Preparation and X-ray structural characterization of further stereoisomers of 1,2,5,6,9,10-hexabromocyclododecane

Technical 1,2,5,6,9,10-hexabromocyclododecane (HBCD) consists largely of three diastereomers (α-, β-, and γ-HBCD) produced by the trans addition of bromine to cis,trans,trans-cyclododeca-1,5,9-triene (CDT). However, another seven diastereomers are theoretically possible and may be produced by trans addition of bromine across the double bonds of the other three isomers of 1,5,9-CDT. There are indications that small amounts of the minor HBCD isomers may be present in commercial HBCD mixtures or in products containing this brominated flame retardant (BFR). Such minor components may indeed derive from traces of other 1,5,9-CDTs in the cis, trans, trans starting material, however their formation may also be possible through isomerizations during the processing of this BFR or by bioisomerization subsequent to its release into the environment. Two of the seven additional diastereomers (δ- and ε-HBCD) were synthesized previously from trans,trans,trans-CDT. We now report the preparation of the remaining five diastereomers, ζ-, η-, and θ-HBCD from cis,cis,trans-CDT and ι- and κ-HBCD from cis,cis,cis-CDT, and their characterization by ¹H NMR spectroscopy and X-ray crystallography. The availability of these further diastereomers of HBCD should aid in determining if the minor isomers are present in commercial samples of this BFR, in products containing HBCDs, or in environmental samples. We have also carried out an X-ray crystal structure determination on ε-HBCD, so that crystal structures are now available for all 10 HBCD diastereomers.     

A vehicle emissions system using a car simulator and a geographical information system: Part 1--System description and testing

A methodology for estimating vehicular emissions comprising a car simulator, a basic traffic model, and a geographical information system is capable of estimating vehicle emissions with high time and space resolution. Because of the extent of the work conducted, this article comprises two sections: In Part 1 of this work, we describe the system and its components and use examples for testing it. In Part 2 we will study in more detail the emissions of the sample fleet using the system and will make comparisons with another emission model. The experimental data for the car simulator is obtained using on-board measuring equipment and laboratory Fourier transform IR (FTIR) measurements with a dynamometer following typical driving cycles. The car simulator uses this data to generate emission factors every second. These emission factors, together with information on car activity and velocity profiles of highways and residential and arterial roads in Mexico City in conjunction with a basic traffic model, provide emissions per second of a sample fleet. A geographical information system is used to localize these road emissions.     

Catalyzing success in community-based conservation

Efforts to devolve rights and engage Indigenous Peoples and local communities in conservation have increased the demand for evidence of the efficacy of community-based conservation (CBC) and insights into what enables its success. We examined the human well-being and environmental outcomes of a diverse set of 128 CBC projects. Over 80% of CBC projects had some positive human well-being or environmental outcomes, although just 32% achieved positive outcomes for both (i.e., combined success). We coded 57 total national-, community-, and project-level variables and controls from this set, performed random forest classification to identify the variables most important to combined success, and calculated accumulated local effects to describe their individual influence on the probability of achieving it. The best predictors of combined success were 17 variables suggestive of various recommendations and opportunities for conservation practitioners related to national contexts, community characteristics, and the implementation of various strategies and interventions informed by existing CBC frameworks. Specifically, CBC projects had higher probabilities of combined success when they occurred in national contexts supportive of local governance, confronted challenges to collective action, promoted economic diversification, and invested in various capacity-building efforts. Our results provide important insights into how to encourage greater success in CBC.     

