Determination of naturally occurring MTBE biodegradation by analysing metabolites and biodegradation by-products

Methyl tert-butyl ether (MTBE) is one of the main additives in gasoline. Its degradation is known to be difficult in natural environments. In this study, significant MTBE degradation is demonstrated at a contaminated site in Leuna (eastern Germany). Since the extent of the plume appeared to be constant over the last 5 years, an extended study was performed to elucidate the degradation processes. Special attention was paid to the production, accumulation and degradation of metabolites and by-products. Groundwater samples from 105 monitoring wells were used to measure 20 different substances. During the degradation process, several intermediates such as tert-butyl alcohol (TBA), tert-butyl formate, formate and lactate were produced. However, the potentially carcinogenic by-product methacrylate was not detected in several hundred samples. At the Leuna site, MTBE degradation occurred under microaerobic conditions. In contrast to hydrocarbons and BTEX, there was no evidence for anaerobic MTBE degradation. Among the degradation products, TBA was found to be a useful intermediate to identify MTBE degradation, at least under microaerobic conditions. TBA accumulation was strongly correlated to MTBE degradation according to the kinetic properties of both degradation processes. Since maximum degradation rates (v(max)) and k(m) values were higher for MTBE (v(max)=2.3 mg/l/d and k(m)=3.2 mg/l) than for TBA (v(max)=1.35 mg/l/d and k(m)=0.05 mg/l), TBA significantly accumulated as an intermediate by-product. The field results were supported by bench scale model aquifer experiments.     

An Evaluation of Multiple Objective Decision Support Weighting Techniques in Natural Resource Management

Multiple objective decision support (MODS) is a structured framework for evaluating decision alternatives against multiple, and often conflicting, criteria. Its ability to handle complex trade-offs in a variety of quantitative and qualitative units gives it much potential in the field of natural resource management (NRM). A key component of MODS is the process used to obtain information from decision makers on the relative importance of evaluative criteria. Ranking algorithms then use this information to determine the relative value of each decision alternative. This paper explores how practising community based NRM decision makers respond to five generic methods for weighting the criteria. It presents a study in which 55 decision makers throughout five regions in Queensland, Australia, applied MODS to evaluate environmental projects seeking funding under the Australian Natural Heritage Trust. Weighting methods applied include fixed point scoring, rating, ordinal ranking, a graphical method and paired comparisons. Decision makers evaluated each weighting method in terms of ease of use and of how much it helped clarify the decision problem. Results show that decision makers felt uncomfortable applying fixed point scoring and generally preferred to express their preferences through ordinal ranking. This has implications for the types of ranking algorithms that can be applied to evaluate the decision alternatives.     

Is flower scent influencing host plant selection of leaf-galling sawflies (Hymenoptera, Tenthredinidae) on willows?

Though it is known that flower scent not only attracts pollinators but also herbivores, little is known about the importance of flower scent on the distribution of leaf herbivores among individuals within a plant species. In this study we determined the distribution of galls induced by the sawfly Pontania proxima (Serville 1823) (Hymenoptera, Tenthredinidae, Nematinae) on flowering and non-flowering representatives of several clones belonging to Salix fragilis and S. × rubens (Salicaceae). Further, amounts and composition of scent of flowering and non-flowering twigs were compared (dynamic headspace-gas chromatography–mass spectrometry, DHS-GC–MS), and a scent sample collected from flowering twigs of S. fragilis was tested by coupled gas chromatography and electroantennographic detection (GC-EAD) on the antennae of P. proxima females. The results show that the presence of flower catkins on plants led to a higher degree of allocation with galls, but the number of galls differed not between flowering and non-flowering plants. The DHS-GC–MS analyses revealed that the total amount of flower scent emitted per flowering twig is about 90 times higher than the scent emitted by a non-flowering twig. Further, several compounds were emitted only by flowering but not by non-flowering twigs. In the GC-EAD analyses, antennae consistently responded not only to green leaf volatiles, but also to compounds emitted only by the flowers (e.g. 1,4-dimethoxybenzene). These flower scent compounds are suggested to affect the host plant choice by attracting more sawflies from the distance to flowering plants compared to non-flowering plants. The EAD-active compounds emitted from vegetative plant parts are assumed to act as long-distance signals especially when flowers are absent on host plants, e.g. during the oviposition period of the second generation of P. proxima.     

