Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Moderating effects of political skill,perceived control,and job‐related self‐efficacy on the relationship between negative affectivity and physiological strain

The present study examined whether employees high in negative affectivity (NA) are destined to experience strain at a higher level than those low in NA. We used data collected from 230 employees to investigate the moderating effects of political skill, as a form of interpersonal control, on the relationship between NA and physiological strain. As hypothesized, NA was positively related to physiological strain (i.e., facial muscle tension as measured by electromyography (EMG)), and political skill buffered this effect such that the relationship was weaker among employees who were higher in political skill. Tests of mediated moderation further suggested the means by which political skill moderates the NA/strain relationship; specifically, the results were consistent with the idea that perceived control and, in turn, job‐related efficacy explain the moderating effect of political skill. Strengths and limitations of the study, practical implications, and directions for future research are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Induced cytochrome P450 1A activity in cichlid fishes from Guandu River and Jacarepaguá Lake, Rio de Janeiro, Brazil

The induction of cytochrome P4501A-mediated activity (e.g. ethoxyresorufin-O-deethylation, EROD) has been used as a biomarker for monitoring fish exposure to AhR-receptor ligands such as polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and polychlorinated dibenzo-dioxins/furans (PCDD/Fs). In this study we found that hepatic EROD is induced in fish ("Nile tilapia", Oreochromis niloticus and "acará", Geophagus brasiliensis) from the Guandu River (7-17-fold) and Jacarepaguá Lake (7-fold), Rio de Janeiro, Brazil. Since both cichlid fish are consumed by the local population and the Guandu River is the main source of the drinking water supply for the greater Rio de Janeiro metropolitan area, pollution by cytochrome P4501A-inducing chemicals is a cause for concern and should be further investigated in sediments, water and biota. We additionally showed that EROD activity in the fish liver post-mitochondrial supernatant-simpler, cheaper and less time consuming to prepare than the microsomal fraction-is sufficiently sensitive for monitoring purposes.     

Solid-phase extraction followed by liquid chromatography-time-of-flight-mass spectrometry to evaluate pharmaceuticals in effluents. A pilot monitoring study

The present work provides a multi-residue analytical method for determining a selection of 20 pharmaceuticals from diverse therapeutical classes in hospital effluent wastewater. The method is based on the simultaneous extraction of the target compounds by solid phase extraction (SPE), followed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) analysis. Using TOF-MS, accurate mass measurements within 2 ppm error were obtained for most of the pharmaceuticals studied. Empirical formula information can be obtained by this method, allowing the unequivocal identification of the target compounds in the samples. Validation studies showed that LC-TOF-MS analysis is a valuable new tool for identification and quantification of pharmaceuticals in wastewater. Recoveries, using Oasis HLB cartridges at pH 7, were higher than 75% for all pharmaceuticals, except for ranitidine, 4-methylaminoantipyrine (4-MAA), cefotaxime and omeprazole, which needed specific pH conditions for their extraction. Linearity of response over two orders of magnitude was demonstrated (r > 0.99). Matrix effects resulting in suppression of the response were observed. For most of the compounds ion suppression was less than 39%, except for metronidazole, carbamazepine 10,11-epoxide, naproxen and erythromycin, where the signal suppression was 42%, 59%, 46% and 95%, respectively. A simple and effective approach to minimize or avoid matrix interferences was the 1 : 4 dilution of the SPE extracts. Method detection limits (MDLs) and quantification limits (MQLs) ranged between 4-115 ng l(-1) and 14-384 ng l(-1), respectively. The precision of the method, calculated as relative standard deviation (RSD), ranged from 1.1-19.8% and 1.7-21.7% for intra- and inter-day, respectively. The developed analytical method was applied to the analysis of hospital effluent wastewater during a survey study. 18 of the 20 pharmaceuticals studied were detected at concentration levels of microg l(-1), reaching in some cases concentrations over 100 microg l(-1), and in the case of the analgesic and antipyretic dipyrone metabolite, higher than 1000 microg l(-1).     

