mycotoxin zearalenone impairs reproduction in fish

Zearalenone (ZON) is one of the worldwide most common mycotoxins and exhibits estrogenic activity in the range of natural steroid estrogens such as 17β-estradiol (E2). The occurrence of ZON has been reported in drainage water, soil, wastewater effluents and rivers, but its ecotoxicological effects on fish have hardly been investigated.In this study the estrogenic potency of the ZON was compared to E2 in a recombinant yeast estrogen screen (rYES) and the effects of waterborne ZON exposure on reproduction, physiology and morphology of zebrafish (Danio rerio) were investigated in a 42-day reproduction experiment. E2 as well as ZON evoked a sigmoid concentration-response curve in the rYES with a mean EC₅₀ of 2 and 500 μg/L, respectively, resulting in an E2:ZON EC₅₀ ratio of 1:250. Exposure to ZON for 21 days reduced relative spawning frequency at 1000 and 3200 ng/L to 38.9 and 37.6%, respectively, and relative fecundity at 100, 320, 1000 and 3200 ng/L to 74.2, 41.7, 43.8 and 16.7%, respectively, in relation to the 21-day pre-exposure period. A 4.4 and 8.1 fold induction of plasma vitellogenin (VTG) was observed in male zebrafish at 1000 and 3200 ng/L ZON, respectively. Exposure to ZON did not affect fertility, hatch, embryo survival and gonad morphology of zebrafish.The results of this study demonstrate that although ZON possesses a moderate estrogenic potency in vitro, it exhibits a comparably strong effect on induction of VTG and reproduction in vivo. This indicates that ZON might contribute to the overall estrogenic activity in the environment and could therefore pose a risk for wild fish in their natural habitat.     

Elevated levels of selenium in the typical diet of Amazonian riverside populations

Selenium (Se) intake is generally from food, whose Se content depends on soil Se and plant accumulation. For humans, adequate Se intake is essential for several selenoenzymes. In the Lower Tapajós region of the Brazilian Amazon, Se status is elevated with large inter-community variability. Se intake in this region, where Hg exposure is among the highest in the world, may be important to counteract mercury (Hg) toxicity.The present study was conducted in 2006 with 155 persons from four communities of the Lower Tapajós. The objectives were: i) to evaluate Se content in their typical diet and drinking water; ii) to compare food Se concentrations with respect to geographic location; and iii) to examine the contribution of consumption of different food items to blood Se.More than 400 local foods and 40 drinking water samples were collected. Participants responded to an interview-administered food frequency questionnaire and provided blood samples. Food, water and blood Se levels were assessed by ICP-MS. Since Brazil nuts may also contain significant levels of barium (Ba) and strontium (Sr), these elements were likewise analyzed in nuts.The highest Se concentrations were found in Brazil nuts, but concentrations were highly variable (median: 13.9 µg/g; range: 0.4-158.4 μg/g). Chicken, game meat, eggs and beef also contained considerable levels of Se, with median concentrations from 0.3 to 1.4 μg/g. There was no particular geographic distribution of food Se. Se concentration in drinking water was very low (< 1.4 µg/L). Blood Se covered a (103-1500 μg/L), and was positively related to regular consumption of Brazil nuts, domestic chicken and game meat. Brazil nuts were found to contain highly variable and often very high concentrations of Ba (88.0 µg/g, 1.9-1437 µg/g) and Sr (38.7 µg/g, 3.3-173 µg/g).Further studies should address multiple nutrient/toxic interactions in the diet and related effects on health.     

Modelling denitrification at the catchment scale

The objective of this work was to evaluate the importance of heterotrophic denitrification in the fate of nitrogen surpluses at the catchment scale. For that purpose we modified the denitrification module of TNT2 model and calibrated the model on a small catchment where denitrification measurements had been performed in different locations. The main interest of the TNT2 model is its ability to simulate the dynamics of the zones where soil and shallow water table interact, making it possible to spatialize the denitrification process. Daily water and nitrogen flux at the outlet were relatively well simulated (Nash of 0.85 and 0.77). In average, the model correctly simulates the denitrification measurements (R = 0.68). Nitrogen flux towards the atmosphere, at the catchment scale (4.70 g N m^− 2 year^− 1), is of the same order of magnitude as the soluble N flux in the stream. The model was able to reproduce the distribution of denitrification in the riparian (mean of 9.26 g N m^− 2 year^− 1) and hillslope (mean of 3.45 g N m^− 2 year^− 1) domains of the catchment. The results confirm the importance of riparian denitrification, but show also that hillslope soils contribute significantly (60%) to the whole catchment denitrification. The variations of denitrification rates, and also of nitrate concentrations in stream were not very well simulated by the model, highlighting the complexity of the spatial and temporal controls of nitrogen dynamics in areas with high inputs of nitrogen fertilizers, especially under organic forms.     

