Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

Wintering French Mallard and Teal Are Heavier and in Better Body Condition than 30?Years Ago: Effects of a Changing Environment?

Animal populations are exposed to large-scale anthropogenic impact from e.g. climate change, habitat alteration and supplemental stocking. All of these may affect body condition in wintering dabbling ducks, which in turn may affect an individual’s survival and reproductive success. The aim of this study was to assess whether there have been morphometric changes in Mallard (Anas platyrhynchos) and Teal (Anas crecca) over the last 30 years at a major wintering site. Body mass and condition increased from the 1950s–1960s to the 2000s in both species. The increase in body mass amounted to as much as 11.7%, with no corresponding change in body size. Improved body condition was maintained from early to mid-winter, but then converged with historical values for late winter. Our interpretation is that increasingly benign ambient winter conditions permit ducks to maintain better energetic “safety margins” throughout winter, and that converging spring departure values may be related to evolutionary flight energetic optima. The observed changes are consistent with large-scale climate amelioration and local/regional habitat improvement (both anthropogenic).     

Smaller farm size and ruminant animals are associated with increased supply of non-provisioning ecosystem services

To balance trade-offs between livestock’s negative environmental impacts and their positive contributions (e.g. maintaining semi-natural grasslands, varied agricultural landscapes and crop rotations), a better understanding is needed of how the supply of ecosystem services differs across farms. We analysed a suite of indicators for non-provisioning ecosystem services on a large subset of Swedish farms (71% of farms, covering 82% of agricultural land) and related these to farm type, farm size and livestock density. The analysed indicators exhibited clear geographical patterns with hotspots especially in less productive regions. Controlling for this spatial variation we still found that small-scale and ruminant farms were associated with more varied landscapes, small-scale habitats, semi-natural grasslands and better crop sequences compared to nearby farms specialised in crop production, while farms specialising in monogastric livestock were associated with less varied landscapes and inferior crop sequences. Results for cultural ecosystem services indicated that farms with more semi-natural grassland were associated with more visitors and more likely located within designated recreation or nature conservation areas.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-022-01726-y.     

Against the current: rewiring rigidity trap dynamics in urban water governance through civic engagement

This paper investigates how the agency of local residents can affect persistent and unsustainable practices in urban water supply governance. Using a case study from Bangalore, India, we analyze a social–ecological trap which developed after a shift to external water provision paired with rapid urbanization. The reluctance of forsaking initial investments in infrastructure and competence, and the subsequent loss of the local network of lakes built for harvesting rainwater, reinforced dependence on external sources while undermining groundwater levels in the city. These feedbacks made water scarcity a structurally persistent feature of Bangalore. This situation started to change when local residents recently started organizing to preserve and restore Bangalore’s lakes. By entering collaborative management agreements with municipal authorities, these lake groups have restored and established effective protection of five lakes. Through a case study of this civic engagement we show that the lake restorations have the potential to counteract trap mechanisms by restoring ecological functions, and by reducing water scarcity as groundwater levels rise and authorities are relieved from maintenance and monitoring tasks. Importantly, these lake groups have also created opportunities for over a dozen similar groups to form across the city. This demonstrates that social movements can be an important source of change in social–ecological traps.     

Top-down control inhibits spatial self-organization of a patterned landscape

Regular, self-organized spatial patterns in primary producers have been described in a wide range of ecosystems and are predicted to affect community production and resilience. Although consumers are abundant in most systems, the effect of trophic interactions on pattern formation in primary producers remains unstudied. We studied the effects of top-down control by herbivores on a self-organized landscape of regularly spaced, diatom-covered hummocks alternating with water-filled hollows on an intertidal mudflat in The Netherlands. Spatial patterns developed during spring but were followed by a rapid collapse in summer, leading to a flat landscape with low diatom densities and little variation in sediment bed level. This dramatic decline co-occurred with a gradual increase of benthic herbivores. A manipulative field experiment, where benthic herbivores were removed from the sediment, revealed that both diatom growth and hummock formation were inhibited by the activity of benthic herbivores. Our study provides clear evidence of top-down control of spatial self-organized patterns by benthic herbivores within a biological-geomorphic landscape.     

Relevance of rangeland degradation in semiarid northeastern South Africa to the nonequilibrium theory.

