Aerobic biodegradability of the calcium channel antagonist verapamil and identification of a microbial dead-end transformation product studied by LC-MS/MS

In recent years pharmaceuticals and personal care products have been detected in increasing concentrations in hospital effluents, sewage treatment plants (STP) as well as in different environmental compartments such as surface water, groundwater and soil. Little is known about the elimination of these substances during sewage treatment or about the formation of potential metabolites in the environment caused by bacterial biotransformation. To assess the biodegradability of the popular cardiovascular drug verapamil and the possible formation of potential microbial degradation products, two tests from the OECD series were used in the present study: the widely used Closed Bottle test (OECD 301 D) and the modified Zahn-Wellens test (OECD 302 B). In the Closed Bottle test, a screening test that simulates the conditions of an environmental surface water compartment, no biological degradation was observed for verapamil at concentrations of 2.33mgl(-1). In the Zahn-Wellens test, a test for inherent biodegradability which allows evaluation of aerobic degradation at high bacterial density, only a partial biological degradation was found. Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MSn) revealed 2-(3,4-dimethoxyphenyl)-2-isopropyl-5-(methylamino)pentane nitrile, already known as D617 (Knoll nomenclature), a metabolite of mammalian metabolism, which is the major degradation product and dead-end transformation product of aerobic degradation of verapamil.     

Solubility of antimony and other elements in samples taken from shooting ranges

The aim of this study was to determine whether or not Sb and other elements (Ni, Cu, Bi, Tl, and Hg) originating from Pb alloy (2-5 wt. % Sb) bullets become more soluble as a result of weathering and what mechanisms possibly control their solubility. Samples were taken from bank material behind the targets at seven Swiss shooting ranges. The samples were dried, sieved, analyzed, and subjected to leaching experiments. Total average concentrations of Sb ranged from 0.5 to 13.8 g kg(-1). In the leaching experiments, Sb was almost exclusively present in solution as the oxidized species Sb(V) in concentrations of up to 5 mg L(-1). The Ca mineral Ca[Sb(OH)6]2 is suggested to control dissolved Sb(V) concentrations in soils at high concentrations. Oxalate extractions suggested that approximately 50% of Sb [predominantly Sb(V)] in the <0.5-mm fraction was adsorbed to Fe (hydr)oxides and possibly other minerals, such as calcite, that are soluble at pH 2. However, it is possible that only a fraction of the oxalate-extractable Sb(V) is reversibly bound to mineral surfaces. It was concluded that the release of Sb is significant and considerably higher than the other elements under investigation and that the mechanisms controlling Sb mobility should be further investigated.     

Temporal and local trends of PCDD/F levels in cow's milk in Switzerland

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined in 30 Swiss cow's milk samples collected at dairy farms in the vicinity to point sources, in rural/alpine areas distant to known sources, and from tanks in large industrial milk processing plants. The contaminant concentrations in samples collected in 2001 were compared to data from analyses conducted in 1984 and 1990/1991 at the same sites. In 2001, the PCDD/F levels in milk from farms near point sources (0.63+/-0.26 ng I-TEQ/kg milk fat) are slightly but significantly higher in than milk from remote areas (0.36+/-0.09 ng I-TEQ/kg milk fat). Consumer milk collected at the processing plants had intermediary levels (0.51+/-0.19 ng I-TEQ/kg milk fat). However, milk in 2001 was significantly less contaminated than the samples collected in 1990/1991 and 1984. This trend is particularly pronounced near point sources but is also apparent in consumer milk and milk from remote areas. No geographical gradient in the atmospheric input of PCDD/F in Switzerland was found. The reduction in PCDD/F levels in dairy milk is paralleled by and correlated to the remediation of known PCDD/F emitting industries, as enforced by federal authorities.     

Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland)

Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.     

CDM Projects under the Kyoto Protocol: A Methodology for Sustainability Assessment – Experiences from South Africa and Uruguay

Under the Clean Development Mechanism (CDM) of the Kyoto Protocol, industrialised countries may finance greenhouse gases mitigation projects in developing countries. The Kyoto Protocol explicitly requires that the CDM shall assist developing countries to achieve sustainable development. However, a clear definition of sustainability for CDM projects is still debatable. MATA-CDM (Multi-Attributive Assessment of CDM Projects) is an approach that facilitates a quantitative assessment of potential projects regarding their contribution to sustainable development. This paper presents applications of MATA-CDM in two different countries. In South Africa, the application was done mainly for academic and demonstrative purposes, whereas in Uruguay it was implemented together with the responsible Designated National Authority (DNA). The work in both countries included the selection of sustainability criteria and measurable indicators. Experts weighted the criteria using personal interviews and a multi-stakeholder workshop. This method was applied to three potential CDM projects in South Africa and one in Uruguay. Results show that under the conditions of this study, the MATA-CDM approach yet fails to yield a perfect quantitative overall sustainability assessment of CDM projects but that several findings could be useful to further develop the approach with the aim to translate the vague term sustainable development to a mainstream project level. Valuable experience was in particular collected with different stakeholder processes to perform criteria weighting.     

