A new condensed toluene mechanism for Carbon Bond: CB05-TU

Toluene is ubiquitous in urban atmospheres and is a precursor to tropospheric ozone and aerosol (smog). An important characteristic of toluene chemistry is the tendency of some degradation products (e.g., cresols and methyl-catechols) to form organic nitro and nitrate compounds that sequester NOx (NO and NO₂) from active participation in smog formation. Explaining the NOx sinks in toluene degradation has made mechanism development more difficult for toluene than for many other organic compounds. Another challenge for toluene is explaining sources of radicals early in the degradation process. This paper describes the development of a new condensed toluene mechanism consisting of 26 reactions, and evaluates the performance of CB05 with this new toluene scheme (Toluene Update, TU) against 38 chamber experiments at 7 different environmental chambers, and provides recommendations for future developments. CB05 with the current toluene mechanism (CB05-Base) under-predicted the maximum O₃ and O₃ production rate for many of these toluene–NOx chamber experiments, especially under low-NOx conditions ([NOx]_t=0 < 100 ppb). CB05 with the new toluene mechanism (CB05-TU) includes changes to the yields and reactions of cresols and ring-opening products, and showed better performance than CB05-Base in predicting the maximum O₃, O₃ formation rate, NOx removal rate and cresol concentration. Additional environmental chamber simulations with xylene–NOx experiments showed that the TU mechanism updates tended to improve mechanism performance for xylene.     

Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.     

Uncertainty in health risks due to anthropogenic primary fine particulate matter from different source types in Finland

The emission-exposure and exposure-response (toxicity) relationships are different for different emission source categories of anthropogenic primary fine particulate matter (PM_2.5). These variations have a potentially crucial importance in the integrated assessment, when determining cost-effective abatement strategies. We studied the importance of these variations by conducting a sensitivity analysis for an integrated assessment model. The model was developed to estimate the adverse health effects to the Finnish population attributable to primary PM_2.5 emissions from the whole of Europe. The primary PM_2.5 emissions in the whole of Europe and in more detail in Finland were evaluated using the inventory of the European Monitoring and Evaluation Programme (EMEP) and the Finnish Regional Emission Scenario model (FRES), respectively. The emission-exposure relationships for different primary PM_2.5 emission source categories in Finland have been previously evaluated and these values incorporated as intake fractions into the integrated assessment model. The primary PM_2.5 exposure-response functions and toxicity differences for the pollution originating from different source categories were estimated in an expert elicitation study performed by six European experts on air pollution health effects. The primary PM_2.5 emissions from Finnish and other European sources were estimated for the population of Finland in 2000 to be responsible for 209 (mean, 95% confidence interval 6–739) and 357 (mean, 95% CI 8–1482) premature deaths, respectively. The inclusion of emission-exposure and toxicity variation into the model increased the predicted relative importance of traffic related primary PM_2.5 emissions and correspondingly, decreased the predicted relative importance of other emission source categories. We conclude that the variations of emission-exposure relationship and toxicity between various source categories had significant impacts for the assessment on premature deaths caused by primary PM_2.5.     

Simulation of biological uptake of uranium and radium in an industrially polluted area

Distribution of ²³⁸U and ²²⁶Ra in soils and plants of an industrially polluted area are considered. The dependence between the biological uptake coefficients (BUCs) for the plant species studied and the radionuclide concentrations in soil can be approximated by a decreasing power function. Species differences in radionuclide uptake are demonstrated.     

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.     

Evaluating Conservation Program Success with Landsat and SWAT

In the United States, many state and federally funded conservation programs are required to quantify the water quality benefits resulting from their efforts. The objective of this research was to evaluate the impact of conservation practices subsidized by the Oklahoma Conservation Commission on phosphorus and sediment loads to Lake Wister. Conservation practices designed to increase vegetative cover in grazed pastures were evaluated using Landsat imagery and the Soil and Water Assessment Tool (SWAT). Several vegetative indices were derived from Landsat imagery captured before and after the implementation of conservation practices. Collectively, these indicators provided an estimate of the change in vegetative soil cover attributable to conservation practices in treated fields. Field characteristics, management, and changes in vegetative cover were used in the SWAT model to simulate sediment and phosphorus losses before and after practice implementation. Overall, these conservation practices yielded a 1.9% improvement in vegetative cover and a predicted sediment load reduction of 3.5%. Changes in phosphorus load ranged from a 1.0% improvement to a 3.5% increase, depending upon initial vegetative conditions. The use of fertilizers containing phosphorus as a conservation practice in low-productivity pastures was predicted by SWAT to increase net phosphorus losses despite any improvement in vegetative cover. This combination of vegetative cover analysis and hydrologic simulation was a useful tool for evaluating the effects of conservation practices at the basin scale and may provide guidance for the selection of conservation measures subsidized in future conservation programs.     

