Assessing the toxicity and teratogenicity of pond water in north-central minnesota to amphibians

BACKGROUND: Incidence of amphibian deformities have increased in recent years, especially in the northern region of the United States. While many factors have been proposed as being responsible for generating deformities (e.g., contaminants, ultraviolet radiation [UV], parasites), no single cause has been definitively established. METHODS: To determine whether waterborne chemicals are responsible for amphibian deformities in ponds in north-central Minnesota, we deployed semipermeable membrane devices (SPMDs) in an impacted and a reference site to accumulate lipophilic contaminants. We then exposed native tadpoles (northern leopard frogs; Rana pipiens) to the SPMD extracts combined with two agricultural pesticides (atrazine, carbaryl) at two levels of UV radiation. RESULTS AND DISCUSSION: UV radiation alone caused a slight increase in hatching success and tadpole growth rate. Deformity rate among hatchlings was high following exposure to SPMD extracts from the reference site in the absence of UV, suggesting that chemicals present at this site are broken down by UV to less harmful forms, or become less bioavailable. Conversely, impacted site SPMD extracts caused hatchling deformities only in the presence of UV, suggesting that UV potentiates the teratogenicity of the compounds present there. Impacted site SPMD extracts significantly increased the number of bony triangles among metamorphs, a common deformity observed at this site. The incidence of skin webbings increased significantly with SPMD extracts from both sites as well as with our pesticide control containing atrazine and carbaryl alone. CONCLUSIONS: Higher deformity rates among tadpoles reared in the presence of UV radiation and SPMD extracts from sites where deformities are common indicates a chemical compound (or compounds) in the water at this site may be causing the deformities. RECOMMENDATIONS AND OUTLOOK: It is important to examine the effects of chemical stressors in the presence of other natural stressors (e.g., UV radiation) to gain a better understanding of how multiple stressors work to impact amphibians and amphibian populations.     

A Biomimetic Approach to the Detection and Identification of Estrogen Receptor Agonists in Surface Waters Using Semipermeable Membrane Devices (SPMDs) and Bioassay-Directed Chemical Analysis (12 pp)

Goal, Scope and Background Some anthropogenic pollutants posses the capacity to disrupt endogenous control of developmental and reproductive processes in aquatic biota by activating estrogen receptors. Many anthropogenic estrogen receptor agonists (ERAs) are hydrophobic and will therefore readily partition into the abiotic organic carbon phases present in natural waters. This partitioning process effectively reduces the proportion of ERAs readily available for bioconcentration by aquatic biota. Results from some studies have suggested that for many aquatic species, bioconcentration of the freely-dissolved fraction may be the principal route of uptake for hydrophobic pollutants with logarithm n-octanol/water partition coefficient (log Kow) values less than approximately 6.0, which includes the majority of known anthropogenic ERAs. The detection and identification of freely-dissolved readily bioconcentratable ERAs is therefore an important aspect of exposure and risk assessment. However, most studies use conventional techniques to sample total ERA concentrations and in doing so frequently fail to account for bioconcentration of the freely-dissolved fraction. The aim of the current study was to couple the biomimetic sampling properties of semipermeable membrane devices (SPMDs) to a bioassay-directed chemical analysis (BDCA) scheme for the detection and identification of readily bioconcentratable ERAs in surface waters. Methods SPMDs were constructed and deployed at a number of sites in Germany and the UK. Following the dialytic recovery of target compounds and size exclusion chromatographic clean-up, SPMD samples were fractionated using a reverse-phase HPLC method calibrated to provide an estimation of target analyte log Kow. A portion of each HPLC fraction was then subjected to the yeast estrogen screen (YES) to determine estrogenic potential. Results were plotted in the form of 'estrograms' which displayed profiles of estrogenic potential as a function of HPLC retention time (i.e. hydrophobicity) for each of the samples. Where significant activity was elicited in the YES, the remaining portion of the respective active fraction was subjected to GC-MS analysis in an attempt to identify the ERAs present. Results and Discussion Estrograms from each of the field samples showed that readily bioconcentratable ERAs were present at each of the sampling sites. Estimated log Kow values for the various active fractions ranged from 1.92 to 8.63. For some samples, estrogenic potential was associated with a relatively narrow range of log Kow values whilst in others estrogenic potential was more widely distributed across the respective estrograms. ERAs identified in active fractions included some benzophenones, various nonylphenol isomers, benzyl butyl phthalate, dehydroabietic acid, sitosterol, 3-(4-methylbenzylidine)camphor (4-MBC) and 6-acetyl-1,1,2,4,4,7-hexamethyltetralin (AHTN). Other tentatively identified compounds which may have contributed to the observed YES activity included various polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives, methylated benzylphenols, various alkylphenols and dialkylphenols. However, potential ERAs present in some active fractions remain unidentified. Conclusions and Outlook Our results show that SPMD-YES-based BDCA can be used to detect and identify readily bioconcentratable ERAs in surface waters. As such, this biomimetic approach can be employed as an alternative to conventional methodologies to provide investigators with a more environmentally relevant insight into the distribution and identity of ERAs in surface waters. The use of alternative bioassays also has the potential to expand SPMD-based BDCA to include a wide range of toxicological endpoints. Improvements to the analytical methodology used to identify ERAs or other target compounds in active fractions in the current study could greatly enhance the applicability of the methodology to risk assessment and monitoring programmes.     

