Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol

Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared.     

Humic acid in ice: Photo-enhanced conversion of nitrogen dioxide into nitrous acid

Laboratory studies on the heterogeneous conversion of nitrogen dioxide into nitrous acid on irradiated ice films containing humic acid are described. It was found that the presence of light in the visible range of the solar spectrum significantly enhances the rate of nitrous acid release from a humic acid doped ice film. This process might contribute to observed HONO production in snow, where the NO₂ is thought to originate from nitrate photolysis. Analysis of the experimental data based on the Langmuir Hinshelwood model framework allowed quantification of the observed dependencies of the nitrous acid production rate on nitrogen dioxide concentration. The observed dependencies on the humic acid concentration as well as on the irradiation intensity were used to estimate light-driven HONO fluxes for environmental snow covers.     

A free-enzyme catalyst for the bioremediation of environmental atrazine contamination

Herbicide contamination from agriculture is a major issue worldwide, and has been identified as a threat to freshwater and marine environments in the Great Barrier Reef World Heritage Area in Australia. The triazine herbicides are of particular concern because of potential adverse effects, both on photosynthetic organisms and upon vertebrate development. To date a number of bioremediation strategies have been proposed for triazine herbicides, but are unlikely to be implemented due to their reliance upon the release of genetically modified organisms. We propose an alternative strategy using a free-enzyme bioremediant, which is unconstrained by the issues surrounding the use of live organisms. Here we report an initial field trial with an enzyme-based product, demonstrating that the technology is technically capable of remediating water bodies contaminated with the most common triazine herbicide, atrazine.     

The impact of urbanization on tropical mangroves (Fortaleza,Brazil): Evidence from PAH distribution in sediments

This investigation represents the first environmental diagnosis of the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments from a tropical mangrove in Fortaleza, northeastern Brazil. Sediment cores from six sampling stations in the Cocó and Ceará Rivers were retrieved in June-July 2006 to determine 17 priority PAHs. The total PAH concentrations (Σ_PAHs) ranged from 3.04 to 2234.76 μg kg^?1(Cocó River) and from 3.34 to 1859.21 μg kg^?1 (Ceará River). These levels are higher than those of other cities with more industrial development. PAH concentrations did not reach probable effect levels (PELs). However, from 4.5 to 87.5% of individual PAH concentrations can occasionally cause adverse biological effects for aquatic organisms. The PAH molecular ratios indicate that the PAHs in the sediment core were derived mainly from petroleum, wood, and charcoal combustion (pyrogenic source), and that atmospheric deposition and urban runoff may serve as important pathways for PAH input to the sediment. Clearly, the Σ_PAHs in sediments collected in the Cocó and Ceará Rivers indicate that ongoing pollution is more severe than past pollution.     

A performance evaluation of the National Air Quality Forecast Capability for the summer of 2007

This paper provides a performance evaluation of the real-time, CONUS-scale National Air Quality Forecast Capability (NAQFC) that supported, in part, its transition into operational status. This evaluation focuses primarily on discrete forecasts for the maximum 8-h O₃ concentrations covering the 4-month period, June through September, 2007, using measurements obtained from EPA's AIRNow network. Results indicate that the 2007 NAQFC performed as well or better than previous configurations, despite the expansion of the forecast domain into the western half of the nation that is dominated by complex terrain. The mean, domain-wide, season-long correlation was 0.70. When examined over time, the domain-wide correlations exhibit a fairly consistent nature, with values exceeding 0.60 (0.70) over 90% (55%) of the days. The NAQFC systematically over-predicted the 8-h O₃ concentrations, continuing a trend established by earlier NAQFC configurations, though to a lesser degree. The summer-long mean forecast value of 53.2 ppb was 4.2 ppb higher than the observed value, resulting in a domain-wide Normalized Mean Bias (NMB) of 8.7%. Most of the over-prediction is associated with observed concentrations less than 50 ppb. In fact the model tends to under-predict when concentrations exceed 70 ppb. As with the bias, the error associated with the latest configuration was also lower. The summer-long Root Mean Square Error of 13.0 ppb (Normalized Mean Error (NME) = 20.4%) represented marked improvements over earlier forecasts. Examination of the spatial distribution of both the NMB and NME reveals that the NAQFC was generally within 25% for the NME and 25% for the NMB over a majority of the domain. Several areas of poorer performance, where the NMB and NME often exceed 25% and in some cases 50%, were noted. These areas include southern California, where the NAQFC tended to under-predict concentrations (especially on weekends) and the southeast Atlantic and Gulf coasts regions, where the model over-predicted. Subsequent analysis revealed that the incorrect temporal allocation of precursor emissions was likely the source of the under-prediction in southern California, while inaccurate simulation of PBL heights likely contributed to the over-prediction in the coastal regions.     

