Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

Organic aerosol characterization by complementary measurements of chemical bonds and molecular fragments

Organic aerosol chemical markers from normalized concentrations of independent measurements of mass fragments (using Aerosol Mass Spectrometry, AMS) are compared to bond-based functional groups (from Fourier Transform Infrared spectroscopy, FTIR) during eight field projects in the western hemisphere. Several field projects show weak correlations between alcohol group fractions and m/z 60 fractions, consistent with the organic hydroxyl groups and the fragmentation of saccharides, but the weakness of the correlations indicate chemical differences among the relationships for ambient aerosols in different regions. Carboxylic acid group fractions and m/z 44 fractions are correlated weakly for three projects, with correlations expected for aerosols dominated by di-acid compounds since their fragmentation is typically dominated by m/z 44. Despite differences for three projects with ratios of m/z 44 to m/z 57 fragments less than 10, five projects showed a linear trend between the project-average m/z 44 to m/z 57 ratio and the ratio of acid and alkane functional groups. While this correlation explains only a fraction of the fragment and bond variability measured, the consistency of this relationship at multiple sites indicates a general agreement with the interpretation of the relative amount of m/z 44 as a carboxylic acid group marker and m/z 57 as an alkane group marker.     

Exploring the Crowding–Satisfaction Relationship in Recreational Boating

Along with the growing boating population and the number of boats in use on limited inland waterways, boater expectations of setting density, safety perceptions, and the associated impacts on their experience (e.g., satisfaction) are becoming increasingly important. The primary purpose of this article was to explore a recreational boating crowding–satisfaction model derived from previous work using safety and enjoyment as mediating variables. We also tested our crowding–satisfaction model among day and overnight users. Our analysis revealed no significant difference between day and overnight users for any of the relationships tested in our model. Our final model indicated as respondents’ expectations for seeing people increased along with their feelings of being crowded, they were more inclined to consider the conditions on the lake as being unsafe. They were also more inclined to indicate that the number of people they had seen on the lake detracted from their boating experience. Respondents’ satisfaction was tied to their perceptions of crowding. Mediating variables illustrated that the relationship was conditioned by perceptions of safety and enjoyment. Analysis of the indirect effect observed in our study illustrate that when the number of people seen on the lake exceed respondents’ expectations, their perceptions of safety and enjoyment both decline, resulting in lower satisfaction. These findings have implications for managing recreational boating use on inland lake systems. Given the role played by expectations in our model, efforts to communicate with boaters about conditions on these waterways is important for helping them plan their boating experience and avoid situations they consider unsafe or unsatisfactory.     

Investigation of the Jahn Foundry and CTA Acoustics dust explosions: similarities and differences

The Jahn Foundry in Springfield, Massachusetts and CTA Acoustics in Corbin, Kentucky experienced devastating dust explosions in 1999 and 2003, respectively. At the time, Jahn Foundry was a gray iron casting facility that used phenolic resin powder as a binder for sand molds. CTA Acoustics was a manufacturer of thermal acoustic insulation that used phenolic resin powder as a binder for fiberglass mats. In both facilities the phenolic resin was able to migrate from the process, accumulate in the facility, and fuel catastrophic dust explosions.In this paper we review Exponent's investigation of the two incidents and identify root causes of the incidents and applicable standards that, if followed, could have prevented or mitigated the incidents. Throughout the paper we identify similarities and differences between the two facilities. For instance, in both facilities hazardous levels of dust had been allowed to accumulate due, in part, to inadequate housekeeping. However, a significant difference between the two facilities was that Jahn Foundry had no dust collection systems while the CTA Acoustics facility had dust collection systems designed to minimize the release of dust into the plant. The paper summarizes lessons learned from these two incidents that should be remembered when designing new facilities and analyzing hazards at existing facilities.     

Research priorities for managing the impacts and dependencies of business upon food,energy, water and the environment

Delivering access to sufficient food, energy and water resources to ensure human wellbeing is a major concern for governments worldwide. However, it is crucial to account for the ‘nexus’ of interactions between these natural resources and the consequent implications for human wellbeing. The private sector has a critical role in driving positive change towards more sustainable nexus management and could reap considerable benefits from collaboration with researchers to devise solutions to some of the foremost sustainability challenges of today. Yet opportunities are missed because the private sector is rarely involved in the formulation of deliverable research priorities. We convened senior research scientists and influential business leaders to collaboratively identify the top forty questions that, if answered, would best help companies understand and manage their food-energy-water-environment nexus dependencies and impacts. Codification of the top order nexus themes highlighted research priorities around development of pragmatic yet credible tools that allow businesses to incorporate nexus interactions into their decision-making; demonstration of the business case for more sustainable nexus management; identification of the most effective levers for behaviour change; and understanding incentives or circumstances that allow individuals and businesses to take a leadership stance. Greater investment in the complex but productive relations between the private sector and research community will create deeper and more meaningful collaboration and cooperation.     