According to the nonequilibrium theory, livestock grazing has a limited effect on long-term vegetation productivity of semiarid rangelands, which is largely determined by rainfall. The communal lands in northeastern South Africa contain extensive degraded areas which have been mapped by the National Land Cover (NLC) program. Much evidence suggests that long-term heavy grazing is the cause of this degradation. In order to test for the prevalence of nonequilibrium dynamics, we determined the relative effects of rainfall- and grazing-induced degradation on vegetation productivity. The vegetation production in the NLC degraded areas was estimated using growth-season sums of the Normalized Difference Vegetation Index (sigmaNDVI), calculated using data from both the Advanced Very High Resolution Radiometer (AVHRR) (1985-2003) and Moderate-resolution Imaging Spectroradiometer (MODIS) (2000-2005). On average, rainfall and degradation accounted for 38% and 20% of the AVHRR sigmaNDVI variance and 50% and 33% of the MODIS sigmaNDVI variance, respectively. Thus, degradation had a significant influence on long-term vegetation productivity, and therefore the rangelands did not behave according to the nonequilibrium model, in which grazing is predicted to have a negligible long-term impact.     

“There is nothing political in it”: triggers of local political leaders' engagement in climate adaptation

Local government is attributed a vital role in climate-change adaptation. Previous studies contend that conflicting priorities, insufficient institutional incentives and knowledge of risks, and inadequate resources all impede local climate adaptation. Though the importance of local political support in enabling climate adaptation is widely acknowledged, the views of local politicians have rarely been analysed. Drawing on semi-structured interviews with local politicians in Sweden, we explore what affects their engagement in climate adaptation. The study claims that climate adaptation contrary to mitigation is not viewed as political beyond directing attention and sanctioning guidelines set by officials. A limited number of interviewees claim a more strategic political role in adaptation. The combined effect of institutional incentives (e.g. fragmented national guidelines, unappealing goals, and lack of funding), relative weight in local politics, and ability to exercise political leadership (e.g. campaign value, public and media pressure, and lack of ideology) is perceived as too insignificant to trigger strong political engagement. In less-populous municipalities, adaptive measures were highly valued for demonstrating political action.     

Non-invasive prenatal detection of achondroplasia in size-fractionated cell-free DNA by MALDI-TOF MS assay

Achondroplasia is the most common form of short-limbed dwarfism in humans and is caused by mutations in the FGFR3 gene. Currently, prenatal diagnosis of this disorder relies on invasive procedures. Recent studies have shown that fetal single gene point mutations could be detected in cell-free DNA (cf-DNA) from maternal plasma by either the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) assay with single allele base extension reaction (SABER) approach or the size fractionation of cf-DNA in maternal plasma. Here, we combined the two approaches to non-invasively examine the fetal G1138A mutation in maternal plasma. cf-DNA was extracted from maternal plasma samples obtained from two pregnant women at risk for achondroplasia. The fetal G1138A mutation was determined by the analysis of size-fractionated cf-DNA in maternal plasma using MALDI-TOF MS with SABER approach and homogenous MassEXTEND (hME) assay, respectively. The fetal G1138A mutation was detectable in the two achondroplasia-affected pregnancies by the analysis of cf-DNA in maternal plasma using MALDI-TOF MS. However, the size-fractionation approach led to a more precise detection of the fetal mutation in both analyses. This analysis would be suitable for non-invasive prenatal diagnosis of diseases caused by fetal single gene point mutations. Copyright © 2007 John Wiley & Sons, Ltd.     

Driving forces for import of waste for energy recovery in Sweden.

Between 1996 and 2002, the Swedish import of so-called yellow waste for energy recovery increased. The import mainly consisted of separated wood waste and mixes of used wood and paper and/or plastics that was combusted in district heat production plants (DHPPs). Some mixed waste was imported to waste incineration plants for energy recovery (10% of the import of yellow waste for energy recovery in 2002). The import came primarily from Germany, the Netherlands, Norway, Denmark and Finland. We identified six underlying driving forces for this recent increase of imported waste which are outlined and their interactive issues discussed. --The energy system infrastructure, which enables high energy recovery in Sweden. --The energy taxation, where high Swedish taxes on fossil fuels make relatively expensive solid biofuels the main alternative for base load production of district heat. --The quality of the waste-derived fuels, which has been higher in the exporting countries than in Sweden. --The bans on landfilling within Europe and the shortage of waste treatment capacity. --Taxes on waste management in Europe. --Gate fee differences between exporting countries and Sweden. In the future, the overall strength of these driving forces will probably be weakened. A Swedish tax on waste incineration is being investigated. In other European countries, the ambition to reach the Kyoto targets and increase the renewable electricity production could improve the competitiveness of waste-derived fuels in comparison with fossil fuels. Swedish DHPPs using waste-derived fuels will experience higher costs after the Waste Incineration Directive is fully implemented. The uncertainty about European waste generation and treatment capacity, however, might have a large influence on the future gate fees and thus also on the yellow waste import into Sweden.