Chicken manure enhanced yield and quality of field-grown kale and collard greens

Organic matter and nutrients in municipal sewage sludge (SS) and chicken manure (CM) could be recycled and used for land farming to enhance fertility and physical properties of soils. Three soil management practices were used at Kentucky State University Research Farm, Franklin County, to study the impact of soil amendments on kale (Brassica oleracea cv. Winterbar) and collard (Brassica oleracea cv. Top Bunch) yields and quality. The three soil management practices were: (i) SS mixed with native soil at 15 t acre^?1, (ii) CM mixed with native soil at 15 t acre^?1, and (iii) no-mulch (NM) native soil for comparison purposes. At harvest, collard and kale green plants were graded according to USDA standards. Plants grown in CM and SS amended soil produced the greatest number of U.S. No. 1 grade of collard and kale greens compared to NM native soil. Across all treatments, concentrations of ascorbic acid and phenols were generally greater in kale than in collards. Overall, CM and SS enhanced total phenols and ascorbic acid contents of kale and collard compared to NM native soil. We investigated the chemical and physical properties of each of the three soil treatments that might explain variability among treatments and the impact of soil amendments on yield, phenols, and ascorbic acid contents of kale and collard green grown under this practice.     

Economic sustainability and the preservation of environmental assets

The core requirement of sustainability is that current economic activities should not result in an excessive burden on future generations. This criterion is general enough to imply different decision rules for the preservation of environmental assets. Neoclassical economics does not have a sustainability criterion for environmental assets independent of the intertemporal efficiency criterion, which allocates environmental and man-made capital based on projected monetary benefits and costs. This criterion is examined in terms of the feasibility of valuing the benefits of environmental assets, the substitution possibilities between natural and man-made capital, and the ethical grounds for using efficiency as the sole determinant of the allocation of environmental assets. An alternative ecological sustainability criterion is the preservation of safe minimum levels of environmental assets in physical terms rather than the dollar value of a composite of natural and man-made capital. Safe minimum standards for environmental assets constrain the efficiency criterion in order to ensure the sustainability of economic systems. It is argued that the ecological approach to sustainability should limit the economic approach for decisions involving the allocation of environmental assets.     

Reductive dehalogenation: A subsurface bioremediation process

Introduction and large-scale production of synthetic halogenated organic chemicals over the last fifty years has resulted in a group of contaminants that tend to persist in the environment and resist both biotic and abiotic degradation. The low solubility of these types of contaminants, along with their toxicity and tendency to accumulate in food chains, make them particularly relevant targets for remediation activities. Among the mechanisms that result in dehalogenation of some classes of organic contaminants are stimulation of metabolic sequences through introduction of electron donor and acceptor combinations; addition of nutrients to meet the needs of dehalogenating microorganisms; possible use of engineered microorganisms; and use of enzyme systems capable of catalyzing reductive dehalogenation. The current state of research and development in the area of reductive dehalogenation is discussed along with possible technological application of relevant processes and mechanisms to remediation of soil and groundwater contaminated with chlorinated organics. In addition, an overview of research needs is suggested, which might be of interest for development of in-situ systems to reduce the mass of halogenated organic contaminants in soil and groundwater.