Incorporating multidimensional behavior into a risk management tool for a critically endangered and migratory species

Conservation of migratory species exhibiting wide-ranging and multidimensional behaviors is challenged by management efforts that only utilize horizontal movements or produce static spatial–temporal products. For the deep-diving, critically endangered eastern Pacific leatherback turtle, tools that predict where turtles have high risks of fisheries interactions are urgently needed to prevent further population decline. We incorporated horizontal–vertical movement model results with spatial–temporal kernel density estimates and threat data (gear-specific fishing) to develop monthly maps of spatial risk. Specifically, we applied multistate hidden Markov models to a biotelemetry data set (n = 28 leatherback tracks, 2004–2007). Tracks with dive information were used to characterize turtle behavior as belonging to 1 of 3 states (transiting, residential with mixed diving, and residential with deep diving). Recent fishing effort data from Global Fishing Watch were integrated with predicted behaviors and monthly space-use estimates to create maps of relative risk of turtle–fisheries interactions. Drifting (pelagic) longline fishing gear had the highest average monthly fishing effort in the study region, and risk indices showed this gear to also have the greatest potential for high-risk interactions with turtles in a residential, deep-diving behavioral state. Monthly relative risk surfaces for all gears and behaviors were added to South Pacific TurtleWatch (SPTW) ( https://www.upwell.org/sptw ), a dynamic management tool for this leatherback population. These modifications will refine SPTW's capability to provide important predictions of potential high-risk bycatch areas for turtles undertaking specific behaviors. Our results demonstrate how multidimensional movement data, spatial–temporal density estimates, and threat data can be used to create a unique conservation tool. These methods serve as a framework for incorporating behavior into similar tools for other aquatic, aerial, and terrestrial taxa with multidimensional movement behaviors.     

The Baltic Sea spring phytoplankton bloom in a changing climate: an experimental approach

The response of the Baltic Sea spring bloom was studied in mesocosm experiments, where temperatures were elevated up to 6°C above the present-day sea surface temperature of the spring bloom season. Four of the seven experiments were carried out at different light levels (32–202?Wh?m^?2 at the start of the experiments) in the different experimental years. In one further experiment, the factors light and temperature were crossed, and in one experiment, the factors density of overwintering zooplankton and temperature were crossed. Overall, there was a slight temporal acceleration of the phytoplankton spring bloom, a decline of peak biomass and a decline of mean cell size with warming. The temperature influence on phytoplankton bloom timing, biomass and size structure was qualitatively highly robust across experiments. The dependence of timing, biomass, and size structure on initial conditions was tested by multiple regression analysis of the y-temperature regressions with the candidate independent variables initial light, initial phytoplankton biomass, initial microzooplankton biomass, and initial mesozooplankton (=copepod) biomass. The bloom timing predicted for mean temperatures (5.28°C) depended on light. The peak biomass showed a strong positive dependence on light and a weaker negative dependence on initial copepod density. Mean phytoplankton cell size predicted for the mean temperature responded positively to light and negatively to copepod density. The anticipated mismatch between phytoplankton supply and food demand by newly hatched copepod nauplii occurred only under the combination of low light and warm temperatures. The analysis presented here confirms earlier conclusions about temperature responses that are based on subsets of our experimental series. However, only the comprehensive analysis across all experiments highlights the importance of the factor light.     

Metabolic enzyme activities in shallow- and deep-water chondrichthyans: implications for metabolic and locomotor capacity

Biochemical indices of white (WM) and red muscle (RM) aerobic and anaerobic metabolic capacity were measured in 14 species of benthic and benthopelagic chondrichthyans from a depth of ~90 to 2,200 m to evaluate the relationship between metabolic capacity and depth of occurrence, phylogeny, and locomotor mode. Maximal activities of the enzymes citrate synthase, malate dehydrogenase (MDH), lactate dehydrogenase (LDH), and pyruvate kinase (PK) were analyzed in muscle tissue at 10 °C. These were combined with previously published elasmobranch data in order to represent a comprehensive range of depths, phylogeny, and locomotor modes (i.e., benthic, benthopelagic, pelagic). Significant decreases in WM PK and LDH activities and a lack of significant trends in RM enzyme activities with increasing median depth of occurrence (MDO) indicate a depth-related reduction in both burst-locomotor and metabolic capacity. These trends are consistent with the “visual-interactions hypothesis.” Phylogeny and locomotor mode had little influence on enzyme activities compared to MDO, and the present study suggests similar activities in co-occurring demersal sharks and rays. Overall, the present study indicates low metabolic capacities in deep-sea chondrichthyans, which is important to consider when managing deep-sea fisheries.     

