Stoffflussanalyse von quartären Ammoniumverbindungen für die Schweiz

Background, aim, and scope Compared to other micropollutants such as pesticides or pharmaceuticals, less attention has been paid to biocides so far. A prioritisation of the biocides currently used in Switzerland in terms of pollution of waters revealed that quaternary ammonium compounds (QAC), the isothiazolinones chloromethylisothiazolinone and benzisothiazolinone as well as Irgarol exhibit the highest risk potential. The QAC benzalkoniumchloride (BAC) and didecyldimethylammoniumchloride (DDAC-C10) are used in considerable amounts and have a high biological activity. Materials and methods The emissions of selected QAC in waters and soil and the predicted environmental concentrations (PECs) were estimated by means of a substance flow analysis (SFA). The study was based on data from the Swiss products register, on literature, contacts to producers and users as well as on own assumptions. Results and discussion The consumption of BAC (four homologues) and DDAC-C10 in biocidal applications in Switzerland amounts to 90 and 30 tons annually. The most important applications are disinfectants for public health areas, food and feed areas as well as wood preservatives. The total emissions to the environment of all five substances account for approximately 11?t/a. The PECs in surface waters and sediments vary from values slightly lower than the predicted no-effect concentration (PNEC) to roughly three orders of magnitude below the PNEC. However, concentrations above the PNEC are possible at certain locations, particularly downstream of wastewater treatment plants (WWTP) effluents and sewer overflows. Effects on aquatic organisms can therefore not be excluded. Three BAC homologues could not be assessed, as there were no PNEC values available. Conclusions The contribution of emissions from WWTP (punctual emissions) to the environment is only about one tenth and relatively low compared to diffuse emissions. This means that measures for the emission reduction focussing only on end-of-pipe solutions in WWTP will not reduce the emissions significantly. Moreover, for the evaluation of measures, attention has to be paid to the fact that biocides such as the selected QAC are often also applied in non-biocidal applications (e.?g. three times higher volumes in the case of BAC). Recommendations and perspectives SFA serves as a useful tool for early recognition of environmental problems caused by chemicals. This allows recommending appropriate risk reduction measures in the production, the use and the end-of-life phase. It is advisable to use the SFA already in the development stage of chemicals and later on as a quality control tool. The relevant sources of chemicals and sinks in the environment can thus be determined in complex systems, even in absence of extensive measurements or product registers with consumption figures by means of estimations and scenarios.     

Gas-phase reaction of (E)-β-farnesene with ozone: Rate coefficient and carbonyl products

The gas-phase ozonolysis of (E)-β-farnesene was investigated in a 3.91 m³ atmospheric simulation chamber at 296 ± 2 K and relative humidity of around 0.1%. The relative rate method was used to determine the reaction rate coefficient of (4.01 ± 0.17) × 10^?16 cm³ molecule^?1 s^?1, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate coefficients for the reference compounds (γ-terpinene, cis-cyclooctene and 1,5-cyclooctadiene). Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, methylglyoxal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one, and (E)-4-methyl-8-methylenedeca-4,9-dienal. A detailed mechanism for the gas-phase ozonolysis of (E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of (E)-β-farnesene with ozone has a lifetime of around 1 h and is another possible source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.     

Temporal processes that contribute to nonlinearity in vegetation responses to ozone exposure and dose

Ozone interacts with plant tissue through distinct temporal processes. Sequentially, plants are exposed to ambient O₃ that (1) moves through the leaf boundary layer, (2) is taken up into plant tissue primarily through stomata, and (3) undergoes chemical interaction within plant tissue, first by initiating alterations and then as part of plant detoxification and repair. In this paper, we discuss the linkage of the temporal variability of apoplastic ascorbate with the diurnal variability of defense mechanisms in plants and compare this variability with daily maximum O₃ concentration and diurnal uptake and entry of O₃ into the plant through stomata. We describe the quantitative evidence on temporal variability in concentration and uptake and find that the time incidence for maximum defense does not necessarily match diurnal patterns for maximum O₃ concentration or maximum uptake. We suggest that the observed out-of-phase association of the diurnal patterns for the above three processes produces a nonlinear relationship that results in a greater response from the higher hourly average O₃ concentrations than from the lower or mid-level values. The fact that these out-of-phase processes affect the relationship between O₃ exposure/dose and vegetation effects ultimately impact the ability of flux-based indices to predict vegetation effects accurately for purposes of standard setting and critical levels. Based on the quantitative aspect of temporal variability identified in this paper, we suggest that the inclusion of a diurnal pattern for detoxification in effective flux-based models would improve the predictive characteristics of the models. While much of the current information has been obtained using high O₃ exposures, future research results derived from laboratory biochemical experiments that use short but elevated O₃ exposures should be combined with experimental results that use ambient-type exposures over longer periods of time. It is anticipated that improved understanding will come from future research focused on diurnal variability in plant defense mechanisms and their relationship to the diurnal variability in ambient O₃ concentration and stomatal conductance. This should result in more reliable O₃ exposure standards and critical levels.     

