Assessment of the natural attenuation of chlorinated ethenes in an anaerobic contaminated aquifer in the Bitterfeld/Wolfen area using stable isotope techniques, microcosm studies and molecular biomarkers

The in situ degradation of chlorinated ethenes was assessed in an anaerobic aquifer using stable isotope fractionation approaches, microcosm studies and taxon specific detection of specific dehalogenating groups of bacteria. The aquifer in the Bitterfeld/Wolfen region in Germany contained all chlorinated ethenes, benzene and toluene as contaminants. The concentrations and isotope composition of the chlorinated ethenes indicated biodegradation of the contaminants. Microcosm studies confirmed the presence of in situ microbial communities capable of the complete dechlorination of tetrachloroethene. Taxon specific investigation of the microbial communities indicated the presence of various potential dechlorinating organisms including Dehalococcoides, Desulfuromonas, Desulfitobacterium and Dehalobacter. The integrated approach, using metabolite spectra, molecular marker analysis and isotope studies, provided several lines of evidence for natural attenuation of the chlorinated ethenes.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

The organic carbon derived from sewage sludge as a key parameter determining the fate of trace metals

In a sandy agricultural soil of south-west of France, continuously cultivated with maize and amended with sewage-sludge over 20 years, the behavior of three trace metals (Cu, Pb, and Zn) was studied during the sludge applications (1974-1993) and after its cessation (1993-1998). Using the delta13C analysis, the dynamics of different sources of organic matter were followed in order to elucidate the influence of the sludge-derived organic matter on the fate of trace metals in the soil and its particle size fractions. This study revealed that sludge-derived organic matter contributed to the formation of macroaggregates through the binding of preexisting microaggregates. These macroagreggates were thus responsible for the accumulation of trace metals in the coarsest fraction as well as for the protection of maize-derived organic matter against biodegradation. After sludge application ceased, the disaggregation of macroaggregates occurred simultaneously with high losses in Cu and Pb. On the contrary, Zn appeared less affected by the cessation of sludge application, with only a location change from coarse to fine fractions.     

Mercury in hair and blood from residents of Phnom Penh (Cambodia) and possible effect on serum hormone levels

High concentration of mercury (Hg) in hair has been reported for Cambodians. To confirm the Hg contamination occurring through intake, Hg concentrations were determined in both hair and blood of residents (n=20) from Phnom Penh, Cambodia. Mercury concentrations in the hair and blood were 0.69-190microg g(-1) dry wt and 5.2-58microg l(-1), respectively, which were lower than those from Hg contaminated or high fish intake regions, but were higher than those from non-contaminated regions. Some female subjects had hair and blood Hg levels exceeding the threshold values for neurotoxic effects. Interestingly, serum estrone and estradiol levels were positively correlated with blood Hg level for both males and females, indicating possible induction of female hormones by Hg exposure in Cambodians.     

Thyroid ultrasound volume, structure and function after long-term high exposure of large population to polychlorinated biphenyls, pesticides and dioxin

We examined 2,046 adults (834 males and 1,212 females aged 20-75 years) from polluted district in East Slovakia (POLL) and two neighboring upstream and upwind located districts of background pollution (BCGR). By ultrasound we estimated the thyroid volume (ThV), hypoechogenicity (HYE), nodules and cysts. Serum levels of thyrotropin (TSH), thyroperoxidase antibodies (TPOab) and thyroglobulin were estimated by electrochemiluminiscent assay and these of 15 PCB congeners, p,p'-DDE, p,p'-DDT, hexachlorobenzene (HCB) and hexachlorocyclohexane by high-resolution gas chromatography. In 320 subjects also selected hydroxylated and methylsulfonated PCB metabolites, polychlorinated dibenzo-dioxins (PCDDs), -furans (PCDFs), five dioxin-like coplanar and eight mono-ortho PCB congeners were estimated. Urinary iodine was measured by automatic microplate method. Reciprocal positive association was found between three major POPs (PCBs, DDE and HCB), the levels of these and also PCDDs plus PCDFs in polluted area being considerably higher than in background pollution area. ThV in groups of males and females from POLL with high PCBs level was significantly higher (p<0.001 by t-test) then in age and sex matched groups from BCGR with low PCBs level. In 1,048 males and females aged <60 years with serum PCBs level >1,000 ng g(-1) lipid (median=1,756 ng g(-1)) a significant effect of age on ThV was found (p<0.01 by ANOVA), while in 921 respective subjects with PCBs level <1,000 ng g(-1) (median=661 ng g(-1)) it was not. These findings supported the view on the additional effect of PCBs on ThV other than that of age. Since the urinary iodine in both districts showed optimal range, any interfering effect of unsatisfactory iodine intake on ThV may be excluded. The frequency of autoimmune thyroiditis signs such as HYE, increased serum level of TPOab and TSH resulting in subclinical or overt thyroid hypofunction was positively associated with sex, age and organochlorine levels. The increase of such frequency in males with POPs levels was much more abrupt than that in females. No considerable differences in the frequency of thyroid nodules as related to PCBs level were found.     