Larval competition in weevils Revena rubiginosa (Coleoptera: Curculionidae) preying on seeds of the palm Syagrus romanzoffiana (Arecaceae)

Inter- and intraspecific local resource competition may lead to the selection of specific adaptive individual characteristics to overcome interference competition. A highly selective scenario is predictable for interference competition among seed preying weevil larvae that live in and feed upon a single host seed. This scenario is found in Syagrus romanzoffiana palm seeds which are predated by Revena rubiginosa (Curculionidae) larvae. Although multiple infestation of one seed by weevil larvae can occur, invariably only one individual survives and develops in each host seed. A strong competition between the first instar larvae in a restricted window of host fruit development stages leads to physical interactions of conspecifics by ovicide or direct fighting using falcate mandibles. The occurrence of this type of mandible is synchronized with fruit development and restricted to instars with probable competition, as infestation occurs only while the endocarp is soft. Only after lignification of the endocarp the larva changes into the next instar. Mandibles of subsequent instars differ markedly from those of the first instar. The new mandibles can scrape the solid endosperm but are unable to perforate and kill conspecifics. These findings give strong evidence for the selective pressure of intraspecific competition, where special behaviour, mandible morphology and synchronization of its changes with the seed development contribute to individual benefit that involves the killing of conspecifics, since one host seed can only maintain a single larva throughout its complete development.     

Transient dynamics of pelagic producer-grazer systems in a gradient of nutrients and mixing depths

Phytoplankton-grazer dynamics are often characterized by long transients relative to the length of the growing season. Using a phytoplankton-grazer model parameterized for Daphnia pulex with either flexible or fixed algal carbon:nutrient stoichiometry, we explored how nutrient and light supply (the latter by varying depth of the mixed water column) affect the transient dynamics of the system starting from low densities. The system goes through an initial oscillation across nearly the entire light-nutrient supply space. With flexible (but not with fixed) algal stoichiometry, duration of the initial algal peak, timing and duration of the subsequent grazer peak, and timing of the algal minimum are consistently accelerated by nutrient enrichment but decelerated by light enrichment (decreasing mixing depth) over the range of intermediate to shallow mixing depths. These contrasting effects of nutrient vs. light enrichment are consequences of their opposing influences on food quality (algal nutrient content): algal productivity and food quality are positively related along a nutrient gradient but inversely related along a light gradient. Light enrichment therefore slows down grazer growth relative to algal growth, decelerating oscillatory dynamics; nutrient enrichment has opposite effects. We manipulated nutrient supply and mixing depth in a field enclosure experiment. The experimental results were qualitatively much more consistent with the flexible than with the fixed stoichiometry model. Nutrient enrichment increased Daphnia peak biomass, decreased algal minimum biomass, decreased the seston C:P ratio, and accelerated transient oscillatory dynamics. Light enrichment (decreasing mixing depth) produced the opposite patterns, except that Daphnia peak biomass increased monotonously with light enrichment, too. Thus, while the model predicts the possibility of the "paradox of energy enrichment" (a decrease in grazer biomass with light enrichment) at high light and low nutrient supply, this phenomenon did not occur in our experiment.     

Application of a novel modeling tool with multistressor functionality to support management of organic contaminants in the Baltic Sea

Organic contaminants constitute one of many stressors that deteriorate the ecological status of the Baltic Sea. When managing environmental problems in this marine environment, it may be necessary to consider the interactions between various stressors to ensure that averting one problem does not exacerbate another. A novel modeling tool, BALTSEM-POP, is presented here that simulates interactions between climate forcing, hydrodynamic conditions, and water exchange, biogeochemical cycling, and organic contaminant transport and fate in the Baltic Sea. We discuss opportunities to use the model to support different aspects of chemicals management. We exemplify these opportunities with a case study where two emission-reduction strategies for a chemical used in personal care products (decamethylcyclopentasiloxane) are evaluated, and where the confounding influence of future climate change and eutrophication on the impact of the emission-reduction strategies are assessed.