Bromination of 2-methoxydiphenyl ether to an average of tetrabrominated 2-methoxydiphenyl ethers

Brominated 2-phenoxyanisoles (2-methoxydiphenyl ethers, 2-MeO-BDEs) are a class of halogenated natural products, produced by algae and sponges. Especially two tetrabrominated isomers, i.e. 2′-MeO-BDE 68 (BC-2) and 6-MeO-BDE 47 (BC-3), have also been frequently determined in environmental and food samples. In addition, 2-MeO-BDEs are under discussion as metabolites of polybrominated diphenyl ethers (PBDEs). In this study, we synthesized the backbone 2-methoxydiphenyl ether and brominated it to an average degree of four bromine substituents. The reaction mixture only contained one major product (∼90%) along with three further MeO-BDEs and ∼5% hydroxylated BDEs. In all likelihood, the HO-BDEs were formed in a side reaction by cleavage of the methoxy group. The major MeO-BDE was identified as 6′-methoxy-2,3′,4,4′-tetrabromodiphenyl ether (6′-MeO-BDE-66). The HO-BDEs were separated by KOH/n-hexane partitioning, and the resulting 2-MeO-BDEs were fractionated by means of high-speed counter-current chromatography (HSCCC). Due to the excellent enrichment facilities of HSCCC, some 15 MeO-BDEs, mainly present at traces only, could be detected in 26 fractions, and eight of them could be characterized by nuclear magnetic resonance spectroscopy (NMR). Only two of the compounds - 2′-MeO-BDE 68 and 6-MeO-BDE 123 - had been characterized as natural products while the prominent halogenated natural product 6-MeO-BDE 47 was not detected at all in the reaction product. The “non-natural” 2-MeO-BDEs may be useful internal standards in trace analysis.     

Performance of firefighters' protective clothing after heat exposure.

Heat and mechanical protection properties of 6 fabric combinations commonly used in firefighters' protective clothing were assessed before and after different heat treatment. It was shown that after heat exposure, the values obtained were generally lower than in the original state. The mechanical properties of the materials were more affected by heat than by heat protective properties. In 2 cases, degradation started before a visible change in the material could be observed, which might be potentially dangerous for the end user who will not realize the alteration of the material.     

Mercury reduction studies to facilitate the thermal decontamination of phosphor powder residues from spent fluorescent lamps

This work investigates the thermal release of mercury from phosphor powder of spent fluorescent lamps. The treatment conditions and the ability of various reducing agents (primarily sodium borohydride) to lower the overall heating temperature required to improve the release of Hg have been evaluated. Hg species in samples were monitored in a thermal desorption atomic absorption spectrometer system, and total mercury was analyzed in a cold vapor atomic absorption spectrometer. Sodium borohydride was the best reducing agent among the ones studied. However, citric acid presented a high capacity to weaken mercury bonds with the matrix. When the sample was crushed with sodium borohydride for 40min in a mass ratio of 10:1 (sample:reducing agent) and submitted to thermal treatment at 300 degrees C for 2h, the concentration of mercury in a phosphor powder sample with 103mgkg(-1) of mercury reached 6.6mgkg(-1).     

Headwater Influences on Downstream Water Quality

We investigated the influence of riparian and whole watershed land use as a function of stream size on surface water chemistry and assessed regional variation in these relationships. Sixty-eight watersheds in four level III U.S. EPA ecoregions in eastern Kansas were selected as study sites. Riparian land cover and watershed land use were quantified for the entire watershed, and by Strahler order. Multiple regression analyses using riparian land cover classifications as independent variables explained among-site variation in water chemistry parameters, particularly total nitrogen (41%), nitrate (61%), and total phosphorus (63%) concentrations. Whole watershed land use explained slightly less variance, but riparian and whole watershed land use were so tightly correlated that it was difficult to separate their effects. Water chemistry parameters sampled in downstream reaches were most closely correlated with riparian land cover adjacent to the smallest (first-order) streams of watersheds or land use in the entire watershed, with riparian zones immediately upstream of sampling sites offering less explanatory power as stream size increased. Interestingly, headwater effects were evident even at times when these small streams were unlikely to be flowing. Relationships were similar among ecoregions, indicating that land use characteristics were most responsible for water quality variation among watersheds. These findings suggest that nonpoint pollution control strategies should consider the influence of small upland streams and protection of downstream riparian zones alone is not sufficient to protect water quality.     