Ambient ultraviolet radiation induces protective responses in soybean but does not attenuate indirect defense

We investigated the effects of ambient ultraviolet (UV) radiation on (i) the performance and chemistry of soybean plants, (ii) the performance of Spodoptera frugiperda and (iii) the foraging behavior of the herbivore's natural enemy Cotesia marginiventris which exploits herbivore-induced plant volatiles (VOC) for host location. The accumulation of protective phenolics was faster in plants receiving ambient UV than in controls exposed to sun light lacking UV. Accordingly, isorhamnetin- and quercetin-based flavonoids were increased in UV exposed plants. No UV effects were found on the performance and feeding behavior of S. frugiperda. Herbivore-damaged plants emitted the same VOC when grown under ambient or attenuated UV for 5, 10 or 30 days. Consequently, C. marginiventris was attracted but did not discriminate between exposed and unexposed soybeans. In summary, ambient UV radiation affected soybean morphology and physiology but did not destabilize interactions between trophic levels.     

Ecological risk assessment of organic waste amendments using the species sensitivity distribution from a soil organisms test battery

Safe amendment rates (the predicted no-effect concentration or PNEC) of seven organic wastes were estimated from the species sensitivity distribution of a battery of soil biota tests and compared with different realistic amendment scenarios (different predicted environmental concentrations or PEC). None of the wastes was expected to exert noxious effects on soil biota if applied according either to the usual maximum amendment rates in Europe or phosphorus demands of crops (below 2 tonnes DM ha⁻¹). However, some of the wastes might be problematic if applied according to nitrogen demands of crops (above 2 tonnes DM ha⁻¹). Ammonium content and organic matter stability of the studied wastes are the most influential determinants of the maximum amendment rates derived in this study, but not pollutant burden. This finding indicates the need to stabilize wastes prior to their reuse in soils in order to avoid short-term impacts on soil communities.     

Comparison of solid-phase and eluate assays to gauge the ecotoxicological risk of organic wastes on soil organisms

Development of methodologies to assess the safety of reusing polluted organic wastes in soil is a priority in Europe. In this study, and coupled with chemical analysis, seven organic wastes were subjected to different aquatic and soil bioassays. Tests were carried out with solid-phase waste and three different waste eluates (water, methanol, and dichloromethane).Solid-phase assays were indicated as the most suitable for waste testing not only in terms of relevance for real situations, but also because toxicity in eluates was generally not representative of the chronic effects in solid-phase.No general correlations were found between toxicity and waste pollutant burden, neither in solid-phase nor in eluate assays, showing the inability of chemical methods to predict the ecotoxicological risks of wastes. On the contrary, several physicochemical parameters reflecting the degree of low organic matter stability in wastes were the main contributors to the acute toxicity seen in collembolans and daphnids.     

Eutrophication and Sedimentation Patterns in Complete Exploitation of Water Resources Scenarios: An Example from Northwestern Semi-arid Mexico

Water requirements to supply human needs lead water stakeholders to store more water during surplus periods to fulfil the demand during – not only – scarcity periods. At the reservoirs, mostly those in semi-arid regions, water level then fluctuates extremely between rises and downward during one single year. Besides of water management implications, changes on physical, chemical and biological dynamics of these drawdown and refilling are little known yet. This paper shows the results, throughout a year, on solids, nutrients (N and P), chlorophyll-a, and sedimentation changes on the dynamics, when the former policy was applied in a reservoir from the semi-arid Northwestern Mexico. Water level sinusoidal trend impinged changes on thermal stratification and mixing, modifying nutrient cycling and primary producer responses. According to nitrogen and phosphorus concentration as well as chlorophyll-a, reservoir was mesotrophic, becoming hypertrophic during drawdown. Nutrient concentrations were high (1.22 ± 0.70 and 0.14 ± 0.12 mg P l⁻¹), increasing phosphorus and lowering N:P significantly throughout the study period, although no intensive agricultural, no urban development, neither industrial activities take place in the watershed. This suggests nutrient recycling complex mechanisms, including nutrient release from the sediment–water interface as the main nutrient pathway when shallowness, at the same time as mineralization, increases. Outflows controlled nitrogen and phosphorus availability on the ecosystem while organic matter depended on river inflows. As on other subtropical aquatic ecosystems, nitrogen limited primary productivity (Spearman correlation R = 0.75) but chlorophyll-a seasonal pattern showed an irregular trend, prompting other no-nutrient related limitants. Shallowness induced a homogeneous temporal pattern on water quality. This observed temporal variability was mainly explained statistically by changes on solids (mineral and organic), chlorophyll-a and flows (62.3%). Annual sedimentation rates of total solids ranged from 11.73 to 16.29 kg m⁻² year⁻¹ with organic matter comprising around 30%. N:P ratio on sedimentation rates were as high as could be expected in a resuspension dominated ecosystem, and spatially inverse related with N:P ratio on bottom sediments. Distance from river inlet into the reservoir reveals a marked spatial heterogeneity on solid and nitrogen sedimentation, showing the system dependence on river inflows and supporting resuspension as the main phosphorus pathway. Accretion rates (2.19 ± 0.40 cm year⁻¹) were not related to hydrological variability but decreased with the distance to the river input. Total sediment accumulation (9,895 tons km⁻² year⁻¹) denotes siltation as other serious environmental problem in reservoirs but possibly not related with operational procedures.