Arsenic microdistribution and speciation in toenail clippings of children living in a historic gold mining area

Arsenic is naturally associated with gold mineralisation and elevated in some soils and mine waste around historical gold mining activity in Victoria, Australia. To explore uptake, arsenic concentrations in children's toenail clippings and household soils were measured, and the microdistribution and speciation of arsenic in situ in toenail clipping thin sections investigated using synchrotron-based X-ray microprobe techniques. The ability to differentiate exogenous arsenic was explored by investigating surface contamination on cleaned clippings using depth profiling, and direct diffusion of arsenic into incubated clippings. Total arsenic concentrations ranged from 0.15 to 2.1 µg/g (n = 29) in clipping samples and from 3.3 to 130 µg/g (n = 22) in household soils, with significant correlation between transformed arsenic concentrations (Pearson's r = 0.42, P = 0.023) when household soil was treated as independent. In clipping thin sections (n = 2), X-ray fluorescence (XRF) mapping showed discrete layering of arsenic consistent with nail structure, and irregular arsenic incorporation along the nail growth axis. Arsenic concentrations were heterogeneous at 10 × 10 µm microprobe spot locations investigated (< 0.1 to 13.3 µg/g). X-ray absorption near-edge structure (XANES) spectra suggested the presence of two distinct arsenic species: a lower oxidation state species, possibly with mixed sulphur and methyl coordination (denoted As^≈ III_{(-S, -CH3)}); and a higher oxidation state species (denoted As^≈ V_(-O)). Depth profiling suggested that surface contamination was unlikely (n = 4), and XRF and XANES analyses of thin sections of clippings incubated in dry or wet mine waste, or untreated, suggested direct diffusion of arsenic occurred under moist conditions. These findings suggest that arsenic in soil contributes to some systemic absorption associated with periodic exposures among children resident in areas of historic gold mining activity in Victoria, Australia. Future studies are required to ascertain if adverse health effects are associated with current levels of arsenic uptake.     

Bacterial responses to Cu-doped TiO2 nanoparticles

The toxicity of Cu-doped TiO₂ nanoparticles (NPs, 20 nm), synthesized by a flame aerosol reactor, to Mycobacterium smegmatis and Shewanella oneidensis MR-1, is the primary focus of this study. Both doped and non-doped TiO₂ NPs (20 nm) tended to agglomerate in the medium solution, and therefore did not penetrate into the cell and damage cellular structures. TiO₂ particles (< 100 mg/L) did not apparently interfere with the growth of the two species in aqueous cultures. Cu-doped TiO₂ NPs (20 mg/L) significantly reduced the M. smegmatis growth rate by three fold, but did not affect S. oneidensis MR-1 growth. The toxicity of Cu-doped TiO₂ NPs was driven by the release of Cu²⁺ from the parent NPs. Compared to equivalent amounts of Cu²⁺, Cu-doped TiO₂ NPs exhibited higher levels of toxicity to M. smegmatis (P-value < 0.1). Addition of EDTA in the culture appeared to significantly decrease the anti-mycobacterium activity of Cu-doped TiO₂ NPs. S. oneidensis MR-1 produced a large amount of extracellular polymeric substances (EPS) under NP stress, especially extracellular protein. Therefore, S. oneidensis MR-1 was able to tolerate a much higher concentration of Cu²⁺ or Cu-doped TiO₂ NPs. S. oneidensis MR-1 also adsorbed NPs on cell surface and enzymatically reduced ionic copper in culture medium with a remediating rate of 61 µg/(liter?OD₆₀₀? hour) during its early exponential growth phase. Since the metal reducing Shewanella species can efficiently “clean” metal-oxide NPs, the activities of such environmentally relevant bacteria may be an important consideration for evaluating the ecological risk of metal-oxide NPs.     

Effect of chromium on the level of IL-12 and IFN-gamma in occupationally exposed workers

