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841.
Díaz-de-Mera Y Aranda A Bravo I Rodríguez D Rodríguez A Moreno E 《Environmental science and pollution research international》2008,15(7):584-591
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. 相似文献
842.
Kelly L. Zellars Pamela L. Perrewé Ana M. Rossi Bennett J. Tepper Gerald R. Ferris 《组织行为杂志》2008,29(5):549-571
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. 相似文献
843.
Laura K.M. Donorfio Author Vitae Lisa A. D'Ambrosio Author Vitae Author Vitae 《Journal of Safety Research》2008,39(6):555-561
Problem
The purpose of this research was to examine the impact of age and health on patterns of driving and self-regulation among older adults who still drive.Method
This analysis presents the results of a nationwide survey of drivers who are 50 + (N = 3,824, 53.11% response rate), focusing on questions about the impact of their self-reported health on attitudes toward and self-regulation of driving.Results
The data indicate that as age increases, so too does reported self-regulation of driving, increasing sharply among those ages 70 and older. The data also indicate that respondent's reported confidence in driving and their enjoyment of driving decline as they age. Health status bears a significant relationship with all three of these variables, positively related to confidence in driving skills and to enjoyment in driving, but negatively related to self-regulation reports. As self-reported health declines, respondent's report engages in greater voluntary restrictions of their driving.Discussion
All too often, the driving decision is linked primarily to chronological age. Analysis done here indicates that age alone is not the best indicator of self-regulation and how older adults change their driving behaviors.Summary
This research presents the results of a nationwide survey of 50+ drivers and their self-reported driving, self-regulation behaviors, and health status. Strong support was found for the argument that chronological age is not an adequate measure of self-regulating behaviors and driver safety among those 50+. In particular, it was found that a person's health status and the interaction between age and health are essential considerations in the decisions around self-regulation and driving. People tend to self-regulate more with age, but the effect becomes much more pronounced as health status declines.Impact on industry
In the coming years, if older adults can't get to where they want to go and continue to be viable consumers in our national fabric, all industries will eventually suffer. Transportation is a key component to the nation's social contract with older individuals and their families. 相似文献844.
Parente TE De-Oliveira AC Paumgartten FJ 《Environmental pollution (Barking, Essex : 1987)》2008,152(1):233-238
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. 相似文献
845.
Gómez MJ Malato O Ferrer I Agüera A Fernández-Alba AR 《Journal of environmental monitoring : JEM》2007,9(7):718-729
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). 相似文献
846.
J. W. Chapman Trevor Williams Ana M. Martínez Juan Cisneros Primitivo Caballero Ronald D. Cave Dave Goulson 《Behavioral ecology and sociobiology》2000,48(4):321-327
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 相似文献
847.
Alessandro Fumagalli Bruno Faggion Matteo Ronchini Giorgio Terzaghi Marco Lanfranchi Nicola Chirico Laura Cherchi 《Environmental science and pollution research international》2010,17(3):665-673
Background, aim, and scope
The widespread use of some platinum group elements as catalysts to minimize emission of pollutants from combustion engines produced a constantly growing increase of the concentration of these elements in the environment; their potential toxicological properties explain the increasing interest in routine easy monitoring. We have found that leaves of Prunus laurus cerasus are efficient collectors of particulate with a dimension <60–80 μm, and a simple and reliable procedure was developed to reveal traces of platinum, palladium, and rhodium released from automotive catalysts. The analysis of the dust deposited on the foliage is a direct indicator of traffic pollution. 相似文献848.
Charbel Jose Chiappetta Jabbour Ana Beatriz Lopes de Sousa Jabbour 《International Journal of Green Energy》2016,13(9):907-910
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. 相似文献
849.
Célia Alves Ana I. Calvo Liliana Marques Amaya Castro Teresa Nunes Esther Coz Roberto Fraile 《Environmental science and pollution research international》2014,21(21):12390-12402
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. 相似文献
850.
Changhui Wang Leilei Bai Yuansheng Pei Laura A. Wendling 《Environmental science and pollution research international》2014,21(23):13528-13538
Recycling of drinking water treatment residuals (WTRs) as environment amendments has attracted substantial interest due to their productive reuse concomitant with waste minimization. In the present study, the extractability of metals within six Al/Fe-hydroxide-comprised WTRs collected throughout China was investigated using fractionation, in vitro digestion and the toxicity characteristic leaching procedure (TCLP). The results suggested that the major components and structure of the WTRs investigated were similar. The WTRs were enriched in Al, Fe, Ca, and Mg, also contained varying quantities of As, Ba, Be, Cd, Co, Cr, Cu, K, Mn, Mo, Na, Ni, Pb, Sr, V, and Zn, but Ag, Hg, Sb, and Se were not detected. Most of the metals within the WTRs were largely non-extractable using the European Community Bureau of Reference (BCR) procedure, but many metals exhibited high bioaccessibility based on in vitro digestion. However, the WTRs could be classified as non-hazardous according to the TCLP assessment method used by the US Environmental Protection Agency (USEPA). Further analysis showed the communication factor, which is calculated as the ratio of total extractable metal by BCR procedure to the total metal, for most metals in the six WTRs, was similar, whereas the factor for Ba, Mn, Sr, and Zn varied substantially. Moreover, metals in the WTRs investigated had different risk assessment code. In summary, recycling of WTRs is subject to regulation based on assessment of risk due to metals prior to practical application. 相似文献