Toxicity of tributyltin to willow trees

BACKGROUND: Tributyltin is an organotin compound, used as an antifouling agent in ship paint, with heavy impact on the marine environment. Contaminated dredged harbor sludge is now dumped on land. The toxicity of tributyltin (TBT) to trees has not yet been quantified. Eventually, a vegetation cover on the dumped sludge could be established for the purpose of non-food cash crop production and phytoremediation. METHODS: The phytotoxicity of tributyltin chloride (TBTCl) and tributyltin hydride (TBTH) was measured at pH 4 and at pH 7 using the willow tree transpiration test. Different pH levels of the nutrient solutions were achieved by adding ammonium salt (low pH) or nitrate (high pH) as nitrogen source. RESULTS AND DISCUSSION: At low pH (pH 4), all trees showed symptoms of poor health. Transpiration decreased at concentrations above or equal to 0.1 mg TBTCl/l and 1 mg TBTH/L. The TBT toxicity was more pronounced at pH 7. The trees survived even the highest dose of 10 mg/l TBTCl or TBTH, although their growth and transpiration was strongly reduced. CONCLUSION: In contrast to other organisms, TBTCl and TBTH were less toxic to higher plants. RECOMMENDATIONS AND OUTLOOK: The toxicity of TBT is no hindrance for establishing vegetation on TBT-contaminated sludge. Phytoremediation and cash crop production could be possible with suitable plants.     

Ozone exposure

Increased tropospheric ozone concentrations cause damage to both human health and the environment. To assess the exposure of forest areas and selected tree species to ozone, it is necessary to calculate the ozone exposure distribution. The present article describes the application of an ozone interpolation model to the calculation of the ozone exposure distribution in combination with forest inventory data. The exposure of forest regions to ozone was assessed by means of an AOT40 map (accumulated ozone exposure over a threshold of 40 ppb). The calculation was performed by hourly running of the model during the summer term and accumulation of the patterns that exceeded 40 ppb. The exposure of the primary Austrian tree species to ozone can be assessed due to the spatial relation of ozone exposure and tree species patterns. This spatial relation also allows the verification of assumptions concerning ozone-related tree damage.     

Biodegradability testing of synthetic ester lubricants--effects of additives and usage

The optimised biodegradability test system "O2/CO2 Headspace Test with GC-TCD" is used for the assessment of synthetic ester lubricants. The effects of both additives and usage on biodegradability are examined and discussed. Ester based cutting fluids and hydraulic fluids with and without additives are used under defined conditions at machine tools and hydraulic and plain bearing test benches. The lubricants are characterised additionally with respect to kinematic viscosity, acidity and elemental composition. Furthermore, a formulated mineral oil is characterised before and after usage at an hydraulic test bench. The results clearly show that the mineral oil is far less biodegradable than the ester oils and that their biodegradability is not affected by usage. Biodegradability of the ester oils is mainly depending on the characteristics of the base fluids and not affected by the additives. Antioxidants are influencing stability respectively biodegradability indirectly, since they prevent oxopolymerisation effects. Other effects of usage on biodegradation are not detected. In this context, the antioxidants ensure ready biodegradability and have a positive effect on the environmental fate of synthetic ester lubricants.     

Determination of selected pharmaceuticals and caffeine in sewage and seawater from Tromsø/Norway with emphasis on ibuprofen and its metabolites

Selected pharmaceuticals, among them analgesics, ss-blockers and anti-depressants as well as caffeine, the anti-bacterial triclosan and the insect repellent N,N-diethyl-3-toluamide (DEET) were determined in different sewage samples (sewage treatment plants, hospital effluents) from Troms?/Norway and in seawater from Troms?-Sound, into which the sewage is discharged. While caffeine, triclosan, ibuprofen and its major metabolites hydroxy- and carboxy-ibuprofen were present in all sewage samples, additional pharmaceuticals were observed in sewage containing hospital effluents. Concentrations were in the range of 20-293 microg/l (caffeine), 0.2-2.4 microg/l (triclosan) and 0.1-20 microg/l (sum ibuprofen + metabolites). In seawater, only caffeine (7-87 ng/l), DEET (0.4-13 ng/l) and ibuprofen + metabolites (sum concentration < LOQ-7.7 ng/l) were detected. Ibuprofen and its metabolites hydroxy- and carboxy-ibuprofen were quantified individually by use of the respective reference compounds. Relative amounts of the three compounds were determined in different types of water showing characteristic patterns, with hydroxy-ibuprofen being the major component in sewage whereas carboxy-ibuprofen was dominant in seawater samples. The patterns which were compared to those observed in similar samples from Germany indicated different transformation behaviour under limnic and marine conditions.     

