Reductive debromination of nonabrominated diphenyl ethers by sodium borohydride and identification of octabrominated diphenyl ether products

A method was developed to study reductive transformation of highly brominated diphenyl ethers (BDEs). The method development is a part of a broader project where it will be used to determine the susceptibility of environmental pollutants to reductive conditions, in an attempt to create a scheme for determination of chemical’s persistence. This paper focuses on identification of octabrominated diphenyl ether transformation products from reductive debromination of the three nonabrominated diphenyl congeners (nonaBDE), BDE-206, -207 and -208. Sodium borohydride was used to explore the reductive debromination of the nonaBDEs. The transformation products were collected at two time-points and identified products were quantified by GC-MS. The reduction of the nonaBDEs lead primarily to debrominated products, mainly octaBDEs. The three nonabrominated DEs gave isomer-related transformation product patterns. BDE-207 and BDE-208 showed a propensity for ortho-debromination in the initial reaction step, while no discrimination between initial debromination positions was seen for BDE-206. All three nonabrominated DEs displayed a preferred initial debromination on the fully brominated DE ring.     

Exposure to moderate concentrations of tropospheric ozone impairs tree stomatal response to carbon dioxide

With rising concentrations of both atmospheric carbon dioxide (CO₂) and tropospheric ozone (O₃), it is important to better understand the interacting effects of these two trace gases on plant physiology affecting land-atmosphere gas exchange. We investigated the effect of growth under elevated CO₂ and O₃, singly and in combination, on the primary short-term stomatal response to CO₂ concentration in paper birch at the Aspen FACE experiment. Leaves from trees grown in elevated CO₂ and/or O₃ exhibited weaker short-term responses of stomatal conductance to both an increase and a decrease in CO₂ concentration from current ambient level. The impairement of the stomatal CO₂ response by O₃ most likely developed progressively over the growing season as assessed by sap flux measurements. Our results suggest that expectations of plant water-savings and reduced stomatal air pollution uptake under rising atmospheric CO₂ may not hold for northern hardwood forests under concurrently rising tropospheric O₃.     

Soil nitrogen transformations under elevated atmospheric CO₂ and O₃ during the soybean growing season

We investigated the influence of elevated CO₂ and O₃ on soil N cycling within the soybean growing season and across soil environments (i.e., rhizosphere and bulk soil) at the Soybean Free Air Concentration Enrichment (SoyFACE) experiment in Illinois, USA. Elevated O₃ decreased soil mineral N likely through a reduction in plant material input and increased denitrification, which was evidenced by the greater abundance of the denitrifier gene nosZ. Elevated CO₂ did not alter the parameters evaluated and both elevated CO₂ and O₃ showed no interactive effects on nitrifier and denitrifier abundance, nor on total and mineral N concentrations. These results indicate that elevated CO₂ may have limited effects on N transformations in soybean agroecosystems. However, elevated O₃ can lead to a decrease in soil N availability in both bulk and rhizosphere soils, and this likely also affects ecosystem productivity by reducing the mineralization rates of plant-derived residues.     

Comparing universal kriging and land-use regression for predicting concentrations of gaseous oxides of nitrogen (NOx) for the Multi-Ethnic Study of Atherosclerosis and Air Pollution (MESA Air)

BACKGROUND: Epidemiological studies that assess the health effects of long-term exposure to ambient air pollution are used to inform public policy. These studies rely on exposure models that use data collected from pollution monitoring sites to predict exposures at subject locations. Land use regression (LUR) and universal kriging (UK) have been suggested as potential prediction methods. We evaluate these approaches on a dataset including measurements from three seasons in Los Angeles, CA. METHODS: The measurements of gaseous oxides of nitrogen (NOx) used in this study are from a "snapshot" sampling campaign that is part of the Multi-Ethnic Study of Atherosclerosis and Air Pollution (MESA Air). The measurements in Los Angeles were collected during three two-week periods in the summer, autumn, and winter, each with about 150 sites. The design included clusters of monitors on either side of busy roads to capture near-field gradients of traffic-related pollution. LUR and UK prediction models were created using geographic information system (GIS)-based covariates. Selection of covariates was based on 10-fold cross-validated (CV) R(2) and root mean square error (RMSE). Since UK requires specialized software, a computationally simpler two-step procedure was also employed to approximate fitting the UK model using readily available regression and GIS software. RESULTS: UK models consistently performed as well as or better than the analogous LUR models. The best CV R(2) values for season-specific UK models predicting log(NOx) were 0.75, 0.72, and 0.74 (CV RMSE 0.20, 0.17, and 0.15) for summer, autumn, and winter, respectively. The best CV R(2) values for season-specific LUR models predicting log(NOx) were 0.74, 0.60, and 0.67 (CV RMSE 0.20, 0.20, and 0.17). The two-stage approximation to UK also performed better than LUR and nearly as well as the full UK model with CV R(2) values 0.75, 0.70, and 0.70 (CV RMSE 0.20, 0.17, and 0.17) for summer, autumn, and winter, respectively. CONCLUSION: High quality LUR and UK prediction models for NOx in Los Angeles were developed for the three seasons based on data collected for MESA Air. In our study, UK consistently outperformed LUR. Similarly, the 2-step approach was more effective than the LUR models, with performance equal to or slightly worse than UK.     