A contextual framework for understanding good practice in integrated catchment management

Principles of good practice for collaborative resource management were derived from the literature and their use studied in a range of integrated catchment management processes. Desk-based reviews and interviews with participants allowed the principles to be refined and described within a framework that illustrates the interrelationships between core principles, enabling principles, precursors to a project and the influence of external factors on such collaborative processes. The findings illustrate the importance of these relationships in understanding how success is defined and under what conditions successful outcomes can be achieved. Understanding how these procedural aspects influence outcomes contributes to the wider literature on collaborative resource management that often treats processes separately from their context.     

Better than their reputation: enhancing the validity of contingent valuation mail survey results through citizen expert groups

Although contingent valuation is the dominant technique for the valuation of public projects, especially in the environmental sector, the high costs of contingent valuation surveys prevent the use of this method for the assessment of relatively small projects. The reason for this cost problem is that typically only contingent valuation studies which are based on face-to-face interviews are accepted as leading to valid results. Particularly in countries with high wages, face-to-face surveys are extremely costly considering that for a valid contingent valuation study a minimum of 1000 completed face-to-face interviews is required. This paper tries a rehabilitation of mail surveys as low-budget substitutes for costly face-to-face surveys. Based on an empirical contingent valuation study in Northern Thailand, it is shown that the validity of mail surveys can be improved significantly if so-called Citizen Expert Groups are employed for a thorough survey design.     

Reply to Discussion1 - by George Ice,George Brown,John Gravelle,C. Rhett Jackson,Jeff Light,Timothy Link,Douglas Martin,Dale McGreer,and Arne Skaugset2 “Stream Temperature Relationships to Forest Harvest in Western Washington”3

Pollock, Michael M. and Timothy J. Beechie, 2010. Reply to Discussion –“Stream Temperature Relationships to Forest Harvest in Western Washington” by George Ice, George Brown, John Gravelle, C. Rhett Jackson, Jeff Light, Timothy Link, Douglas Martin, Dale McGreer, and Arne Skaugset. Journal of the American Water Resources Association (JAWRA) 46(4): 843-847. DOI: 10.1111/j.1752-1688.2010.00456.x     

Comparison of selected nutrients and bacteria from common contiguous soils inside and outside swine lagoon effluent spray fields after long-term use

Swine (Sus scofa domestica) lagoon effluent is a valuable resource. In the U.S. Mid-South it is applied from April to September to fertilize grass hay in spray-irrigated fields. Lagoon levels of nutrients and bacteria, and soil levels of nutrients have been documented, but little was known of effluent bacterial levels in soil. The present study examined levels of selected effluent bacteria and nutrients in soils inside and outside spray fields after >15 yr of effluent irrigation. Samples were collected February to March 2009 from contiguous soils spanning adjacent irrigated and nonirrigated areas. Separate soil cores for bacterial and nutrient tests were collected in pairs <10 cm apart. Five cores each were collected at 15-m intervals and combined, respectively, to comprise inside and outside samples from each of 20 soils (four each from five farms/spray fields). Analyses of data combined across all soils showed higher pH and Mehlich-3-extracrable (M3-) P, Mg, K, Na, Cu, and Zn inside than outside spray fields, while total N, total C, M3-Ca, and M3-Mn did not differ. Bacterial levels were higher inside than outside spray fields for heterotrophic plate counts, thermotolerant coliforms, Staphylococcus spp., and Clostridium perfringens, but levels of Escherichia coli and Enterococcus spp. were not different. Cultural presence/absence tests for three pathogens (Listeria spp., Campylobacter spp., and Salmonella spp.) detected only Listeria spp., which did not differ inside (23% positive samples) and outside (28% positive). Molecular tests detected all three pathogens at low levels that were not different inside and outside. We found no evidence of cumulative buildup of Campylobacter spp., Listeria spp., or Salmonela s. in spray field soils.