Incomplete aerobic degradation of the antidiabetic drug Metformin and identification of the bacterial dead-end transformation product Guanylurea

Active pharmaceutical ingredients as well as personal care products are detected in increasing prevalence in different environmental compartments such as surface water, groundwater and soil. Still little is known about the environmental fate of these substances. The type II antidiabetic drug Metformin has already been detected in different surface waters worldwide, but concentrations were significantly lower than the corresponding predicted environmental concentration (PEC). In human and mammal metabolism so far no metabolites of Metformin have been identified, so the expected environmental concentrations should be very high.To assess the aerobic biodegradability of Metformin and the possible formation of degradation products, three Organisation of Economic Cooperation and Development (OECD) test series were performed in the present study.In the Closed Bottle test (OECD 301 D), a screening test that simulates the conditions of an environmental surface water compartment, Metformin was classified as not readily biodegradable (no biodegradation). In the Manometric Respiratory test (OEDC 301 F) working with high bacterial density, Metformin was biodegraded in one of three test bottles to 48.7% and in the toxicity control bottle to 57.5%. In the Zahn-Wellens test (OECD 302 B) using activated sludge, Metformin was biodegraded in both test vessels to an extent of 51.3% and 49.9%, respectively.Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MS(n)) showed in the tests vessels were biodegradation was observed full elimination of Metformin and revealed Guanylurea (Amidinourea, Dicyandiamidine) as single and stable aerobic bacterial degradation product. In another Manometric Respiratory test Guanylurea showed no more transformation. Photodegradation of Guanylurea was also negative.A first screening in one of the greatest sewage treatment plant in southern Germany found Metformin with high concentrations (56.8 μg L⁻¹) in the influent (PEC = 79.8 μg L⁻¹), but effluent concentration was much lower (0.76 μg L⁻¹) whereas Guanylurea was detected in a low influent and high effluent concentration (1.86 μg L⁻¹). These data support the experimental findings in the OECD tests and analytical results of other studies, that Metformin under aerobic conditions can bacterially be degraded to the stable dead-end transformation product Guanylurea.     

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.     

Modeling riverine nutrient transport to the Baltic Sea: a large-scale approach

We developed for the first time a catchment model simulating simultaneously the nutrient land-sea fluxes from all 105 major watersheds within the Baltic Sea drainage area. A consistent modeling approach to all these major watersheds, i.e., a consistent handling of water fluxes (hydrological simulations) and loading functions (emission data), will facilitate a comparison of riverine nutrient transport between Baltic Sea subbasins that differ substantially. Hot spots of riverine emissions, such as from the rivers Vistula, Oder, and Daugava or from the Danish coast, can be easily demonstrated and the comparison between these hot spots, and the relatively unperturbed rivers in the northern catchments show decisionmakers where remedial actions are most effective to improve the environmental state of the Baltic Sea, and, secondly, what percentage reduction of riverine nutrient loads is possible. The relative difference between measured and simulated fluxes during the validation period was generally small. The cumulative deviation (i.e., relative bias) [Sigma(Simulated - Measured)/Sigma Measured x 100 (%)] from monitored water and nutrient fluxes amounted to +8.2% for runoff, to -2.4% for dissolved inorganic nitrogen, to +5.1% for total nitrogen, to +13% for dissolved inorganic phosphorus and to +19% for total phosphorus. Moreover, the model suggests that point sources for total phosphorus compiled by existing pollution load compilations are underestimated because of inconsistencies in calculating effluent loads from municipalities.     

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.     

One century of hydrological monitoring in two small catchments with different forest coverage

Long-term data on precipitation and runoff are essential to draw firm conclusions about the behavior and trends of hydrological catchments that may be influenced by land use and climate change. Here the longest continuous runoff records from small catchments (<1 km(2)) in Switzerland (and possibly worldwide) are reported. The history of the hydrological monitoring in the Sperbel- and Rappengraben (Emmental) is summarized, and inherent uncertainties in the data arising from the operation of the gauges are described. The runoff stations operated safely for more than 90% of the summer months when most of the major flood events occurred. Nevertheless, the absolute values of peak runoff during the largest flood events are subject to considerable uncertainty. The observed differences in average, base, and peak runoff can only partly be attributed to the substantial differences in forest coverage. This treasure trove of data can be used in various ways, exemplified here with an analysis of the generalized extreme value distributions of the two catchments. These distributions, and hence flood return periods, have varied greatly in the course of one century, influenced by the occurrence of single extreme events. The data will be made publicly available for the further analysis of the mechanisms governing the runoff behavior of small catchments, as well as for testing stochastic and deterministic models.