Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

Using a reduced Common Representative Intermediates (CRIv2-R5) mechanism to simulate tropospheric ozone in a 3-D Lagrangian chemistry transport model

A reduced chemical scheme (CRIv2-R5) which describes ozone formation from the tropospheric degradation of methane and 22 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been applied in a global-3D chemistry transport model (STOCHEM). The scheme, which contains 220 species in 609 reactions, has been used to simulate ozone and its precursors for the meteorological year of 1998 and the results have been compared with those from STOCHEM runs with its original chemistry. Compared with the original chemistry scheme, the degradation of a larger number of more reactive VOCs in the CRI scheme results in the formation (and their consequent transportation) of more NO_x active reservoirs thus leading to formation of more ozone away from land-based sources. Conversely, the more reactive VOCs also lead to greater removal of OH in continental areas and greater formation of OH in marine environments. STOCHEM run with the CRI scheme simulates more ozone (by up to 10 ppb), which results in better agreement with observed vertical ozone profiles. The CRI scheme transforms the globally and annually integrated ozone budget for the considered year in STOCHEM from a net loss of ?55 Tg yr^?1 to a net gain of +50 Tg yr^?1.     

Sea salt concentrations across the European continent

The oceans are a major source for particles that play an important role in many atmospheric processes. In Europe sea salt may contribute significantly to particulate matter concentrations. We have compiled sodium concentration data as a tracer for sea salt for 89 sites in Europe to provide more insight in the distribution of sea salt across Europe. The annual average sea salt concentrations above land were estimated to range between 0.3 and almost 13 μg m^?3. Maximum concentrations are found at the Irish coast. At coastal sites along the Atlantic and North Sea coast concentrations tend to be around 5 μg m^?3. More inland locations up to about 300 km away from the coast tend to show concentrations between 2 and 5 μg m^?3, whereas sites further away from the coast are characterized by lower concentrations. An analysis of the representativity of the data with respect to a long term average showed that the long average is associated with a standard deviation of around 15%. The compilation of observations provides an improved overview of sea salt concentrations in Europe as well as an improved basis for model validation. Verification of the results of the LOTOS-EUROS model learned that the model represents well the spatial variability of the observed sea salt concentrations very well. However, the absolute concentrations are significantly overestimated due to large uncertainties in the emission and dry deposition parameterizations. Using the high explained variability in the gradients across Europe, the bias-corrected modelled distribution serves as a best estimate of the sea salt distribution across Europe for 2005.     

High and low value fish chains in the Mekong Delta: challenges for livelihoods and governance

This paper investigates the structure, function and wealth distribution within the Pangasius hypophthalmus and Henicorhynchus spp./Labiobarbus spp. value chains in the Mekong Delta of Vietnam. The analysis is driven by key questions relating to the form and function of value chains, their contribution to the livelihoods of farmers and fishers, the effectiveness of government policy and the potential for value chain governance mechanisms, such as contracts and certification, to steer towards sustainable production. The results indicate that actors in the high value Pangasius hypopthalmus export chain have a higher potential income, but face considerably higher economic vulnerability from global markets. Alternatively, Henichorhychus/Labiobarbus spp. fishers are severely constrained in their ability to negotiate higher prices for their fish but appear to be less vulnerable to economic and environmental change. The paper concludes that for value chain governance to improve the livelihoods of fishers and farmers in both high and low value chains, new arrangements are needed that better accommodate customary institutions and informal market relations.     

Universal criteria for assessing the ecological state of soil algocenoses

A set of criteria allowing demarcation between algocenoses is proposed. These criteria characterize the species composition, group of dominants, and taxonomic and ecological structure of algocenoses.     

Carbon Storage in Soil Size Fractions Under Two Cacao Agroforestry Systems in Bahia, Brazil

