Study of the spontaneous ignition of stoichiometric tetrafluoroethylene–air mixtures at elevated pressures

The Ignition Temperature (IT) of stoichiometric tetrafluoroethylene–air mixtures on hot walls was determined in a 3-dm³-reactor. Tests at elevated pressure conditions were performed, namely at 5, 15 and 25 bar(a), showing a decrease of the IT with the initial pressure. Furthermore, the measured ignition temperatures of stoichiometric tetrafluoroethylene–air mixtures were lower than the ignition temperatures required for the decomposition pure tetrafluoroethylene (Minimum Ignition Temperature of Decomposition, MITD) reported in previous works.Equations from the Semenov thermal explosion theory on spontaneous ignition were used to identify approximate combustion kinetics of tetrafluoroethylene from the experimental results. The determined kinetics was used for the prediction of the IT of stoichiometric tetrafluoroethylene-air by simplified calculation methods. A very good agreement with the experimental results was observed.     

When do you procrastinate? Sleep quality and social sleep lag jointly predict self‐regulatory failure at work

This study investigates antecedents of procrastination, the tendency to delay the initiation or completion of work activities. We examine this phenomenon from a self‐regulation perspective and argue that depleted self‐regulatory resources are an important pathway to explain why and when employees procrastinate. The restoration of self‐regulatory resources during episodes of non‐work is a prerequisite for the ability to initiate action at work. As sleep offers the opportunity to replenish self‐regulatory resources, employees should procrastinate more after nights with low‐quality sleep and shorter sleep duration. We further propose that people's social sleep lag amplifies this relationship. Social sleep lag arises if individuals' preference for sleep and wake times, known as their chronotype, is misaligned with their work schedule. Over five consecutive workdays, 154 participants completed a diary study comprising online questionnaires. Multilevel analyses showed that employees procrastinated less on days when they had slept better. The more employees suffered from social sleep lag, the more they procrastinated when sleep quality was low. Day‐specific sleep duration, by contrast, was not related to procrastination. We discuss the role of sleep for procrastination in the short run and relate our findings to research highlighting the role of sleep for well‐being in the long run. Copyright © 2016 John Wiley & Sons, Ltd.     

Toxicity of emerging energetic soil contaminant CL-20 to potworm Enchytraeus crypticus in freshly amended or weathered and aged treatments

We investigated the toxicity of an emerging polynitramine energetic material hexanitrohexaazaisowurtzitane (CL-20) to the soil invertebrate species Enchytraeus crypticus by adapting then using the Enchytraeid Reproduction Test (ISO/16387:2003). Studies were designed to develop ecotoxicological benchmark values for ecological risk assessment of the potential impacts of accidental release of this compound into the environment. Tests were conducted in Sassafras Sandy Loam soil, which supports relatively high bioavailability of CL-20. Weathering and aging procedures for CL-20 amended into test soil were incorporated into the study design to produce toxicity data that better reflect soil exposure conditions in the field compared with the toxicity in freshly amended soils. Concentration-response relationships for measurement endpoints were determined using nonlinear regressions. Definitive tests showed that toxicities for E. crypticus adult survival and juvenile production were significantly increased in weathered and aged soil treatments compared with toxicity in freshly amended soil, based on 95% confidence intervals. The median effect concentration (EC50) and EC20 values for juvenile production were 0.3 and 0.1 mg kg-1, respectively, for CL-20 freshly amended into soil, and 0.1 and 0.035 mg kg-1, respectively, for weathered and aged CL-20 soil treatments. These findings of increased toxicity to E. crypticus in weathered and aged CL-20 soil treatments compared with exposures in freshly amended soils show that future investigations should include a weathering and aging component to generate toxicity data that provide more complete information on ecotoxicological effects of emerging energetic contaminants in soil.     

Toxicity of the explosive metabolites hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) and hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) to the earthworm Eisenia fetida

Toxicity of hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) to earthworm was evaluated. Both MNX and TNX had lethal and sublethal effects on earthworms. Exposure to MNX- or TNX-contaminated soil caused a significant concentration-dependent decrease in earthworm survival and growth. The lowest observed lethal concentration (LOLC) for both MNX and TNX was 100 and 200 mgkg(-1) soil dry weight in the sandy loam soil and in the silt loam soil, respectively. No earthworms survived for 14 days in MNX- or TNX-spiked soil at 500 mgkg(-1) soil dry weight. After 7 days exposure, the lowest observed effect concentration (LOEC) for earthworm growth was 50 mgkg(-1) soil dry weight for TNX and 100 mgkg(-1) soil dry weight for MNX in both soil types. The LC20 and LC50 for MNX in sandy loam soil were 114 and 262 mgkg(-1) and for TNX, they were 114 and 254 mgkg(-1) soil dry weight, respectively. The corresponding values for MNX and TNX in silt loam soil were 234 and 390 mgkg(-1) soil dry weight, respectively, and 200 and 362 mgkg(-1) soil dry weight, respectively. After 35 days exposure, earthworm growth was reduced 8-39% by TNX in sandy loam soil, whereas TNX only inhibited earthworm growth 5-18% at the same concentration range in silt loam soil. LC20 and LC50 for TNX were slightly lower than for MNX; this indicates that TNX was more toxic than MNX. No significant morphological or developmental abnormalities were observed in earthworms surviving exposure.     

