Influence of temperature on the chemical removal of 3-methylbutanal,trans-2-methyl-2-butenal,and 3-methyl-2-butenal by OH radicals in the troposphere

Absolute rate coefficients for the gas-phase reactions of OH radical with 3-methylbutanal (k₁), trans-2-methyl-2-butenal (k₂), and 3-methyl-2-butenal (k₃) have been obtained with the pulsed laser photolysis/laser-induced fluorescence technique. Gas-phase concentration of aldehydes was measured by UV absorption spectroscopy at 185 nm. Experiments were performed over the temperature range of 263–353 K at total pressures of helium between 46.2 and 100 Torr. No pressure dependence of all k_i (i = 1–3) was observed at all temperatures. In contrast, a negative temperature dependence of k_i (i.e., k_i increases when temperature decreases) was observed in that T range. The resulting Arrhenius expressions (±2σ) are: k₁(T) = (5.8 ± 1.7)×10^?12 exp{(499 ± 94)/T} cm³ molecule^?1 s^?1, k₂(T)=(6.9 ± 0.9)×10^?12 exp{(526 ± 42)/T} cm³ molecule^?1 s^?1, k₃(T)=(5.6 ± 1.2)×10^?12 exp{(666 ± 54)/T} cm³ molecule^?1 s^?1.The tropospheric lifetimes derived from the above OH-reactivity trend are estimated to be higher for 3-methylbutanal than those for the unsaturated aldehydes. A comparison of the tropospheric removal of these aldehydes by OH radicals with other homogeneous degradation routes leads to the conclusion that this reaction can be the main homogeneous removal pathway. However, photolysis of these aldehydes in the actinic region (λ > 290 nm) could play an important role along the troposphere, particularly for 3-methyl-2-butenal. This process could compete with the OH reaction for 3-methylbutanal or be negligible for trans-2-methyl-2-butenal in the troposphere.     

Indirect assessment of economic damages from the Prestige oil spill: consequences for liability and risk prevention

The social losses arising from the Prestige oil spill exceed the compensation granted under the IOPC (International Oil Pollution Compensation) system, with losses estimated at 15 times more than the applicable limit of compensations. This is far above the level of costs for which those responsible for hydrocarbons spills are liable. The highest market losses correspond to sectors of extraction, elaboration and commercialisation of seafood. However, damages to non-commercial natural resources could constitute an outstanding group of losses for which further primary data are needed: these losses would only be compensable under the current system by means of a refund for cleaning and restoration costs. Results show that, in Europe, the responsibility for oil spills in maritime transport is limited and unclear. The consequence of this is net social losses from recurrent oil spills and internationally accepted incentives for risky strategies in the marine transport of hydrocarbons.     

Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH₂C(CH₃)C(O)OCH₃ (MMA), CH₂CHC(O)OCH₃ (MAC) and CH₂C(CH₃)C(O)O(CH₂)₃CH₃ (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10^?10 cm³ molecule^?1 s^?1) as follows: k_(Cl+MMA) = 2.82 ± 0.93, k_(Cl+MAC) = 2.04 ± 0.54 and k_(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm³ molecule^?1 s^?1): k_(Cl+MMA) = (13.9 ± 7.8) × 10^?15 exp[(2904 ± 420)/T], k_(Cl+MAC) = (0.4 ± 0.2) × 10^?15 exp[(3884 ± 879)/T], k_(Cl+BMA) = (0.98 ± 0.42) × 10^?15 exp[(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log k_OH = 1.09 log k_Cl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.     

Climate change and natural disasters: macroeconomic performance and distributional impacts

Commonly occurring natural events become natural disasters when they affect the population through death and injury, and/or through the destruction of natural and physical capital on which people rely for their livelihood and quality of life. Climate change plays a role in that it tends to increase the frequency and intensity of weather-related natural disasters. Additionally, climate change may put people at risk by influencing access to water, coastal flooding, disease and hunger, and leaving them with a more degraded environment, leading, in turn, to increased vulnerability. The purpose of this paper is to present a review and synthesis of the literature and case studies addressing differential impacts of climate change-related natural disasters on a society and its economy. Developed and developing countries show different vulnerabilities to natural disasters. Even within countries, impacts vary significantly across population and economic sectors. When losses from natural disasters are large, their cumulative effect can have notable macroeconomic impacts, which feed back to further pronounce existing income inequalities and lower income levels. Impacts tend to be most pronounced for women, the young and elderly, and people of ethnic or racial minorities.

Aiding multi-level decision-making processes for climate change mitigation and adaptation

Progress towards climate change aware regional sustainable development is affected by actions at multiple spatial scales and governance levels and equally impacts actions at these scales. Many authors and policy practitioners consider therefore that decisions over policy, mitigation strategies and capacity for adaptation to climate change require construction and coordination over multiple levels of governance to arrive at acceptable local, regional and global management strategies. However, how such processes of coordination and decision-aiding can occur and be maintained and improved over time is a major challenge in need of investigation. We take on this challenge by proposing research-supported methods of aiding multi-level decision-making processes in this context. Four example regionally focussed multi-level case studies from diverse socio-political contexts are outlined—estuarine management in Australia’s Lower Hawkesbury, flood and drought management in Bulgaria’s Upper Iskar Basin, climate policy integration in Spain’s Comunidad Valenciana and food security in Bangladesh’s Faridpur District—from which insights are drawn. Our discussion focuses on exploring these insights including: (1) the possible advantages of informal research-supported processes and specifically those that provide individual arenas of participation for different levels of stakeholders; (2) the complexity of organisation processes required for aiding multi-level decision-making processes; and (3) to what extent progress towards integrated regional policies for climate change aware sustainable development can be achieved through research-supported processes. We finish with a speculative section that provides ideas and directions for future research.     

