Gas-phase chemistry of benzyl alcohol: Reaction rate constants and products with OH radical and ozone

A bimolecular rate constant, k_{OH+Benzyl alcohol}, of (28 ± 7) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with benzyl alcohol, at (297 ± 3) K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k_{O3+Benzyl alcohol}, of approximately 6 × 10^?19 cm³ molecule^?1 s^?1 was determined by monitoring the decrease in benzyl alcohol concentration over time in an excess of ozone (O₃). To more clearly define part of benzyl alcohol's indoor environment degradation mechanism, the products of the benzyl alcohol + OH were also investigated. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to positively identify benzaldehyde, glyoxal and 4-oxopentanal as benzyl alcohol/OH reaction products. The elucidation of other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible benzyl alcohol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.     

Influence of air mass source region on nanoparticle events and hygroscopicity in central Virginia,U.S.

During autumn, 2006, variation in the frequency of aerosol nucleation events, as inferred from nanoparticle growth events, and associated hygroscopicity were investigated as a function of air mass transport history at a mixed deciduous forest in central Virginia, U.S. Above-canopy size distributions of aerosols between 0.012 and 0.700 μm diameter, size-resolved particle hygroscopicity at eight dry diameters between 0.012 and 0.400 μm, and cloud condensation nuclei (CCN) activity were characterized. Air mass back trajectories were clustered to identify source regions. Growth events were most frequent in fast-moving air masses (mean = 9 m s^?1) that originated over the north central U.S. Under these flow regimes, mean values for preexisting sub-μm aerosol number concentrations (4700 cm^?3), corresponding surface area (142 μm² cm^?3), air temperature (6.2 °C), and relative humidity (RH, 49.4%) were relatively low compared to other regimes. Under stagnant flow conditions (mean = 3 m s^?1), mean number concentrations were higher (>6000 cm^?3) and size fractions <0.1 μm diameter exhibited enhanced hygroscopicity compared to other source regions. These results indicate that precursors emitted into relatively clean, cold, and dry air transported over the southeastern U.S. reacted to form condensable intermediates that subsequently produced new aerosols via nucleation and growth. This pathway was an important source for CCN. During events in October, nanoparticles were produced in greater numbers and grew more rapidly compared to November and December.     

Analysis of cloud and precipitation chemistry at Whiteface Mountain,NY

Federal and state programs over the past two decades have resulted in the reduction of emissions of precursors of acid rain. Concomitant with these changes, measured concentrations of acidity in precipitation and in watersheds have shown a downward trend or improvement. However, another pathway for these precursors is through cloud and fog events that often tend to occur at high-elevation regions affecting the fauna and flora as well. In this study we report on long-term measurements of cloud water and precipitation chemistry made from 1994 onwards at a high-elevation location, Whiteface Mountain NY, in the northeastern United States. Trends and inter-relationship between the ions were examined along with ambient SO₂ measurements and Adirondack lakes chemistry data.     

Analysis of air pollution data at a mixed source location using boosted regression trees

This paper explores the use of boosted regression trees to draw inferences concerning the source characteristics at a location of high source complexity. Models are developed for hourly concentrations of nitrogen oxides (NO_X) close to a large international airport. Model development is discussed and methods to quantify model uncertainties developed. It is shown that good explanatory models can be developed and further, allowing for interactions between model variables significantly improves the model fits compared with non-interacting models. Methods are used to determine which variables exert most influence over predicted concentrations and to explore the NO_X dependency for each. Model predictions are used to estimate aircraft take-off contributions to total concentrations of NO_X and determine how these predictions are affected by annual variations in meteorological conditions and runway use patterns. Furthermore, the results relating to the aircraft contributions to total NO_X concentration are compared with those from a more detailed independent field campaign. Finally, we find empirical evidence that plumes from larger aircraft disperse more rapidly from the point of release compared with smaller aircraft. The reasons for this behaviour and the implications are discussed.     

Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry

The high-molecular weight water-soluble organic compounds present in atmospheric aerosols underwent functional-group characterization using liquid chromatography tandem mass spectrometry (LC-MS/MS), with a focus on understanding the chemical structure and origins of humic-like substances (HULIS) in the atmosphere. Aerosol samples were obtained from several locations in North America at times when primary sources contributing to organic aerosol were well-characterized: Riverside, CA, Fresno, CA, urban and peripheral Mexico City, Atlanta, GA, and Bondville, IL. Chemical analysis targeted identification and quantification of functional groups, such as aliphatic, aromatic, and bulk carboxylic acids, organosulfates, and carbohydrate-like substances that comprise species with molecular weights (MW) 200–600 amu. Measured high-MW functional groups were compared to modeled primary sources with the purpose of identifying associations between aerosol sources, high-MW aerosol species, and HULIS. Mobile source emissions were linked to high-molecular weight carboxylic acids, especially aromatic acids, biomass burning was associated with carboxylic acids and carbohydrate-like substances, and secondary organic aerosol (SOA) correlated well with the total amount of HULIS measured, whereas organosulfates showed no correlation with aerosol sources and exhibited unique spatial trends. These results suggested the importance of motor vehicles, biomass burning, and SOA as important sources of precursors to HULIS. Structural characteristics of atmospheric HULIS were compared to terrestrial humic and fulvic acids and revealed striking similarities in chemical structure, with the exception of organosulfates which were unique to atmospheric HULIS.     