Chromium may affect humoral and cellular immunity, acting on T lymphocytes as well as on granulocytes and monocytes cells. Cytokines play an important role in the immune balance. In this study, the level of IL-12 and IFN-γ were evaluated in the sera and PHA/LPS stimulated culture supernatant of human PBMCs of healthy volunteers and occupationally exposed chromium workers. All the workers were highly exposed to chromium having mean of 104.65 ± 77.21 µg/dL (range 23.7-316.8 µg/dL). A suspension of exposed and unexposed human PBMC (0.5 × 10⁶ cells/ml) prepared and cultured in RPMI-1640 supplemented with 10% FCS for 18 h in the presence or absence of LPS (10 ng/ml) which used for stimulation of IL-12 and IFN-γ. The level of IL-12 and IFN-γ were evaluated in the sera samples as well as LPS stimulated and unstimulated culture supernatant of h-PBMCs of chromium exposed workers. In these chromium exposed workers the level of IL-12 was 433.66 ± 197.49 pg/ml and 983.45 ± 330.99 pg/ml in LPS stimulated culture supernatant of normal individuals and highly chromium exposed workers, which was significant (P < 0.05). Although the level of IL-12 was (78.61 ± 61.03 pg/ml to 146.52 ± 46.37 pg/ml) elevated in unstimulated culture supernatant of h-PBMCs of chromium exposed individuals as compared to control, but it was not significant. This observation also suggests that a significant increase in IFN-γ production in LPS stimulated and unstimulated culture supernatant of h-PBMCs of chromium exposed workers as compared to control. However, IFN-γ level have a significant positive correlation between blood chromium level (r = 0.833, t = 6.3872, P 0.05) and exposure time (in years) (r = 0.8916, t = 8.3540, P 0.05) of the occupationally exposed workers.     

Brominated flame retardants in Belgian home-produced eggs: levels and contamination sources

The extent and the sources of contamination with brominated flame retardants (BFRs), such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), in home-produced eggs from free-foraging chicken of Belgian private owners were investigated. Various factors, such as seasonal variability, exposure of chickens through diet (kitchen waste) and soil, and elimination of BFRs through eggs and faeces were assessed. PBDEs were more important than HBCD in terms of concentrations and detection frequency. Concentrations of PBDEs and HBCD in Belgian home-produced eggs were relatively low and comparable with reported levels from other European countries and the US. The concentrations of PBDEs (sum of 13 congeners, including BDE 209) ranged between not detected and 32 ng/g lipid weight (lw), with medians of 3.0 and < 2.0 ng/g lw for the autumn 2006 and spring 2007 campaigns, respectively. When present, BDE 209 was the major PBDE congener (45% of sum PBDEs). When BDE 209 was not detected, the PBDE profile was composed of PentaBDE (BDE 99 and BDE 47), with, in some cases, higher contribution of OctaBDE (BDE 183 and BDE 153). HBCD was also detected (< 0.4 and 2.9 ng/g lw for the autumn 2006 and spring 2007 campaigns, respectively), but at lower detection frequency. The highest HBCD value was 62 ng/g lw. The similarity between profiles and seasonal variations in the concentrations of BFRs in soil and eggs indicate that soil is an important source, but not the sole source, for eggs laid by free-foraging chicken. The contamination of eggs with PBDEs and HBCD appears to be of low concern for public health and the contribution of eggs to the total daily intake of PBDEs appears to be limited (10% for chicken owners and 5% for the average Belgian consumer).     

Enhanced removal of polychlorinated biphenyls from alfalfa rhizosphere soil in a field study: The impact of a rhizobial inoculum

Polychlorinated biphenyls (PCB) are persistent pollutants in soil environments where they continue to present considerable human health risks. Successful strategies to remediate contaminated soils are needed that are effective and of low cost. Bioremediation approaches that include the use of plants and microbial communities to promote degradation of PCB have significant potential but need further assessment under field conditions. The effects of growth of alfalfa (Medicago sativa L.) and inoculation with a symbiotic nitrogen fixing bacterium (Rhizobium meliloti) on the removal of polychlorinated biphenyls (PCB) from rhizosphere soil were evaluated in a field experiment. The initial PCB content of the soil ranged from 414 to 498 µg kg⁻¹. PCB removal for the rhizosphere soil was enhanced in the planted treatments, an average of 36% decrease in PCB levels compared to a 5.4% decrease in the unplanted soil, and further enhanced when plants were inoculated with the symbiotic Rhizobium (an average of 43% decrease) when evaluated at 90 days after planting. Plant biomass production was higher in the inoculated treatment. The total PCB content was increased from 3.30 µg kg⁻¹ to 26.72 µg kg⁻¹ in plant shoots, and from 115.07 µg kg⁻¹ to 142.23 µg kg⁻¹ in roots in the inoculated treatment compared to the planted treatment. Increased colony forming units (cfu) of total heterotrophic bacteria, biphenyl-degrading bacteria and fungi were observed in the rhizosphere of inoculated plants. PCB removal from the rhizosphere soil was not significantly correlated with the direct PCB uptake by the plants in any of the treatments but was significantly correlated with the stimulation of rhizosphere microflora. Changes in the soil microbial community structure in the planted and inoculated treatment were observed by profiling of bacterial ribosomal sequences. Some bacteria, such as Flavobacterium sp., may have contributed to the effective degradation of PCB and deserve further investigation.     