Does cannibalism in Spodoptera frugiperda (Lepidoptera: Noctuidae) reduce the risk of predation?

The incidence of cannibalism of larval Spodoptera frugiperda (Lepidoptera: Noctuidae) on maize under field conditions was investigated using field cages. Cannibalism was found to account for approximately 40% mortality when maize plants were infested with two or four fourth-instar larvae over a 3-day period. Field trials examined the effect of larval density on the prevalence of natural enemies of S. frugiperda. The abundance of predators (earwigs, staphylinids, other predatory beetles, and Chrysoperla spp.) was significantly greater on maize plants with higher levels of larval feeding damage, while the relationship between predator abundance and number of S. frugiperda larvae per plant was less clear. As larval damage is probably a more reliable indicator of previous larval density than numbers collected at an evaluation, this indicates that predation risk will be greater for larvae living in large groups. Parasitism accounted for 7.1% mortality of larvae in sorghum, and involved six species of Hymenoptera and Tachinidae. There was no effect of larval density or within-plant distribution on the probability of larval attack by parasitoids. The selective benefits of cannibalism, in relation to the risk of predation and parasitism, are discussed. Received: 23 March 2000 / Accepted: 24 June 2000     

Demystifying the challenges and barriers to manage,develop, and transfer clean and green technologies in Brazilian academic research groups: Some empirical evidence

This work presents empirical evidence of the main challenges in managing/leading academic research groups on clean and green technologies in Brazilian universities. We also present evidence about the main barriers to the effective creation of innovation and technology transfer of these clean and green technologies. Empirical evidence come from PhD researchers/academics who lead/manage official research groups on clean (environmental, green) technologies. Results show the following: (a) The main challenges of managing research groups are the lack of an innovative culture, the lack of partnership with an industrial sector, and the necessity of keeping laboratories updated; (b) the main barriers to innovation and technology transfer are difficulties in not having enough researchers and staff members, assessments of academic performance that do not consider innovation, and an uncertain national legislation on clean technology. Based on these and others’ findings, we suggest that policymakers working on clean and green technologies pay attention to act and develop initiatives focusing on the following: providing direct financial support for laboratory improvement, linking academics and practitioners from the industrial sector, and providing training and development programs on clean and green technologies’ legislation and financial issues, such as the payoff of clean and green technologies and opportunities from green investors.     

Particulate matter in the indoor and outdoor air of a gymnasium and a fronton

An indoor/outdoor monitoring programme of PM₁₀ was carried out in two sports venues (a fronton and a gymnasium). Levels always below 50 μg m^?3 were obtained in the fronton and outdoor air. Due to the climbing chalk and the constant process of resuspension, concentrations above 150 μg m^?3 were registered in the gymnasium. The chalk dust contributed to CO₃ ^2? concentrations of 32?±?9.4 μg m^?3 in this sports facility, which represented, on average, 18 % of the PM₁₀ mass. Here, the carbonate levels were 128 times higher than those registered outdoors. Much lower concentrations, around 1 μg m^?3, were measured in the fronton. The chalk dust is also responsible for the high Mg²⁺ concentrations in the gym (4.7?±?0.89 μg m^?3), unfolding a PM₁₀ mass fraction of 2.7 %. Total carbon accounted for almost 30 % of PM₁₀ in both indoor spaces. Aerosol size distributions were bimodal and revealed a clear dependence on physical activities and characteristics of the sports facilities. The use of climbing chalk in the gymnasium contributed significantly to the coarse mode. The average geometric mean diameter, geometric standard deviation and total number of coarse particles were 0.77 μm, 2.79 cm^?3 and 28 cm^?3, respectively.     

