Feasibility study of preparation and certification of reference materials for nitrogen dioxide and sulfur dioxide in diffusive samplers

This paper presents the results of a feasability study for the preparation and certification of reference materials (RMs) for nitrogen dioxide (NO(2)) and sulfur dioxide (SO(2)) in diffusive samplers. RMs for NO(2) were prepared by exposure to gas mixtures in a chamber while the RMs for SO(2) were prepared by liquid spiking. Certification of RMs for NO(2) was found feasible with a certified uncertainty of 5.8% and a proposed shelf life of 5 years. The uncertainty was calculated with contribution from the homogeneity of preparation, stability and transport of the CRMs and from an external verification of the certified value. To reach 5.8% of uncertainty, the contribution of the differences between the results of analysis by ion chromatography and colorimetry must be eliminated. It is proposed to solve this by pre-extracting the samplers with water before analysis. The results of this study indicate that the samplers are stable for at least two years before and after exposure when stored in a refrigerator. By contrast, the certification of RMs for SO(2) was found to not be feasible due to instability problems. This instability was attributed to reaction of sulfate on the walls of the samplers. Alternatively, the preparation of RMs by simultaneous exposure to SO(2) and NO(2) has been tested. Satisfying homogeneities has been reached both for NO(2) and SO(2).     

Superoxide dismutase in the marine sponge <Emphasis Type="Italic">Cliona celata</Emphasis>

The aim of this work is to investigate the activity of the antioxidant enzyme superoxide dismutase in the cosmopolitan sponge Cliona celata (Grant, 1826), since this enzyme has been described as a useful biomarker for marine pollution in other marine invertebrates. The quantification of the catalytic activity for superoxide dismutase is quite complex because its substrate is an unstable free radical. Several methods have been developed for this enzymatic activity determination; most of them are based on inhibition of a redox reaction involving the superoxide radical. In this work, two methods are compared, for crude sponge extracts, as far as repeatability, reproducibility and sensibility are concerned. The adrenaline oxidation method seems to be the most adequate for these determinations. Statistical treatment of the data indicates that the reference value for the specific superoxide dismutase activity in C. celata should be in the interval [0–535.5] U/mg of total protein in wet tissues, for normal populations.     

New international long-term ecological research on air pollution effects on the Carpathian Mountain forests,Central Europe

An international cooperative project on distribution of ozone in the Carpathian Mountains, Central Europe was conducted from 1997 to 1999. Results of that project indicated that in large parts of the Carpathian Mountains, concentrations of ozone were elevated and potentially phytotoxic to forest vegetation. That study led to the establishment of new long-term studies on ecological changes in forests and other ecosystems caused by air pollution in the Retezat Mountains, Southern Carpathians, Romania and in the Tatra Mountains, Western Carpathians on the Polish-Slovak border. Both of these important mountain ranges have the status of national parks and are Man & the Biosphere Reserves. In the Retezat Mountains, the primary research objective was to evaluate how air pollution may affect forest health and biodiversity. The main research objective in the Tatra Mountains was to evaluate responses of natural and managed Norway spruce forests to air pollution and other stresses. Ambient concentrations of ozone (O(3)), sulfur dioxide (SO(2)), nitrogen oxides (NO(x)) as well as forest health and biodiversity changes were monitored on densely distributed research sites. Initial monitoring of pollutants indicated low levels of O(3), SO(2), and NO(x) in the Retezat Mountains, while elevated levels of O(3) and high deposition of atmospheric sulfur (S) and nitrogen (N) have characterized the Tatra Mountains. In the Retezat Mountains, air pollution seems to have little effect on forest health; however, there was concern that over a long time, even low levels of pollution may affect biodiversity of this important ecosystem. In contrast, severe decline of Norway spruce has been observed in the Tatra Mountains. Although bark beetle seems to be the immediate cause of that decline, long-term elevated levels of atmospheric N and S depositions and elevated O(3) could predispose trees to insect attacks and other stresses. European and US scientists studied pollution deposition, soil and plant chemistry, O(3)-sensitive plant species, forest insects, and genetic changes in the Retezat and Tatra Mountains. Results of these investigations are presented in a GIS format to allow for a better understanding of the changes and the recommendations for effective management in these two areas.     

