Trends of perfluorochemicals in Greenland ringed seals and polar bears: Indications of shifts to decreasing trends

Time-series of perfluorinated alkylated substances (PFASs) in East Greenland polar bears and East and West Greenland ringed seals were updated in order to deduce whether a response to the major reduction in perfluoroalkyl production in the early 2000s had occurred. Previous studies had documented an exponential increase of perfluorooctane sulphonate (PFOS) in liver tissue from both species. In the present study, PFOS was still the far most dominant compound constituting 92% (West Greenland ringed seals), 88% (East Greenland ringed seals) and 85% (East Greenland polar bears). The PFOS concentrations increased up to 2006 with doubling times of approximately 6 years for the ringed seal populations and 14 years in case of polar bears. Since then a rapid decrease has occurred with clearing half-lives of approximately 1, 2 and 4 years, respectively. In polar bears perfluorohexane sulphonate (PFHxS) and perfluorooctane sulphonamide (PFOSA) also showed decreasing trends in recent years as do perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA). For the West Greenland ringed seal population perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), PFDA and PFUnA peaked in the mid 2000s, whereas PFNA, PFDA and PFUnA in the East Greenland population have been stable or increasing in recent years. The peak of PFASs in Greenland ringed seals and polar bears occurred at a later time than in Canadian seals and polar bears and considerably later than observed in seal species from more southern latitudes. We suggest that this could be explained by the distance to emission hot-spots and differences in long-range transport to the Arctic.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Extractability of elements in sugar maple xylem along a gradient of soil acidity

Dendrochemistry has been used for the historical dating of pollution. Its reliability is questionable due primarily to the radial mobility of elements in sapwood. In the present study, the extractability of seven elements was characterized to assess their suitability for the monitoring of environmental conditions. Nine mature sugar maple trees (Acer saccharum Marsh.), a wide-ranging species in eastern North America that has suffered decline in past decades, were sampled in three Quebec watersheds along a soil acidity gradient. Five-year groups of annual tree rings were treated by sequential chemical extractions using extractants of varying strength (deionized H2O, 0.05 M HCl, and concentrated HNO(3)) to selectively solubilize the elements into three fractions (water-soluble, acid-soluble, and residual). Monovalent K; divalent Ba, Ca, Cd, Mg, Mn; and trivalent Al cations were found mostly in the water-soluble, acid-soluble, and residual fractions, respectively. Forms more likely to be mobile within the tree (water-soluble and acid-soluble) do not seem to be suitable for temporal monitoring because of potential lateral redistribution in sapwood rings. However, certain elements (Cd, Mn) were responsive to current soil acidity and could be used in spatial variation monitoring. Extractability of Al varied according to soil acidity; at less acidic sites, up to 90% of Al was contained in the residual form, whereas on very acidic soils, as much as 45% was found in the water-soluble and acid-soluble fractions. Sequential extractions can be useful for determining specific forms of metals as key indicators of soil acidification.     

Impacts on industry of Europe's emerging chemicals policy REACh

For Europe, a new regime in chemicals regulation is about to start. After the proposal of the European Commission concerning the Registration, Evaluation and Authorization of Chemicals (REACh) passed its readings in the European Parliament and some differences with the European Council of Ministers were resolved, the regulation will come into force in June 2007. This paper is focused on the question how serious the cost burdens for industry induced by REACh will be, and whether the New European Member States (NMS) which joined the European Union in May 2004 will be able to cope with the regulation. This evaluation has been done by assessing the legislative, administrative and economic framework in New Member States and by analysing real business cases in companies. The empirical showcase business impact studies are at the same time of interest for companies of EU-15 states, other European countries who may implement the regulation, and even for exporters of raw materials and chemicals outside Europe, who will also have to comply with REACh if they market in the European Community. The results give no indications that REACh adoption will bring significant drawbacks to companies in the NMS. The emerging regulation will bring challenges for individual companies, especially for small and medium-sized ones, but for the European chemical industry as a whole, there is no question that it will be able to cope with REACh burdens without losing its global competitiveness.     

The impact of human frequentation on coastal vegetation in a biosphere reserve

We aimed to assess the impacts of recreational trampling on rare species, plant communities and landscape structure in the Iroise Biosphere Reserve (western France). Focusing on coastal grasslands, we first identified indicators discriminating human-induced short grasslands (i.e. maintained short by intensive trampling) from natural short grasslands (i.e. maintained by environmental constraints): the presence of lichens and succulent or woody species, which are known to be highly sensitive to trampling, as well as a shallow soil were good indicators of natural short grasslands. Recreational activities affected the majority of plots containing rare species, but one third of rare species (according to their habitat preference) appeared currently not threatened by recreational activities. The other rare species were found in grasslands with low trampling intensity and were not found in grasslands with greater trampling intensity. One lichen species (Teloshistes flavicans) was not affected by trampling intensity, while two plants species (Scilla verna and Ophioglossum lusitanicum) showed higher abundances when trampling was low to medium. When it occurs in natural short grasslands, tourist trampling reduced drastically plant species richness. However, when considering maritime high grasslands, we observed that species richness was higher under low trampling vs. no trampling, but decreased at higher trampling intensity. At a landscape scale, the mean annual rate of path creation was about 1.6% and tourist trampling has already completely destroyed 3.5ha of natural coastal vegetation. Trampling of maritime-high grassland has also created 31ha of short grasslands, which represent 50.8% of the whole short grassland habitat of the island. Moreover trampling affected respectively, 41% and 15% of natural short grasslands and maritime-high grasslands. One of the main suggestions for managers to minimise trampling impacts should be to protect areas of rocky soil covered by short grassland that are still non-trampled and not impacted. Fortunately, this appears compatible with a relatively free access of visitors to coastal areas, as tourists can be redirected towards maritime-high grasslands, an habitat which is less impacted by tourism in terms of affected surface, soil cover, loss of species, or presence of rare species host.     