Land use influences macroinvertebrate community composition in boreal headwaters through altered stream conditions

Land use is known to alter the nature of land–water interactions, but the potential effects of widespread forest management on headwaters in boreal regions remain poorly understood. We evaluated the importance of catchment land use, land cover, and local stream variables for macroinvertebrate community and functional trait diversity in 18 boreal headwater streams. Variation in macroinvertebrate metrics was often best explained by in-stream variables, primarily water chemistry (e.g. pH). However, variation in stream variables was, in turn, significantly associated with catchment-scale forestry land use. More specifically, streams running through catchments that were dominated by young (11–50 years) forests had higher pH, greater organic matter standing stock, higher abundance of aquatic moss, and the highest macroinvertebrate diversity, compared to streams running through recently clear-cut and old forests. This indicates that catchment-scale forest management can modify in-stream habitat conditions with effects on stream macroinvertebrate communities and that characteristics of younger forests may promote conditions that benefit headwater biodiversity.     

Linking Climate Trends to Population Dynamics in the Baltic Ringed Seal: Impacts of Historical and Future Winter Temperatures

A global trend of a warming climate may seriously affect species dependent on sea ice. We investigated the impact of climate on the Baltic ringed seals (Phoca hispida botnica), using historical and future climatological time series. Availability of suitable breeding ice is known to affect pup survival. We used detailed information on how winter temperatures affect the extent of breeding ice and a climatological model (RCA3) to project the expected effects on the Baltic ringed seal population. The population comprises of three sub-populations, and our simulations suggest that all of them will experience severely hampered growth rates during the coming 90 years. The projected 30 730 seals at the end of the twenty-first century constitutes only 16 % of the historical population size, and thus reduced ice cover alone will severely limit their growth rate. This adds burden to a species already haunted by other anthropogenic impacts.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Learning About the History of Landscape Use for the Future: Consequences for Ecological and Social Systems in Swedish Bergslagen

Barriers and bridges to implement policies about sustainable development and sustainability commonly depend on the past development of social–ecological systems. Production of metals required integration of use of ore, streams for energy, and wood for bioenergy and construction, as well as of multiple societal actors. Focusing on the Swedish Bergslagen region as a case study we (1) describe the phases of natural resource use triggered by metallurgy, (2) the location and spatial extent of 22 definitions of Bergslagen divided into four zones as a proxy of cumulative pressure on landscapes, and (3) analyze the consequences for natural capital and society. We found clear gradients in industrial activity, stream alteration, and amount of natural forest from the core to the periphery of Bergslagen. Additionally, the legacy of top-down governance is linked to today’s poorly diversified business sector and thus municipal vulnerability. Comparing the Bergslagen case study with other similar regions in Russia and Germany, we discuss the usefulness of multiple case studies.     

Building resilience to drought in desertification-prone savannas in Sub-Saharan Africa: The water perspective

Securing sustainable livelihood conditions and reducing the risk of outmigration in savanna ecosystems hosted in the tropical semiarid regions is of fundamental importance for the future of humanity in general. Although precipitation in tropical drylands, or savannas, is generally more significant than one might expect, these regions are subject to considerable rainfall variability which causes frequent periods of water deficiency. This paper addresses the twin problems of “drought and desertification” from a water perspective, focusing on the soil moisture (green water) and plant water uptake deficiencies. It makes a clear distinction between long‐term climate change, meteorological drought, and agricultural droughts and dry spells caused by rainfall variability and land degradation. It then formulates recommendations to better cope with and to build resilience to droughts and dry spells. Coping with desertification requires a new conceptual framework based on green‐blue water resources to identify hydrological opportunities in a sea of constraints. This paper proposes an integrated land/water approach to desertification where ecosystem management supports agricultural development to build social‐ecological resilience to droughts and dry spells. This approach is based on the premise that to combat desertification, focus should shift from reducing trends of land degradation in agricultural systems to water resource management in savannas and to landscape‐wide ecosystem management.     

Soil sensitivity to acidification in Asia: status and prospects

Exceedance of steady-state critical loads for soil acidification is consistently found in southern China and parts of SE Asia, but there is no evidence of impacts outside of China. This study describes a methodology for calculating the time to effects for soils sensitive to acidic deposition in Asia under potential future sulfur (S), nitrogen (N), and calcium (Ca) emission scenarios. The calculations are matched to data availability in Asia to produce regional-scale maps that provide estimates of the time (y) it will take for soil base saturation to reach a critical limit of 20% in response to acidic inputs. The results show that sensitive soil types in areas of South, Southeast, and East Asia, including parts of southern China, Burma, Hainan, Laos, Thailand, Vietnam, and the Western Ghats of India, may acidify to a significant degree on a 0-50 y timescale, depending on individual site management and abiotic and biotic characteristics. To make a clearer assessment of risk, site-specific data are required for soil chemistry and deposition (especially base cation deposition); S and N retention in soils and ecosystems; and biomass harvesting and weathering rates from sites across Asia representative of different soil and vegetation types and management regimes. National and regional assessments of soils using the simple methods described in this paper can provide an appreciation of the time dimension of soil acidification-related impacts and should be useful in planning further studies and, possibly, implementing measures to reduce risks of acidification.