Sediment organic matter and meiofauna community response to long-term fish-farm impact in the Ligurian Sea (Western Mediterranean)

Quantitative and qualitative changes in meiofauna community structure were investigated to assess the impact of a fish farm, which was operating continuously for 15 years (La Spezia Gulf, W Mediterranean). Sediment samples were collected in June, July, September, October 2000 and February 2001 for the analysis of phytopigments (chlorophyll-a and phaeopigments), the biochemical composition of organic matter (proteins, carbohydrates and lipids) and related to meiofaunal parameters.

Sediment organic matter reached extremely high concentrations beneath the fish cages when compared to the control. Particularly lipids, carbohydrates and chlorophyll-a were significantly higher in fish-farm sediments. On a long-term basis meiofauna displayed adaptations in sediments beneath the cages resulting in an increase of density. Organic impact on meiofaunal community structure was evident in terms of an increase of the nematodes to copepods (Ne/Co) and nauplius to copepods (Na/Co) ratios in fish farm sediments. Cumaceans and kinorhynchs were encountered in control sediments, but disappeared in fish-farm samples. These data suggest that meiofauna is a sensitive tool for evaluating the effects of organic enrichment in fish farm impacted areas.     

Sediments distribution of trace metals in a coastal lagoon (Southern Sardinia,Mediterranean Sea): assessment of contamination and ecological risk

Coastal lagoons are subject to several sources of contaminations. To shade light on the contamination level of the Santa Gilla lagoon (Tyrrhenian Sea) we investigated the spatial distribution of Cr, Ni, Pb, Zn and Hg in sediments and their correlation with grain size and organic matter contents. Moreover, sediment contamination levels and the ecological risk associated with metal concentration were assessed using different abiotic indicators. The lagoon is characterised by low levels of contamination, with exceptions for Pb and Hg, whose distribution reflects the position of an old chlor-alkali plant and that of an airport. These results indicate that the restoration put in place 30 years ago have not reached the expected target and that the presence of the airport deserves further attention. In the outer section of the lagoon, where clam fishery occurs, we observed low levels of contamination suggesting that such artisanal fishery could somehow help mobilising metals. We conclude that the area exposed to Hg pollution, though tentatively restored, still suffers of a potential risk of ecosystem deterioration. We pinpoint that further investigations on the mobility, bioavailability and toxicity of metals are needed to finally address the actual impairment of the Santa Gilla lagoon.     

Quantification of mass fluxes and natural attenuation rates at an industrial site with a limited monitoring network: a case study

At many "real world" field sites, the number of available monitoring wells is limited due to economic or geological reasons. Under such restricted conditions, it is difficult to perform a reliable field investigation and to quantify primary lines of evidence for natural attenuation (NA), like the documentation of a decrease of contaminant mass flux in flow direction. This study reports the results of a groundwater investigation at a former manufactured gas plant situated in a Quaternary river valley in southwest Germany. The location, infrastructure and aquifer setting are typical of many industrial sites in Germany. Due to difficult drilling conditions (coarse glaciofluvial gravel deposits and an anthropogenic fill above the aquifer), only 12 monitoring wells were available for the investigation and localisation of the contaminant plume. These wells were situated along three control planes (CP) downgradient from the contaminant source, with four wells along each plane. Based on the sparse set of monitoring wells, field scale mass fluxes and first-order natural attenuation rate constants of benzene, toluene, ethylbenzene, and o-xylene and p-xylene (BTEX) and low molecular weight polycyclic aromatic hydrocarbons (PAH) were estimated utilizing different point scale and also a new integral investigation method. The results show that even at a heterogeneous site with a sparse monitoring network point scale investigation methods can provide reliable information on field scale natural attenuation rates, if a dependable flow model or tracer test data is available. If this information is not available, only the new integral investigation method presented can yield adequate results for the quantification of contaminant mass fluxes under sparse monitoring conditions.     

Bootstrap methods for simultaneous benchmark analysis with quantal response data

A primary objective in quantitative risk assessment is the characterization of risk which is defined to be the likelihood of an adverse effect caused by an environmental toxin or chemcial agent. In modern risk-benchmark analysis, attention centers on the “benchmark dose” at which a fixed benchmark level of risk is achieved, with a lower confidence limits on this dose being of primary interest. In practice, a range of benchmark risks may be under study, so that the individual lower confidence limits on benchmark dose must be corrected for simultaneity in order to maintain a specified overall level of confidence. For the case of quantal data, simultaneous methods have been constructed that appeal to the large sample normality of parameter estimates. The suitability of these methods for use with small sample sizes will be considered. A new bootstrap technique is proposed as an alternative to the large sample methodology. This technique is evaluated via a simulation study and examples from environmental toxicology.