Soil quality assessment in rice production systems: establishing a minimum data set

Soil quality, as a measure of the soil's capacity to function, can be assessed by indicators based on physical, chemical, and biological properties. Here we report on the assessment of soil quality in 21 rice (Oryza sativa) fields under three rice production systems (semi-direct, pre-germinated, and conventional) on four soil textural classes in the Camaqu? region of Rio Grande do Sul, Brazil. The objectives of our study were: (i) to identify soil quality indicators that discriminate both management systems and soil textural classes, (ii) to establish a minimum data set of soil quality indicators and (iii) to test whether this minimum data set is correlated with yield. Twenty-nine soil biological, chemical, and physical properties were evaluated to characterize regional soil quality. Soil quality assessment was based on factor and discriminant analysis. Bulk density, available water, and micronutrients (Cu, Zn, and Mn) were the most powerful soil properties in distinguishing among different soil textural classes. Organic matter, earthworms, micronutrients (Cu and Mn), and mean weight diameter were the most powerful soil properties in assessing differences in soil quality among the rice management systems. Manganese was the property most strongly correlated with yield (adjusted r2 = 0.365, P = 0.001). The merits of sub-dividing samples according to texture and the linkage between soil quality indicators, soil functioning, plant performance, and soil management options are discussed in particular.     

Spiking solvent, humidity and their impact on 2,4-D and 2,4-DCP extractability from high humic matter content soils

The 2,4-dichlorophenoxyacetic acid (2,4-D) is a hormone-like herbicide widely used in agriculture. Although its half life in soil is approximately two weeks, the thousands of tons introduced in the environment every year represent a risk for human health and the environment. Considering the toxic properties of this compound and its degradation products, it is important to assess and monitor the 2,4-D residues in agricultural soils. Furthermore, experiments of phyto/bioremediation are carried out to find economic and environmental friendly tools to restore the polluted soils. Accordingly, it is essential to accurately measure the amount of 2,4-D and its metabolites in soils. There is evidence that 2,4-D extraction from soil samples seriously depends on the physical and chemical properties of the soil, especially in those soils with high content of humic acids. The aim of this work was to assess the variables that influence the recovery and subsequent analysis of 2,4-D and its main metabolite (2,4-dichlorophenol) from those soils samples. The results showed that the recovery efficiency depends on the solvent and method used for the extraction, the amount and kind of solvent used for dissolving the herbicide and the soil water content at the moment of spiking. An optimized protocol for the extraction and quantification of 2,4-D and its main metabolite from soil samples is presented.     

Dietary exposure to PCDD/PCDFs by individuals living near a hazardous waste incinerator in Catalonia, Spain: temporal trend

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were measured in foodstuffs randomly acquired in July 2006 in various locations of Tarragona County (Catalonia, Spain), which are near a hazardous waste incinerator (HWI). A total of 35 composite samples, belonging to various food groups (vegetables, pulses, cereals, fruits, fish and seafood, meat and meat products, eggs, milk, dairy products, and oils and fats) were analyzed by HRGC/HRMS. The dietary intake of PCDD/PCDFs was subsequently determined and compared with a previous survey performed in 2002. For calculations, recent data on consumption of the selected food items were used. Total dietary intake of PCDD/PCDFs for the general population of Tarragona County was estimated to be 27.81 pg WHO-TEQ/day, value notably lower than that found in the 2002 study, 63.80 pg WHO-TEQ/day. Fish and seafood (28%), oils and fats (22%), eggs (17%), and dairy products (11%) were the most important contributors to this intake, while pulses (1%), milk (2%), vegetables (3%) and fruits (3%) showed the lowest contribution to total WHO-TEQ. The current PCDD/PCDF intake is also considerably lower than the intake estimated in 1998 for the population of the same geographical area, 210.1 pg I-TEQ/day, when a baseline study was carried out during the construction of the HWI. The present intake is also compared with the dietary intakes of PCDD/PCDFs recently (2006-2007) reported for a number of regions and countries.