Acute toxicity tests with Daphnia magna, Americamysis bahia, Chironomus riparius and Gammarus pulex and implications of new EU requirements for the aquatic effect assessment of insecticides

Threshold concentrations for treatment related effects of 31 insecticides, as derived from aquatic micro-/mesocosm tests, were used to calibrate the predictive value of the European Tier-1 acute effect assessment on basis of laboratory toxicity tests with Daphnia magna, Chironomus spp., Americamysis bahia and Gammarus pulex. The acute Tier-1 effect assessment on basis of Daphnia (EC(50)/100) overall was protective for organophosphates, carbamates and most pyrethroids but not for neonicotinoids and the majority of insect growth regulators (IGRs) in the database. By including the 28-day water-spiked Chironomus riparius test, the effect assessment improves but selecting the lowest value on basis of the 48-h Daphnia test (EC50/100) and the 28-day Chironomus test (NOEC/10) is not fully protective for 4 out of 23 insecticide cases. An assessment on basis of G. pulex (EC(50)/100) is sufficiently protective for 15 out of 19 insecticide cases. The Tier-1 procedure on basis of acute toxicity data (EC(50)/100) for the combination of Daphnia and A. bahia and/or Chironomus (new EU dossier requirements currently under discussion) overall is protective to pulsed insecticide exposures in micro-/mesocosms. For IGRs that affect moulting, the effect assessment on basis of the 48-h Chironomus test (EC(50)/100) may not always be protective enough to replace that of the water-spiked 28-day C. riparius test (NOEC/10) because of latency of effects.     

Use of Remote Sensing Techniques to Determine the Effects of Grazing on Vegetation Cover and Dune Elevation at Assateague Island National Seashore: Impact of Horses

The effects of grazing by feral horses on vegetation and dune topography at Assateague Island National Seashore were investigated using color-infrared imagery, lidar surveys, and field measurements. Five pairs of fenced and unfenced plots (300 m²) established in 1993 on sand flats and small dunes with similar elevation, topography, and vegetation cover were used for this study. Color-infrared imagery from 1998 and field measurements from 2001 indicated that there was a significant difference in vegetation cover between the fenced and unfenced plot-pairs over the study period. Fenced plots contained a higher percentage of vegetation cover that was dominated by American beachgrass (Ammophila breviligulata). Lidar surveys from 1997, 1999, and 2000 showed that there were significant differences in elevation and topography between fenced and unfenced plot-pairs. Fenced plots were, on average, 0.63 m higher than unfenced plots, whereas unfenced plots had generally decreased in elevation after establishment in 1993. Results demonstrate that feral horse grazing has had a significant impact on dune formation and has contributed to the erosion of dunes at Assateague Island. The findings suggest that unless the size of the feral horse population is reduced, grazing will continue to foster unnaturally high rates of dune erosion into the future. In order to maintain the natural processes that historically occurred on barrier islands, much larger fenced exclosures would be required to prevent horse grazing.     

Xenoestrogens in the River Elbe and its tributaries

4-Alkylphenols, 4-alkylphenol ethoxylates, 4-alkylphenoxy carboxylates, bisphenol A, bisphenol F, 4-hydroxyacetophenon, 4-hydroxybenzoic acid and steroid hormones were analyzed in water samples of the River Elbe and its tributaries Schwarze Elster, Mulde, Saale, Havel and Schwinge. Additionally, freshly deposited sediments (FDS, composite samples) of the River Elbe and its tributaries were analyzed. The concentrations in water samples ranged from (in ng/l): bisphenol A 4 to 92, branched nonylphenol 13 to 87, branched nonylphenol ethoxylates <0.5 to 120, 4-tert. nonylphenoxy carboxylates <10 to 940 and 4-hydroxybenzoic acid 4 to 12. Steroid hormones were only detected in the Czech tributaries Jizera and Vltava in concentrations near the limit of quantification. In FDS samples the concentrations amounted to (in g/kg d.w.): bisphenol A 10-380, branched nonylphenol 27-430, branched nonylphenol ethoxylates 24-3700, nonylphenoxy carboxylates <50 and 4-hydroxybenzoic acid 23-4400. Increased bisphenol A concentrations were found in water and FDS samples taken from the Czech-German border at Schmilka and the mouth of the Schwinge (only water sample). According to studies conducted in the Elbe Estuary and the German Bight, the River Elbe must be considered as a major source of pollution for the North Sea in respect of the compounds analyzed. A comparison of bisphenol A concentrations, 4-alkylphenols and the corresponding ethoxylates analyzed in the River Elbe and its tributaries with those found in other German surface waters indicated a low level of contamination. The evaluation of the data based on LOEC-values indicated that the concentrations were well below the effectivity threshold for some 4-alkylphenols. According to recent ecotoxicological investigations, for example, with prosobranch snails, bisphenol A concentrations found in water samples of the River Elbe and its tributaries may well be detrimental to aquatic organisms. On the basis of the monitoring data and its implications for estrogenic potency the inclusion of bisphenol A in the list of priority substances (European Union Directive 2000/60/EC, Annex X) should be considered.     