Organogel Polymers from 10-Undecenoic Acid and Poly(vinyl acetate)

Organogels are used in a variety of high value applications including the removal of toxic solvents from aqueous environments and the time-controlled release of compounds. One of the most promising gelators is a polyvinyl polymer containing medium chain length carboxylic acids. The existing production of this product requires synthesis of vinyl esters containing medium length carboxylic chains. This starting material must be made from an expensive and low yielding transvinylation reaction, which leaves production of useful vinyl esters and, as a result, the organogels themselves, outside the realm of practical chemistry. We have developed a new, more practical production process and used it to directly synthesize a new polymer. This new process utilizes commercially available polyvinyl acetate and accomplishes the transformation with simple hydrolysis and anhydride addition steps. The new polymers form organogels with chloroform, acetone or toluene with swell ratios up to 30. They also show time-controlled release of crystal violet over a 100 h span. This new production process opens the possibility of producing organogels utilizing agricultural resources.     

Echo Chambers of Denial: Explaining User Comments on Climate Change

Although there is a broad consensus among scientists and journalists about the existence of anthropogenic climate change as a global problem, some segments of the population remain doubtful about the human impact on it. The internet provides citizens with opportunities to publicly voice their doubts and user comment sections of online media are a popular form of user-generated content. This study identifies factors that foster comments that are sceptical or supportive of basic assumptions of anthropogenic climate change, drawing on online news in the US, the UK, Germany, India, and Switzerland. The results show that users adapt to the dominant opinion within the respective media outlet: user comment sections serve as echo chambers rather than as corrective mechanisms. Climate change denial is more visible in user comment sections in countries where the climate change debate reflects the scientific consensus on climate change and user comments create niches of denial.     

Acoustic ranging in poison frogs—it is not about signal amplitude alone

Behavioral Ecology and Sociobiology - Colony size is an important predictor of annual survival and reproduction in social insects. By tracking monthly forager turn over, we measured the...     

Apportionment of bioavailable phosphorus loads entering Cayuga Lake,New York

The integration of the phosphorus (P) bioavailability concept into a P loading analysis for Cayuga Lake, New York, is documented. Components of the analyses included the: (1) monitoring of particulate P (PP), soluble unreactive P (SUP), and soluble reactive P (SRP), supported by biweekly and runoff event‐based sampling of the lake's four largest tributaries; (2) development of relationships between tributary P concentrations and flow; (3) algal bioavailability assays of PP, SUP, and SRP from primary tributaries and the three largest point sources; and (4) development of P loading estimates to apportion contributions according to individual nonpoint and point sources, and to represent the effects of interannual variations in tributary flows on P loads. Tributary SRP, SUP, and PP are demonstrated to be completely, mostly, and less bioavailable, respectively. The highest mean bioavailability for PP was observed for the stream with the highest agriculture land use. Point source contributions to the total bioavailable P load (BAP_L) are minor (5%), reflecting the benefit of reductions from recent treatment upgrades. The BAP_L represented only about 26% of the total P load, because of the large contribution of the low bioavailable PP component. Most of BAP_L (>70%) is received during high flow intervals. Large interannual variations in tributary flow and coupled BAP_L will tend to mask future responses to changes in individual inputs.     

Bottom sediment as a source of organic contaminants in Lake Mead, Nevada, USA

Treated wastewater effluent from Las Vegas, Nevada and surrounding communities’ flow through Las Vegas Wash (LVW) into the Lake Mead National Recreational Area at Las Vegas Bay (LVB). Lake sediment is a likely sink for many hydrophobic synthetic organic compounds (SOCs); however, partitioning between the sediment and the overlying water could result in the sediment acting as a secondary contaminant source. Locating the chemical plumes may be important to understanding possible chemical stressors to aquatic organisms. Passive sampling devices (SPMDs and POCIS) were suspended in LVB at depths of 3.0, 4.7, and 6.7 (lake bottom) meters in June of 2008 to determine the vertical distribution of SOCs in the water column. A custom sediment probe was used to also bury the samplers in the sediment at depths of 0-10, 10-20, and 20-30 cm. The greatest number of detections in samplers buried in the sediment was at the 0-10 cm depth. Concentrations of many hydrophobic SOCs were twice as high at the sediment-water interface than in the mid and upper water column. Many SOCs related to wastewater effluents, including fragrances, insect repellants, sun block agents, and phosphate flame retardants, were found at highest concentrations in the middle and upper water column. There was evidence to suggest that the water infiltrated into the sediment had a different chemical composition than the rest of the water column and could be a potential risk exposure to bottom-dwelling aquatic organisms.