Potential Effects of Metals in Reacidified Limed Water Bodies in Norway and Sweden

The goal of this work was to assess risk of chemical andbiological effects of metals in reacidified, limed water bodiesin Norway and Sweden. The risk assessment is based on aliterature review and evaluations of water chemical data fromthe 1995 Nordic Lake Survey. Compared to the pre-liming period,it us unlikely that enhanced remobilization of inorganicaluminium (Al) or other toxic metals (metal bomb hypothesis)from the catchment, the lake sediment and/or the streambed willoccur when limed waters reacidify. Rather, the concentrationsin surface waters are expected to be lower than before limingstarted, because of reduced atmospheric inputs of both strongacids and metals as Cd, Hg, Pb, and Zn during the last 10–20 yr. The concentrations in lakes relative to the biologicaleffect levels, as well as the chemical properties of thedifferent metals suggest that the potential biological risksassociated to reacidification of limed lakes decrease in theorder Al > Cd > Pb. The risks associated with Cr, Cu, Fe, Mn, Ni and Zn are very low and do not have to be consideredexcept in waters with known concentrations larger than the lowest biological risk level. Such waters are very rare (<2%). Aluminium is the metal that should be used to set the limit for judging the risk of biological damage due to reacidification of limed surface waters.     

Modelling critical levels of ozone for the forested area of austria modifications of the aot40 concept

GOAL, SCOPE AND BACKGROUND: Ozone is the most important air pollutant in Europe for forest ecosystems and the increase in the last decades is significant. The ozone impact on forests can be calculated and mapped based on the provisional European Critical Level (AOT40 = accumulated exposure over a threshold of 40 ppb, 10,000 ppb x h for 6 months of one growing season calculated for 24 h day(-1)). For Norway spruce, the Austrian main tree species, the ozone risk was assessed in a basis approach and because the calculations do not reflect the health status of forests in Austria, the AOT40 concept was developed. METHODS: Three approaches were outlined and maps were generated for Norway spruce forests covering the entire area of Austria. The 1st approach modifies the AOT40 due to the assumption that forests have adapted to the pre-industrial levels of ozone, which increase with altitude (AOTalt). The 2nd approach modifies the AOT40 according to the ozone concentration in the sub-stomata cavity. This approach is based on such factors as light intensity and water vapour saturation deficit, which affect stomatal uptake (AOTsto). The 3rd approach combines both approaches and includes the hemeroby. The pre-industrial ozone level approach was applied for autochthonous ('natural') forest areas, the ozone-uptake approach for non-autochthonous ('altered') forest areas. RESULTS AND DISCUSSION: The provisional Critical Level (AOT40) was established to allow a uniform assessment of the ozone risk for forested areas in Europe. In Austria, where ozone risk is assessed with utmost accuracy due to the dense grid of monitoring plots of the Forest Inventory and because the continuously collected data from more than 100 air quality measuring stations, an exceedance up to the five fold of the Critical Level was found. The result could lead to a yield loss of up to 30-40% and to a severe deterioration in the forest health status. However, the data of the Austrian Forest Inventory and the Austrian Forest Damage Monitoring System do not reflect such an ozone impact. Therefore, various approaches were outlined including the tolerance and avoidance mechanisms of Norway spruce against ozone impact. Taking into consideration the adaptation of forests to the pre-industrial background level of ozone, the AOT40 exceedances are markedly reduced (1st approach). Taking into account the stomatal uptake of ozone, unrealistic high amounts of exceedances up to 10,000 ppb x h were found. The modelled risk does not correspond with the health status and the wood increment of the Austrian forests (2nd approach). Consolidating the forgoing two approaches, a final map including the hemeroby was generated. It became clear that the less natural ('altered') forested regions are highly polluted. This means, that more than half of the spruce forests are endangered by ozone impact and AOT40 values of up to 30,000 ppb x h occur (3rd approach). CONCLUSIONS: The approaches revealed that a plausible result concerning the ozone impact on spruce forests in Austria could only be reached by combining pre-industrial ozone levels, ozone flux into the spruce needles and the hemeroby of forests.