Evaluation of residue risk and toxicity of different treatments with diazinon insecticide applied to mushroom crops

ABSTRACT

This work describes the phytotoxic effect of different doses of diazinon and different application times on Agaricus bisporus mycelium, and determines the residue levels in mushrooms from the first three flushes. Mushroom cultivation is a widespread commercial activity throughout the world. The application of insecticide diazinon to the compost or casing layer is a common practice to control two mushroom pests, the phorid Megaselia halterata and the sciarid Lycoriella auripila. Application to the compost does not result in any appreciable fall in yield or quality, and does not delay the harvest time. In contrast, application to the casing led to a slight fall (6.2%) in production and a smaller number of mushrooms although they are larger in size. Residue levels of more than 0.01 ppm are detected in many of the samples analyzed, and raising the question whether the product should continue to be used in mushroom cultivation in the conditions in which it is currently applied.     

Raw sugarcane bagasse as carbon source for xylanase production by Paenibacillus species: a potential degrader of agricultural wastes

Environmental Science and Pollution Research - Paenibacillus species isolated from a variety of natural sources have shown to be important glycoside hydrolases producers. These enzymes play a key...     

Assessment of spent mushroom substrate as sorbent of fungicides: influence of sorbent and sorbate properties

The capacity of spent mushroom substrate (SMS) as a sorbent of fungicides was evaluated for its possible use in regulating pesticide mobility in the environment. The sorption studies involved four different SMS types in terms of nature and treatment and eight fungicides selected as representative compounds from different chemical groups. Nonlinear sorption isotherms were observed for all SMS-fungicide combinations. The highest sorption was obtained by composted SMS from Agaricus bisporus cultivation. A significant negative and positive correlation was obtained between the K(OC) sorption constants and the polarity index values of sorbents and the K(OW) of fungicides, respectively. The statistic revealed that more than 77% of the variability in the K(OW) could be explained considering these properties jointly. The other properties of both the sorbent (total carbon, dissolved organic carbon, or pH) and the sorbate (water solubility) were nonsignificant. The hysteresis values for cyprodinil (log K(OW)= 4) were for all the sorbents much higher (>3) than for other fungicides. This was consistent with the remaining sorption after desorption considered as an indicator of the sorption efficiency of SMS for fungicides. Changes in the absorption bands of fungicides sorbed by SMS observed by FTIR permitted establishing the interaction mechanism of fungicides with SMS. The findings of this work provide evidence for the potential capacity of SMS as a sorbent of fungicides and the low desorption observed especially for some fungicides, although they suggest that more stabilized or humified organic substrates should be produced to enhance their efficiency in environmental applications.     

Potentiation of antifungal effect of a mixture of two antifungal fractions obtained from Baccharis glutinosa and Jacquinia macrocarpa plants

The aim of the present work was to evaluate the effect of mixtures of antifungal fractions extracted from Baccharis glutinosa and Jacquinia macrocarpa plants on the development of the filamentous fungi Aspergillus flavus and Fusarium verticillioides. The minimal inhibitory concentration that inhibited 50% of growth (MIC₅₀) of each plant antifungal fraction was determined from the percentage radial growth inhibition of both fungi. Binomial mixtures made with both plant fractions were used at their MIC₅₀ to determine the Fractional Inhibitory Concentration index (FIC index) for each fungus in order to evaluate their synergistic effect. Each synergistic mixture was analyzed in their effect on spore germination, spore size, spore viability, mitotic divisions, hyphal diameter and length, and number of septa per hypha. Some antifungal mixtures, even at low concentrations, showed higher antifungal effect than those of the individual antifungal fraction. The FIC indices of mixtures that showed the highest antifungal activity against A. flavus and F. verticillioides were 0.5272 and 0.4577, respectively, indicating a synergistic effect against both fungi. Only 12% and 8% of the spores of A. flavus and F. verticillioides, respectively, treated with the synergistic mixtures, were able to germinate, although their viability was not affected. An increase in the number of septa per hypha of both fungi was observed. The results indicated that the synergistic mixtures strongly affected the fungal growth even at lower concentrations than those of the individual plant fractions.     

Managing water services in tropical regions: From land cover proxies to hydrologic fluxes

Watershed investment programs frequently use land cover as a proxy for water-based ecosystem services, an approach based on assumed relationships between land cover and hydrologic outcomes. Water flows are rarely quantified, and unanticipated results are common, suggesting land cover alone is not a reliable proxy for water services. We argue that managing key hydrologic fluxes at the site of intervention is more effective than promoting particular land-cover types. Moving beyond land cover proxies to a focus on hydrologic fluxes requires that programs (1) identify the specific water service of interest and associated hydrologic flux; (2) account for structural and ecological characteristics of the relevant land cover; and, (3) determine key mediators of the target hydrologic flux. Using examples from the tropics, we illustrate how this conceptual framework can clarify interventions with a higher probability of delivering desired water services than with land cover as a proxy.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-014-0578-8) contains supplementary material, which is available to authorized users.