Goals and remedial strategies for water quality and wildlife management in a coastal lagoon--a case-study of Ringkøbing Fjord, Denmark

The aim of this work is (1) to discuss approaches and tools to set management goals using operational indicators for coastal management (i.e., indicators that are easy to measure, understand and predict) and validated predictive models and (2) to discuss remedial strategies for sustainable coastal management regarding water quality and the abundance of fish, waterfowl and large aquatic plants. These approaches are exemplified using data from Ringkøbing Fjord, Denmark, which has undergone two major regime shifts during the last decades. This work discusses the changes taken place during the period from 1980 to 2004 (when there are good empirical data). For Ringkøbing Fjord, which is a very shallow, well-oxygenated lagoon dominated by resuspension processes, we have targeted on the following operational indicators, which are meant to reflect seasonal median values for the entire defined coastal area (the ecosystem scale) and not conditions at individual sites or data from shorter time periods: Secchi depth (as a standard measure of water clarity) and chlorophyll-a concentrations (as a key measure of algal biomass). The operational indicators are regulated by a set of standard abiotic factors, such as salinity, suspended particulate matter (SPM), nutrient concentrations (N and P), coastal morphometry and water exchange. Such relationships are quantified using well-tested, general quantitative models, which illustrate how these indicators are interrelated and how they reflect fundamental aspects of coastal ecosystems. We demonstrate that the regime shift in the lagoon can be modelled and quantitatively explained and is related to changes in salinity and nutrient inflow. A very important threshold is linked to increased salinities in the lagoon. For example, when the mean annual salinity is higher than about 9.5‰, large numbers of saltwater species of clams can survive and influence the structure and function of the ecosystem in profound ways. The model also illustrates the dynamic response to changes in nutrient loading. We have presented several management strategies with the goal of keeping the Secchi depth at 2 m, which would stimulate the growth of higher aquatic plants, which are fundamental for fish production and bird abundance in the lagoon. Given the fact that the Secchi depth depends on many variable factors (temperature, TP-inflow from land, salinity, changes in biomasses of macrophytes and clams, which are accounted for in these simulations), our results indicate that in practice it will likely be very difficult to reach that goal. However, it would be realistic to maintain a Secchi depth of 1.5 m if the variability in salinity is minimized and the mean salinity is kept at about 10.2‰.     

An Approach for Evaluating the Effectiveness of Various Ozone Air Quality Standards for Protecting Trees

We demonstrate an approach for evaluating the level of protection attained using a variety of forms and levels of past, current, and proposed Air Quality Standards (AQSs). The U.S. Clean Air Act requires the establishment of ambient air quality standards to protect health and public welfare. However, determination of attainment of these standards is based on ambient pollutant concentrations rather than prevention of adverse effects. To determine if a given AQS protected against adverse effects on vegetation, hourly ozone concentrations were adjusted to create exposure levels that “just attain” a given standard. These exposures were used in combination with a physiologically-based tree growth model to account for the interactions of climate and ozone. In the evaluation, we used ozone concentrations from two 6-year time periods from the San Bernardino Mountains in California. There were clear differences in the level of vegetation protection achieved with the various AQSs. Based on modeled plant growth, the most effective standards were the California 8-hr average maximum of 70 ppb and a seasonal, cumulative, concentration-weighted index (SUM06), which if attained, resulted in annual growth reductions of 1% or less. Least effective was the 1-hr maximum of 120 ppb which resulted in a 7% annual reduction. We conclude that combining climate, exposure scenarios, and a process-based plant growth simulator was a useful approach for evaluating effectiveness of current or proposed air quality standards, or evaluating the form and/or level of a standard based on preventing adverse growth effects.     

Polymer biodegradation: mechanisms and estimation techniques

Within the frame of the sustainable development, new materials are being conceived in order to increase their biodegradability properties. Biodegradation is considered to take place throughout three stages: biodeterioration, biofragmentation and assimilation, without neglect the participation of abiotic factors. However, most of the techniques used by researchers in this area are inadequate to provide evidence of the final stage: assimilation. In this review, we describe the different stages of biodegradation and we state several techniques used by some authors working in this domain. Validate assimilation (including mineralisation) is an important aspect to guarantee the real biodegradability of items of consumption (in particular friendly environmental new materials). The aim of this review is to emphasise the importance of measure as well as possible, the last stage of the biodegradation, in order to certify the integration of new materials into the biogeochemical cycles. Finally, we give a perspective to use the natural labelling of stable isotopes in the environment, by means of a new methodology based on the isotopic fractionation to validate assimilation by microorganisms.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.