Approximating the distribution of recreational visits from on-site survey data

While convenient and often used, on-site surveys are biased by the fact that users who visit the site more often are proportionately more likely to be sampled. This so-called avidity or size biased sampling results in over-estimating the visitation patterns of the average user. This analysis develops a rule of thumb method that may easily be applied by recreation site managers to visitation data collected on-site in order to infer behavior of the average user of the site. The key assumption that drives the derivation is that the visitation data of users is logarithmically distributed. To evaluate the methodology, we analyze several data sets of recreational users assuming that they reflect the populations of users and from these construct hypothetical on-site samples.     

Predicting land cover using GIS, Bayesian and evolutionary algorithm methods

Modelling land cover change from existing land cover maps is a vital requirement for anyone wishing to understand how the landscape may change in the future. In order to test any land cover change model, existing data must be used. However, often it is not known which data should be applied to the problem, or whether relationships exist within and between complex datasets. Here we have developed and tested a model that applied evolutionary processes to Bayesian networks. The model was developed and tested on a dataset containing land cover information and environmental data, in order to show that decisions about which datasets should be used could be made automatically. Bayesian networks are amenable to evolutionary methods as they can be easily described using a binary string to which crossover and mutation operations can be applied. The method, developed to allow comparison with standard Bayesian network development software, was proved capable of carrying out a rapid and effective search of the space of possible networks in order to find an optimal or near-optimal solution for the selection of datasets that have causal links with one another. Comparison of land cover mapping in the North-East of Scotland was made with a commercial Bayesian software package, with the evolutionary method being shown to provide greater flexibility in its ability to adapt to incorporate/utilise available evidence/knowledge and develop effective and accurate network structures, at the cost of requiring additional computer programming skills. The dataset used to develop the models included GIS-based data taken from the Land Cover for Scotland 1988 (LCS88), Land Capability for Forestry (LCF), Land Capability for Agriculture (LCA), the soil map of Scotland and additional climatic variables.     

How good is GLASOD?

The Global Assessment of Soil Degradation (GLASOD) has been the most influential global appraisal of land quality in terms of environmental policy. However, its expert judgments were never tested for their consistency and could not be reproduced at unvisited sites, while the relationship between the GLASOD assessments of land degradation and the social and economic impact of that degradation remains unclear. Yet, other methodologies that could respond to urgent calls for an updated assessment of the global environmental quality are not operational or, at best, in progress. Therefore, we evaluate the reliability and social relevance of the GLASOD approach and assess its candidacy for new global environmental assessments. The study concentrates on the African continent, capitalizing on new GIS data to delineate and define the characteristics of GLASOD map units. Consistency is tested by comparing expert judgments on soil degradation hazard for similar combinations of biophysical conditions and land use. Reproducibility is evaluated by estimating an ordered logit model that relates the qualitative land degradation classes to easily available information on explanatory variables, the results of which can be used to assess the land degradation at unvisited sites. Finally, a cross-sectional analysis investigates the relation between GLASOD assessments and crop production data at sub-national scale and its association with the prevalence of malnutrition. The GLASOD assessments prove to be only moderately consistent and hardly reproducible, while the counter-intuitive trend with crop production reveals the complexity of the production-degradation relationship. It appears that increasing prevalence of malnutrition coincides with poor agro-productive conditions and highly degraded land. The GLASOD approach can be improved by resolving the differences in conceptualization among experts and by defining the boundaries of the ordered classes in the same units as independent, quantitative land degradation data.     

Increasing exfiltration from pervious concrete and temperature monitoring

Pervious concrete typically has an infiltration rate far exceeding any expectation of precipitation rate. The limiting factor of a retention based pervious concrete system is often defined by how quickly the underlying soil subgrade will infiltrate the water temporarily stored within the concrete and/or aggregate base. This issue is of particular importance when placing a pervious concrete system on compacted fine textured soils. This research describes the exfiltration from twelve pervious concrete plots constructed on a compacted clay soil in eastern Tennessee, USA. Several types of treatments were applied to the clay soil prior to placement of the stone aggregate base and pervious concrete in an attempt to increase the exfiltration rate, including: 1) control – no treatment; 2) trenched – soil trenched and backfilled with stone aggregate; 3) ripped – soil ripped with a subsoiler; and 4) boreholes – placement of shallow boreholes backfilled with sand. The average exfiltration rates were 0.8 cm d⁻¹ (control), 4.6 cm d⁻¹ (borehole), 10.0 cm d⁻¹ (ripped), and 25.8 cm d⁻¹ (trenched). The trenched treatment exfiltrated fastest, followed by the ripped and then the borehole treatments, although the ripped and borehole treatments were not different from one another at the 5% level of significance. The internal temperature of the pervious concrete and aggregate base was monitored throughout the winter of 2006–2007. Although the temperature of the pervious concrete dropped below freezing 24 times, freezing concrete temperatures never coincided with free water being present in the large pervious concrete pores. The coldest recorded air temperature was −9.9 °C, and the corresponding coldest recorded pervious concrete temperature was −7.1 °C. The temperature of the pervious concrete lagged diurnal air temperature changes and was generally buffered in amplitude, particularly when free water was present since the addition of water increases the thermal capacity of the pervious concrete greatly. The temperature of the aggregate base was further buffered to diurnal changes, and no freezing temperatures were recorded.