Stream Invertebrate Communities, Water Quality, and Land-Use Patterns in an Agricultural Drainage Basin of Northeastern Nebraska, USA

We used invertebrate bioassessment, habitat analysis, geographic information system analysis of land use, and water chemistry monitoring to evaluate tributaries of a degraded northeast Nebraska, USA, reservoir. Bimonthly invertebrate collections and monthly water chemistry samples were collected for two years on six stream reaches to identify sources contributing to reservoir degradation and test suitability of standard rapid bioassessment methods in this region. A composite biotic index composed of seven commonly used metrics was effective for distinguishing between differentially impacted sites and responded to a variety of disturbances. Individual metrics varied greatly in precision and ability to discriminate between relatively impacted and unimpacted stream reaches. A modified Hilsenhoff index showed the highest precision (reference site CV = 0.08) but was least effective at discriminating among sites. Percent dominance and the EPT (number of Ephemeroptera, Plecoptera, and Trichoptera taxa) metrics were most effective at discriminating between sites and exhibited intermediate precision. A trend of higher biotic integrity during summer was evident, indicating seasonal corrections should differ from other regions. Poor correlations were evident between water chemistry variables and bioassessment results. However, land-use factors, particularly within 18-m riparian zones, were correlated with bioassessment scores. For example, there was a strong negative correlation between percentage of rangeland in 18-m riparian zones and percentage of dominance in streams (r ² = 0.90, P < 0.01). Results demonstrate that standard rapid bioassessment methods, with some modifications, are effective for use in this agricultural region of the Great Plains and that riparian land use may be the best predictor of stream biotic integrity.     

MEASURING IMPACTS OF WATER RESOURCE DEVELOPMENTS ON THE HUMAN ENVIRONMENT1

The parameters and the measurement procedures described in this paper are seen as being part of the first stage in development of the human environment assessment process. Additional parameters need to be identified, and methods of measuring impacts reflected by the parameters must be developed and refined. Considerations of the human environment and those elements of the natural environment that are of importance to people must be included as an integral part of the environmental impact assessment process. Therefore, there is a need for continuing to identify parameters of the human environment and to develop methods of measuring impacts so that these considerations will become a well-integrated part of the environmental impact assessment process.     

Benzene Exposure Assessment at Indoor, Outdoor and Personal Levels. The French Contribution to the Life MACBETH Programme

Many VOC represent hazards to human health through chronic exposure. Recent European and world-wide legislation proposes limit values for ambient concentrations of these compounds. However, very little experimental data exists for true population exposure. In 1996, the European MACBETH initiative set out to measure population exposure to benzene in six European cities. This study details the French contribution to this program. Six campaigns were carried out, each comprising measurements at 100 outdoor sites and the participation of 50 non-smoking volunteers who wore personal samplers and had passive monitors installed in their homes. Iso-concentration maps were drawn for each campaign and the results showed that outdoor concentrations were significantly lower than indoors. Almost 75% of the volunteers were exposed to mean concentrations higher than the limit value of 5µgm³. It is demonstrated that personal exposure levels cannot be deduced simply by combining indoor and outdoor background concentrations. It is also shown that there is need for better knowledge of the contributions to overall exposure of outdoor microenvironments and the authors hope that future European directives will take this into account.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

Electrolytic debromination of PBDEs in DE-83 technical decabromodiphenyl ether

Electrochemical debromination of the commercial decabromodiphenyl ether flame retardant DE-83 in partly aqueous tetrahydrofuran (THF) solution gave lower brominated congeners by sequential loss of bromine atoms. Hydrodebromination was most facile for the most heavily brominated congeners. It involves initial electron transfer and proton transfer from water, rather than hydrogen atom abstraction from THF, as shown by experiments with deuterated water. The product distribution from electrolysis involves preferential loss of bromine meta- and para- to the ether linkage, comparable with the products of metabolism of BDE-209 in various organisms. Significantly, the environmentally relevant congeners BDE-47, BDE-99, and BDE-154 were not major products of debromination of BDE-209 by the electron transfer mechanism.     

Some issues relating to the use of perfluorooctanesulfonate (PFOS) samples as reference standards

Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.