Ingestion of lead from ammunition and lead concentrations in white-tailed sea eagles (Haliaeetus albicilla) in Sweden

In this study we show for the first time that lead poisoning from ammunition is a significant mortality factor for white-tailed sea eagle (WSE) (Haliaeetus albicilla) in Sweden. We analyzed 118 WSEs collected between 1981 and 2004 from which both liver and kidney samples could be taken. A total of 22% of all eagles examined had elevated (> 6 µg/g d.w.) lead concentrations, indicating exposure to leaded ammunition, and 14% of the individuals had either liver or kidney lead concentrations diagnostic of lethal lead poisoning (> 20 µg/g d.w.). Lead concentrations in liver and kidney were significantly correlated. In individuals with lead levels < 6 µg/g, concentrations were significantly higher in kidney than in liver; in individuals with lead levels > 20 µg/g, concentrations were significantly higher in liver. The lead isotope ratios indicate that the source of lead in individuals with lethal concentrations is different from that of individuals exhibiting background concentrations of lead (< 6 µg/g d.w.) There were no significant sex or age differences in lead concentrations. A study from the Baltic reported in principle no biomagnification of lead, but background lead concentrations in WSE liver in this study were still four to > 10 times higher than concentrations reported for Baltic fish from the same time period. In contrast to other biota there was no decrease in lead concentrations in WSE over the study period. The proportion of lead poisoned WSE remained unchanged over the study period, including two years after a partial ban of lead shot was enforced in 2002 for shallow wetlands. The use of lead in ammunition poses a threat to all raptors potentially feeding on shot game or offal. The removal of offal from shot game and alternatives to leaded ammunition needs to be implemented in order to prevent mortality from lead in raptors and scavengers.     

Releasing behavior of zinc in recirculated bioreactor landfill

The purpose of this research was to determine the releasing behavior of zinc in municipal solid waste (MSW) in landfill site with respect to refuse and leachate as an inseparable system. Two simulated bioreactor landfills, one with leachate recirculation and the other without, were operated in room temperature for 320 days. Results showed that the content of zinc in MSW could amount to 591.29 ± 31.33-632.14 ± 18.98 µg g ^− 1 dry weight ^− 1 (DW ^− 1). It exceeded the set standard for “Environmental quality standard for soil” (≤ 500 µg g ^− 1 DW ^− 1) and had high potential environmental risk. The releasing behavior of zinc in refuse mainly experienced speciation of solid-Zn, Zn²⁺, ZnHCO₃⁺, ZnCO₃, Zn(OH)⁺, Zn(OH)₂, Zn(NH₃)₄²⁺, ZnS, etc. Zinc in refuse showed behaviors of staggered migration and retention, which corresponded with the degradation process of refuse in bioreactor landfill. The Zn²⁺ concentration in leachate, which varied correspondingly with releasing behavior of zinc in refuse, were 0.75 mg L ^− 1 to 3.13 mg L ^− 1 and had no great difference in landfill with different operation modes (CL and RL). However, the amount of Zn²⁺ leached out from refuse, which accounted for 28.70 mg and 130.67 mg after 320 day's operation, respectively. More attention should be paid to the inseparable system including refuse and leachate together.     

Analysis of dissolved microcystins in surface water samples from Kovada Lake, Turkey

Dissolved (extracellular) microcystin (MC) concentrations were determined at 3 sampling stations on Lake Kovada, Turkey. The dominant species of cyanobacteria found in August and September of 2006 were Microcystis aeruginosa, Synechococcus sp., Phormidium limosum, Phormidium formosa and Planktothrix limnetica. MC concentrations in water were measured by ELISA and MC variants were examined by HPLC-PDA. Quantitative analysis by HPLC indicated that five MC variants (MC-LR, -RR, -LA, -LW, -LF) were identified in water samples from Kovada Lake. The maximum concentration of dissolved MC-LW was 98.9 µg l^− 1 in October. MC-LR was only detected in May at a concentration of 0.5 µg l^− 1. The cross reactivity of the antibody (MC10E7) to variants such as MC-LA MC-LW & MC-LF was low. Hence the results determined by ELISA were lower than those determined by HPLC in September and October samples due to differences in the specificity of the antibody to MC variants. Total extraceullar MCs was quantified by ELISA and ranged from 0.73 to 48.5 µg MC-LR equivalents l^− 1, which in some cases exceeded the WHO provisional Guideline Value for MC-LR in drinking water. This study confirms that the lakes of Turkey should be monitored for toxic cyanobacteria and for MCs to avoid or reduce the potential exposure of people to these health hazards.