Perchlorate in fish from a contaminated site in east-central Texas

Perchlorate, a known thyroid endocrine disruptor, contaminates surface waters near military instillations where solid fuel rocket motors are manufactured or assembled. To assess potential perchlorate exposure to fish and the human population which may feed on them, fish were collected around the Naval Weapons Industrial Reserve Plant in McLennan County, TX, and analyzed for the presence of the perchlorate anion. The sampling sites included Lake Waco and Belton Lake, and several streams and rivers within their watersheds. The general tendency was that perchlorate was only found in a few species sampled, and perchlorate was not detected in every individual within these species. When detected in the fish, perchlorate tissue concentrations were greater than that in the water. This may be due to highly variable perchlorate concentrations in the water coupled with individual-level variation in elimination from the body, or to routes of exposure other than water.     

Anionic surfactant remediation of soil columns contaminated by nonaqueous phase liquids

A variety of column experiments have been completed for the purpose of selecting and evaluating suitable surfactants for remediation of nonaqueous phase liquids (NAPLs). The various NAPLs tested in the laboratory experiments were tetrachloroethylene (PCE), trichloroethylene (TCE), jet fuel (JP4) and a dense nonaqueous phase liquid from a site at Hill Air Force Base, UT. Both Ottawa sand and Hill field soil were used in these experiments. Surfactant candidates were first screened using phase behavior experiments and only the best ones were selected for the subsequent column experiments. Surfactants which showed high contaminant solubilization, fast coalescence times, and the absence of liquid crystal phases and gels during the phase behavior experiments were tested in soil column experiments. The primary objective of the soil column experiments was to identify surfactants that recovered at least 99% of the contaminant. The secondary objective was to identify surfactants that show low adsorption and little or no loss of hydraulic conductivity during the column experiments. Results demonstrated that up to 99.9% of the contaminants were removed as a result of surfactant flooding of the soil columns. The addition of xanthan gum polymer to the surfactant solution was shown to increase remediation efficiency as a lower volume of surfactant was required for recovering a given volume of NAPL. Based on these experimental results, guidelines for designing highly efficient and robust surfactant floods have been developed and applied to a field demonstration.     

Change of stream network connectivity under polder-type flood control measure

Polder is usually used for flood control in the river delta area. With the rapid development of urbanization, the dikes or pumps cut the original stream network system, and the stream network connectivity (SNC) and the river system pattern have changed. The dikes or pumps generally force up the river's water level, and regional flood formation mechanisms and processes have changed. In order to quantitatively describe the characteristics of polder-type flood control measure (PFCM) and the change law of SNC, firstly, the streams inside polders were generalized as virtual streams, a hydrological-hydrodynamic model was constructed by connecting Hydrologic Engineering Center-Hydrologic Modeling System and MIKE11 model. Secondly, an SNC evaluation model was constructed based on flow resistance and hydrological process. Finally, the SNC under different scenarios was simulated and evaluated to reveal the influence of the PFCM on SNC. And the dominance analysis method obtained the main control factors of SNC changes. The results showed that the pumps as the main drainage facility under the PFCM, SNC after the opening of the pumps were increased by 0.060, 0.103, and 0.311 for 50%, 30%, and 3% frequency flood scales compared with the pumps closed, respectively. However, compared with the natural stream (without the PFCM), the SNC decreased by 0.391, 0.456, and 0.487, respectively, at the same time of the same flood scale. The PFCM negatively impacted the SNC, and the number of pumps was the main control factor of the SNC.     

Buyer–supplier alliances in the automobile industry: how exit‐voice strategies influence interpersonal relationships

Although automobile manufacturers emphasize that they are building more cooperative, long‐term relationships with their suppliers, we hypothesized and found that buyers are actually pursuing a dual strategy approach, in which they use threats on out‐group suppliers while providing help to in‐group members. Our hypotheses were based on the exit, voice, and loyalty typology, and on research from leader–member exchange theory. We also found that the macro‐level strategy set the context for the micro‐level interactions between buyers and suppliers. The degree to which the buyers and suppliers interacted in a friendly, informal manner depended more on the in‐ or out‐group status of the supplier firm than on the interaction style preferences of the suppliers. These findings are consistent with Mischel's ( 1977 ) theory that individual differences predict behavior under weak environmental conditions but not under strong environments. Compared to buyers, suppliers were more likely to prefer a friendly, informal interaction style. These findings were predicted based on the research on emotional display rules and emotional labor. Copyright © 2000 John Wiley & Sons, Ltd.     

Environmental VOSCs--formation and degradation of dimethyl sulfide, methanethiol and related materials

Volatile organic sulfur compounds (VOSCs) play a major role in the global sulfur cycle. Two components, dimethyl sulfide (DMS) and methanethiol (MT) are formed in large amounts by living systems (e.g. algae, bacteria, plants), particularly in marine environments. A major route to DMS is by action of a lyase enzyme on dimethylsulfoniopropionate (DMSP). DMSP has other roles, for instance as an osmoprotectant and cryoprotectant. Demethiolation of DMSP and other materials leads to MT. A major transport process is release of DMS from the oceans to the atmosphere. Oxidation of DMS in the atmosphere by hydroxyl and nitrate radicals produces many degradation products including CO2, COS, dimethyl sulfoxide, dimethyl sulfone, organic oxyacids of sulfur, and sulfate. These materials also have roles in biotic processes and there are complex metabolic interrelationships between some of them. This review emphasizes the chemical reactions of the organic sulfur cycle. For biotic reactions, details of relevant enzymes are provided when possible.