Shaded perennial agroforestry systems contain relatively high quantities of soil carbon (C) resulting from continuous deposition of plant residues; however, the extent to which the C is sequestered in soil will depend on the extent of physical protection of soil organic C (SOC). The main objective of this study was to characterize SOC storage in relation to soil fraction-size classes in cacao (Theobroma cacao L.) agroforestry systems (AFSs). Two shaded cacao systems and an adjacent natural forest in reddish-yellow Oxisols in Bahia, Brazil were selected. Soil samples were collected from four depth classes to 1 m depth and separated by wet-sieving into three fraction-size classes (>250 μm, 250–53 μm, and <53 μm)—corresponding to macroaggregate, microaggregate, and silt-and-clay size fractions—and analyzed for C content. The total SOC stock did not vary among systems (mean: 302 Mg/ha). On average, 72% of SOC was in macroaggregate-size, 20% in microaggregate-size, and 8% in silt-and-clay size fractions in soil. Sonication of aggregates showed that occlusion of C in soil aggregates could be a major mechanism of C protection in these soils. Considering the low level of soil disturbances in cacao AFSs, the C contained in the macroaggregate fraction might become stabilized in the soil. The study shows the role of cacao AFSs in mitigating greenhouse gas (GHG) emission through accumulation and retention of high amounts of organic C in the soils and suggests the potential benefit of this environmental service to the nearly 6 million cacao farmers worldwide.     

Social learning in a policy-mandated collaboration: community wildfire protection planning in the eastern United States

Policies such as the US Healthy Forests Restoration Act (HFRA) mandate collaboration in planning to create benefits such as social learning and shared understanding among partners. However, some question the ability of top-down policy to foster successful local collaboration. Through in-depth interviews and document analysis, this paper investigates social learning and transformative learning in three case studies of Community Wildfire Protection Planning (CWPP), a policy-mandated collaboration under HFRA. Not all CWPP groups engaged in social learning. Those that did learned most about organisational priorities and values through communicative learning. Few participants gained new skills or knowledge through instrumental learning. CWPP groups had to commit to learning, but the design of the collaborative-mandate influenced the type of learning that was most likely to occur. This research suggests a potential role for top-down policy in setting the structural context for learning at the local level, but also confirms the importance of collaborative context and process in fostering social learning.     

Integrating Environmental and Socio-Economic Indicators of a Linked Catchment–Coastal System Using Variable Environmental Intensity

Can we develop land use policy that balances the conflicting views of stakeholders in a catchment while moving toward long term sustainability? Adaptive management provides a strategy for this whereby measures of catchment performance are compared against performance goals in order to progressively improve policy. However, the feedback loop of adaptive management is often slow and irreversible impacts may result before policy has been adapted. In contrast, integrated modelling of future land use policy provides rapid feedback and potentially improves the chance of avoiding unwanted collapse events. Replacing measures of catchment performance with modelled catchment performance has usually required the dynamic linking of many models, both biophysical and socio-economic—and this requires much effort in software development. As an alternative, we propose the use of variable environmental intensity (defined as the ratio of environmental impact over economic output) in a loose coupling of models to provide a sufficient level of integration while avoiding significant effort required for software development. This model construct was applied to the Motueka Catchment of New Zealand where several biophysical (riverine water quantity, sediment, E. coli faecal bacteria, trout numbers, nitrogen transport, marine productivity) models, a socio-economic (gross output, gross margin, job numbers) model, and an agent-based model were linked. An extreme set of land use scenarios (historic, present, and intensive) were applied to this modelling framework. Results suggest that the catchment is presently in a near optimal land use configuration that is unlikely to benefit from further intensification. This would quickly put stress on water quantity (at low flow) and water quality (E. coli). To date, this model evaluation is based on a theoretical test that explores the logical implications of intensification at an unlikely extreme in order to assess the implications of likely growth trajectories from present use. While this has largely been a desktop exercise, it would also be possible to use this framework to model and explore the biophysical and economic impacts of individual or collective catchment visions. We are currently investigating the use of the model in this type of application.     

Lateral movement of soil fumigants 1,3-dichloropropene and chloropicrin from treated agricultural fields

The soil fumigants 1,3-dichloropropene (1,3-D) and chloropicrin (CP) are often used for controlling soil-borne plant pathogens and parasitic nematodes before reestablishing new vineyards and orchards. To evaluate crop safety and environmental risks with the replant fumigation, four field experiments were performed over 2 yr to examine 1,3-D and CP lateral movement away from the treated fields. Shank injection with or without a virtually impermeable film (V1F) was used in two vineyard fumigation experiments, and spot drip application without tarp cover was used in two orchard experiments. Results showed that 1,3-D and CP gases moved laterally to 6 m from the treated fields when the fumigants were applied by shank injection. The maximum 1,3-D or CP soil gas concentration at 6 m was approximately 10 ng cm(-3) when the fumigated plot was not cover with a tarp. With VIF, the measured maximum concentration increased to approximately 100 ng cm(-3). In the spot drip application, maximum 1,3-D and CP gas concentrations reached approximately 100 ng cm(-3) but at 1.5 m radial distance from the point of fumigant injection.