Single-walled carbon nanotube behavior in representative mature leachate

Escalating production and subsequent incorporation of engineered nanomaterials in consumer products increases the likelihood of nanomaterials being discarded in landfills. Although direct measurement of particle disposal has not yet occurred, life cycle assessments suggest that over 50% of nanomaterials produced will eventually reside in landfills. Laboratory-scale experiments were conducted to evaluate how organics (humic acid: 20-800 mg/L), ionic strength (100-400 mM NaCl), and pH (6-8) typical of mature leachates influence carbon nanotube surface charge, relative stability, and mobility through representative solid waste environments. Results from the batch experiments suggest that the presence of high molecular weight organics, such as humic acid, acts to stabilize carbon nanotubes present in leachate, even at high ionic strengths (>100 mM NaCl). These results also suggest that in mature landfill leachate, as long as humic acid is present, ionic strength (when represented as NaCl) will be a dominant factor influencing nanomaterial stability. Column experiment results indicate the carbon nanotubes may be mobile through solid waste, suggesting particle placement within landfills needs to be examined more closely.     

Is pesticide sorption by constructed wetland sediments governed by water level and water dynamics?

Constructed wetlands (CWs) are used to reduce the pesticide inputs from tile drainage or run-off to surface water. Their effectiveness appears variable and remains to be better characterized and understood. The aim of this study was to assess the influences of two hydraulic parameters (i.e., dynamics and water level) on the sorption process occurring in CWs. Then, two solid/liquid ratios were studied (1/1 and 1/5) to mimic the water level variation in the field, and two agitation speeds were used (none and gentle agitation) to simulate different water dynamics (stagnation and flow pass, respectively). Sorption kinetics and isotherms were obtained for four pesticides with contrasting properties. The pesticide adsorption coefficients were classified as follows: boscalid (BSC) > cyproconazole (CYP) > isoproturon (IPU) ～ dimethachlor (DMT) at any ratio or agitation, in agreement with their water solubilities and K _ow values. The effect of the solid/liquid ratio was evidenced for all conditions. Indeed, the adsorption equilibrium time was reached more quickly for the 1/1 ratio (24–72 h) than for the 1/5 ratio (96–120 h). In addition, the adsorption coefficients (K _f ^ads) were larger for the 1/1 ratio (1.8–11.2 L kg^?1) than for the 1/5 ratio (1.0–5.9 L kg^?1). The agitation effect was ?more evidenced for the 1/5 ratio and for the more hydrophobic molecules, such as BSC and CYP, for which adsorption equilibrium time was never reached with agitation (>120 h), while it was reached at 96 h without agitation. Moreover, the K _f ^ads values were larger with agitation than without agitation for BSC and CYP, whereas they were similar for the two agitations for IPU and DMT. Our results demonstrated that the hydrodynamic function of CWs could influence pesticide sorption with variable effects according to the molecular properties and consequently influence the mitigation effect of CWs throughout the year.     

A Missed Opportunity?: NOAA’s Use of Social Media to Communicate Climate Science

In the current media landscape, organizations often communicate about science directly with publics through online channels rather than relying on journalist gatekeepers. Online platforms present organizations with the opportunity to participate in two-way communication in order to increase engagement with science. The present study examined how the National Oceanic and Atmospheric Administration (NOAA) utilizes social media to interact with publics. Results suggest that NOAA does not fully utilize the dialogic potential of social media, which could enhance both the public’s science literacy and trust in science regarding climate change specifically. This study informs how public relations theory may complement science communication theory and practice as deficit model-thinking transitions to contemporary approaches for public engagement with science.