Rainfall trends in twentieth century over Kerala,India

Attempts were made to study temporal variation in monthly, seasonal and annual rainfall over Kerala, India, during the period from 1871 to 2005. Longterm changes in rainfall determined by Man-Kendall rank statistics and linear trend. The analysis revealed significant decrease in southwest monsoon rainfall while increase in post-monsoon season over the State of Kerala which is popularly known as the “Gateway of summer monsoon”. Rainfall during winter and summer seasons showed insignificant increasing trend. Rainfall during June and July showed significant decreasing trend while increasing trend in January, February and April. Hydel power generation and water availability during summer months are the concern in the State due to rainfall decline in June and July, which are the rainiest months. At the same time, majority of plantation crops are likely to benefit due to increase in rainfall during the post-monsoon season if they are stable and prolonged.     

First REP-LECOTOX Workshop—ecotoxicogenomics: the challenge of integrating genomics/proteomics/metabolomics into aquatic and terrestrial ecotoxicology

Environmental Science and Pollution Research -     

Heavy metal deposition in the Italian “triangle of death” determined with the moss Scorpiurum circinatum

In this study, a biomonitoring project using the moss Scorpiurum circinatum was carried out to evaluate the deposition and biological effects of heavy metals in the area of Acerra (Naples, S Italy), one of the vertices of the sadly called “Italian triangle of death” owing to the dramatic increase in tumours. The results clearly indicated that the study area is heavily polluted by heavy metals, a large proportion of which is likely present in the atmosphere in particulate form. The ultrastructural organization of exposed samples was essentially preserved, but cell membrane pits, cytoplasm vesicles and concentric multilamellar/multivesicular bodies, probably induced by pollution, were found, which may be involved in the tolerance mechanisms to metal pollution in this moss species. Although severe biological effects were not found at the ultrastructural level in the exposed moss, effects on humans, especially after long-term exposure, are to be expected.     

Bait-lamina assay as a tool to assess the effects of metal contamination in the feeding activity of soil invertebrates within a uranium mine area

As part of the tier 2 of a site-specific risk assessment, this study was the first reporting an intensive in situ application of the bait-lamina assay; two exposure periods (7 and 14 days) were tested during four seasons in ten different sites, within a uranium mine area and at two different depths. The most contaminated sites (by deposition of sludge from the effluent treatment pond) were discriminated after 14 days of exposure because extremely low percentages of feeding activity were recorded. Previous sub-lethal ecotoxicological assays, already had demonstrated that the habitat function of these soils is compromised. Nevertheless, seasonality has proved to have a significant influence on responses. Thus to strength conclusions about the impact of contaminants, the in situ bait-lamina assay should be performed on different annual seasons, at least for temperate regions. It was also found that some environmental parameters (e.g. soil moisture and litter) can act as confounding factors in the bait-lamina assay.     

Testing the capability of the chemistry transport model LOTOS-EUROS to forecast PM10 levels in the Netherlands

Since particulate matter has a direct and adverse impact on public health, a good air quality forecast is important. Several European countries presently use statistical forecasting models, which have their limitations, especially for PM10. An alternative approach is to use a chemistry transport model. Here, the ability of the chemical transport model LOTOS-EUROS to forecast PM10 concentrations in the Netherlands was investigated. LOTOS-EUROS models several PM10 components individually. For sulphate, nitrate and ammonium aerosol the evaluation against observations shows that the modelled annual mean concentrations are within 20% of the measured concentration and that the temporal correlation is reasonably good (R > 0.6). For sea salt the model tended to overestimate the measured concentrations. For elemental carbon the correspondence with black smoke observations was reasonable. However, total PM10 is seriously underestimated, due to unmodelled components (secondary organic aerosols, mineral dust) and missing sources. Therefore, a simple bias correction for four seasons was derived based on the years 2004–2006. The model was compared with the Dutch operational statistical model PROPART and ground-level observations. With bias correction, LOTOS-EUROS performed better than PROPART regarding the timing of events. The major flaw of LOTOS-EUROS was that high values (>50 μg m^?3) were still underestimated. Another advantage of LOTOS-EUROS over the statistical model was the more detailed information in space and time, which facilitates communication of the forecast to the general public.