Perceptions matter: household adaptive capacity and capability in two Australian coastal communities

Regional Environmental Change - This paper presents empirical data on household perceptions of capability to adapt to climate hazards and associated capacity needs. Households play an important...     

Organochlorine pesticides in soil under irrigated cotton farming systems in Vertisols of the Namoi Valley, north-western New South Wales, Australia

Organochlorine pesticides (OCPs) such as DDT and DDE have been detected in the surface 0.2 m of Vertisols in the lower Namoi Valley of north western New South Wales, Australia even though they have not been applied to crops since 1982. However, their presence in the deeper soil horizons has not been investigated. The objective of this study was to determine if OCPs were present to a depth of 1.2 m in Vertisols under irrigated cotton farming systems in the lower Namoi Valley of New South Wales. Soil was sampled from the 0-1.2 m depths in three sites, viz. the Australian Cotton Research Institute, ACRI, near Narrabri (149°36′E, 30°12′S), and two cotton farms near Wee Waa (149°27′E, 30°13′S) and Merah North (149°18′E, 30°12′S) in northern New South Wales, Australia. The OCPs detected and their metabolites were α-endosulfan, β-endosulfan, endosulfan sulphate, DDD, DDE, DDT and endrin. The metabolite DDE, a breakdown product of DDT, was the most persistent OCP in all depths analysed. Endosulfan sulphate was the second most persistent followed by endrin > α-endosulfan > β-endosulfan > DDT and DDD. DDT was sprayed extensively in the lower Namoi Valley up to the early 1980s and may explain the persistence of DDE in the majority of soil samples. Dicofol and Dieldrin, two OCPs previously undocumented in Vertisols were also detected. The movement of OCPs into the subsoil of Vertisols may occur when irrigation or rain transports soil colloids and organic matter via preferential flow systems into the deeper layers of a soil profile. Persistence of OCPs was closely correlated to soil organic carbon concentrations. The persistence in soil of OCP’s applied to cotton crops grown more than two decades ago suggests that they could enter the food chain. Their presence at depths of 1.2 m suggests that they could move into groundwater that may eventually be used for domestic and stock consumption.     

Constant Head Injection for Enhanced In Situ Chemical Oxidation

With the successful implementation of in situ chemical oxidation (ISCO) programs to remediate contaminated soil and groundwater aquifers worldwide, ISCO has become established as a traditional remediation technique. On the basis of historical success, expanded ISCO practices are now routinely applied to increasingly difficult geologic environments, including formerly problem locations such as those containing nonaqueous‐phase liquid, fractured bedrock, low‐conductivity media, and highly layered and/or heterogeneous aquifers. Effective delivery of amendment, however, remains the single most important aspect of successful remediation, particularly given the range of potentially applicable delivery methods and site complexities. Selecting the most appropriate technique for any specific site depends upon a clear understanding of the variety of site constraints, including factors such as site conditions, underlying geology, contaminant distribution, technology limitations, and other project‐specific factors. Because the injection program is often the largest cost associated with implementation of an ISCO project, it is critical to develop a cost‐effective injection method for each site. Constant head injection provides a cost‐effective alternative for sites with low‐conductivity lithology(ies). Constant head injection employs a continuous low‐pressure application method to deliver ISCO agents over a long period of time. This synergistic method complements the existing site conditions and heterogeneity, working with the natural conditions, rather than trying to overcome or destroy the site geology using highly aggressive delivery techniques. © 2014 Wiley Periodicals, Inc.     

Water quality characteristics of discharge from reforested loose-dumped mine spoil in eastern Kentucky

Surface mining is a common method for extracting coal in the coal fields of eastern Kentucky. Using the Forestry Reclamation Approach (FRA), which emphasizes the use of minimally compacted or loose-dumped spoil as a growth medium for trees, reclamation practitioners are successfully reestablishing forests. Yet, questions remain regarding the effects FRA has on the quality of waters discharged to receiving streams. To examine the effect of FRA on water quality, this study compared waters that were discharged from three types of spoils: predominantly brown, weathered sandstone (BROWN); predominantly gray, unweathered sandstone (GRAY); and an equal mixture of both aforementioned sandstones and shale (MIXED). The water quality parameters pH, EC, Ca, K, Mg, Na, NO-N, NH-N, SO, Cl, TC, suspended sediment concentration (SSC), settleable solids (SS), and turbidity were monitored over a 2-yr period on six 0.4-ha plots (two replications per spoil type). Generally, levels of Cl, SO, Ca, NO-N, NH-N, SS, SSC, and turbidity decreased over time. The pH for all spoils increased from about 7.5 to 8.5. The EC remained relatively level in the BROWN spoil, whereas the GRAY and MIXED spoils had downward trajectories that were approaching 500 μS cm. The value of 500 μS cm has been reported as the apparent threshold at which certain taxa such as Ephemeroptera (e.g., Mayfly) recolonize disturbed headwater streams of eastern Kentucky and adjacent coal-producing Appalachian states.