Melting and incineration plants of municipal waste. Chemical and biochemical diagnosis of thermal processing samples (emission,residues)

Control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in emissions and thermal residues from incinerators has been a cause of public concern for more than one decade. Recently, several studies showed that other persistent organic pollutants (POPs) such as coplanar polychlorinated biphenyls (co-PCBs) also have dioxin-like activity and are released from incinerators. Therefore, the present study was aimed at making a risk assessment about dioxin-like activity in extracts of thermal waste residues (e.g. combustion gas; fly ash, slag) from incineration and melting processes in Germany and Japan. For this purpose, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), polychlorinated naphthalenes (PCNs) and polyaromatic hydrocarbons (PAHs) were analyzed by chemical analysis. Additionally, 2, 3, 7, 8-TCDD equivalents (EROD-TEQs) were determined by in vitro Micro-EROD bioassay using rat H4IIE hepatoma cells. EROD-TEQs could be correlated to I-TEQ values (from PCDD/Fs/co-PCBs) analyzed by chemical analysis resulting in a maximal sixfold higher estimate. Our study indicates minor influences of co-PCBs, PAHs and PCNs to the sum of dioxin-like toxicity in the extracts of thermal waste residues as determined here. Furthermore, we showed that the levels of dioxins and co-PCBs contained in slag from melting processes and bottom ashes from incineration processes were lower by 1-2 orders of magnitude than that in fly ash.     

Utilising the Synergy between Plants and Rhizosphere Microorganisms to Enhance Breakdown of Organic Pollutants in the Environment (15 pp)

Background Phytoremediation is a promising technology for the cleanup of polluted environments. The technology has so far been used mainly to remove toxic heavy metals from contaminated soil, but there is a growing interest in broadening its applications to remove/degrade organic pollutants in the environment. Both plants and soil microorganisms have certain limitations with respect to their individual abilities to remove/breakdown organic compounds. A synergistic action by both rhizosphere microorganisms that leads to increased availability of hydrophobic compounds, and plants that leads to their removal and/or degradation, may overcome many of the limitations, and thus provide a useful basis for enhancing remediation of contaminated environments.Main Features The review of literature presented in this article provides an insight to the nature of plant-microbial interactions in the rhizosphere, with a focus on those processes that are relevant to the breakdown and/or removal of organic pollutants. Due consideration has been given to identify opportunities for utilising the plant-microbial synergy in the rhizosphere to enhance remediation of contaminated environments.Results and Discussion The literature review has highlighted the existence of a synergistic interaction between plants and microbial communities in the rhizosphere. This interaction benefits both microorganisms through provision of nutrients by root exudates, and plants through enhanced nutrient uptake and reduced toxicity of soil contaminants. The ability of the plant-microbial interaction to tackle some of the most recalcitrant organic chemicals is of particular interest with regard to enhancing and extending the scope of remediation technologies.Conclusions Plant-microbial interactions in the rhizosphere offer very useful means for remediating environments contaminated with recalcitrant organic compounds.Outlook A better knowledge of plant-microbial interactions will provide a basis for improving the efficacy of biological remediations. Further research is, however, needed to investigate different feedback mechanisms that select and regulate microbial activity in the rhizosphere.     

Survey of dioxin sources in the Baltic Region (extended summary)

The present paper summarises the results of the project: 'Survey of Anthropogenic Sources of Dioxins and Furans in the Baltic Region'. As a part of the project, inventories have been carried out in Estonia, Latvia, Lithuania and Poland by applying the toolkit for quantification of dioxin and furan releases developed by UNEP Chemicals. The main route of direct releases to the environment is emission to air. Total emission to air from Poland was estimated at 490 (88-1,300) g I-TEQ/year, whereas the emissions from Estonia, Latvia and Lithuania were estimated as being 14 (2.4-54), 23 (2.6-63) and 17 (2.6-38) g I-TEQ, respectively. In general, the uncertainty on the estimates is very high, and recommendations regarding further development of the inventories have been made, and measures for reducing the releases have been provided.