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.     

Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.     

Investigations of an intense aerosol loading during 2007 cyclone SIDR – A study using satellite data and ground measurements over Indian region

Tropical cyclones are prominent weather systems characterized by high atmospheric pressure gradients and wind speeds. Intense tropical cyclones occur in India during the pre-monsoon (spring), early monsoon (early summer), or post-monsoon (fall) periods. Originating in both the Bay of Bengal (BoB) and the Arabian Sea (AS), these tropical cyclones often attain velocities of more than 100 km h^?1 and are notorious for causing intense rain and storm surge as they cross the Indian coast. In this study, we examine the changes in the aerosol properties associated with an intense tropical cyclone “SIDR”, that occurred during 11–16 November 2007 over BoB. This cyclone, accompanied with very strong surface winds reaching 223 km h^?1, caused extensive damage over Bangladesh. Ground-based measurements of Aerosol Optical Depth (AOD) in the neighboring urban environment of Hyderabad, India, showed significant variations due to changes in wind velocity and direction associated with the cyclone passage. The Terra-MODIS and AVHRR satellite images showed prevalence of dust particles mixed with emissions from anthropogenic sources and biomass-burning AS, while the aerosol loading over BoB was significantly lower. The positive values of Aerosol index (AI) obtained from the Ozone Monitoring Instrument (OMI) suggested the presence of an elevated aerosol layer over the West coast of India, AS and Thar Desert during and after the cyclone episode. Meteorological parameters from the MM5 mesoscale model were used to study the variations in winds associated with the cyclonic activity. Particulate matter loading over the region during the cyclone period increased by ～45% with an accompanying decrease in columnar aerosol optical depth. The variations in Angstrom parameters suggested coarse-mode particle loading due to dust aerosols as observed in satellite data.     

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.     

A computational study of particulate emissions from an open pit quarry under neutral atmospheric conditions

The extraction of minerals from surface mines and quarries can produce significant fugitive dust emissions as a result of site activities such as blasting, road haulage, loading, crushing and stockpiling. If uncontrolled, these emissions can present serious environmental, health, safety and operational issues impacting both site personnel and the wider community.The dispersion of pollutant emissions within the atmosphere is principally determined by the background wind systems characterized by the atmospheric boundary layer (ABL). This paper presents an overview of the construction and solution of a computational fluid dynamics (CFD) model to replicate the development of the internal ventilation regime within a surface quarry excavation due to the presence of a neutral ABL above this excavation. This model was then used to study the dispersion and deposition of fugitive mineral dust particles generated during rock blasting operations. The paths of the mineral particles were modelled using Lagrangian particle tracking. Particles of four size fractions were released from five blast locations for eight different wind directions.The study concluded that dependent on the location of the bench blast within the quarry and the direction of the wind, a mass fraction of between 0.3 and 0.6 of the emitted mineral particles was retained within the quarry. The retention was largest when the distance from the blast location to the downwind pit boundary was greatest.     

A comparison of mesh-adaptive LES with wind tunnel data for flow past buildings: Mean flows and velocity fluctuations

In this paper we address two important aspects of micro-scale urban airflow model evaluation: (a) the identification of key flow features as dictated by the physics of the problem and as captured by the simulations, and (b) the comparison of important model output parameters (mean flows and fluctuations) with experimental data. A series of mesh-adaptive large eddy simulations (LES) was carried out for the study of air flows within two intersecting street canyons with varying building configurations. The novelty of the approach lies in the combination of LES with mesh adaptivity, which allows a variable-filter length and the implementation of an anisotropic eddy-viscosity model. Both coarse and fine-mesh simulations were carried out, using single and parallel-processor systems respectively. The simulations showed clearly that the expected flow patterns such as the street canyon recirculation and the street-mouth vortices, as well as the exchange of air flow at the street intersections, can readily be captured by the mesh-adaptive LES.In addition, the detailed comparisons of mean flows and fluctuations of the resolved velocity field with the measured data showed that the simulation results agreed well with the patterns and trends of the wind tunnel measurements. In most cases the finer-mesh simulations improved considerably the accuracy of the mean flows, especially for the symmetrical configuration. The improvement in the predicted fluctuations was less obvious, with several detector locations underpredicting the measured values, although the overall comparison was also satisfactory. The typical errors for the mean flows for all three building configurations were less than 30%, whilst for the velocity fluctuations less that 40%. Both the simulated means flows and turbulence levels were generally more accurate in the streets parallel to the wind (streamwise direction) than in the streets normal to the wind.     

Influence of organic waste type and soil structure on the bacterial filtration rates in unsaturated intact soil columns

Organic wastes are considered to be a source for the potentially pathogenic microorganisms found in surface and sub-surface water resources. Following their release from the organic waste matrix, bacteria often infiltrate into soil and may be transported to significant depths contaminating aquifers. We investigated the influence of soil texture and structure and most importantly the organic waste properties on the transport and filtration coefficients of Escherichia coli and total bacteria in undisturbed soil columns. Intact soil columns (diameter 16 cm and height 25 cm) were collected from two soils: sandy clay loam (SCL) and loamy sand (LS) in Hamadan, western Iran. The cores were amended with cow manure, poultry manure and sewage sludge at a rate of 10 Mg ha(-1) (dry basis). The amended soil cores were leached at a steady-state flux of 4.8 cm h(-1) (i.e. 0.12 of saturated hydraulic conductivity of the SCL) to a total volume of up to 4 times the pore volume of the columns. The influent (C(0)) and effluent (C) were sampled at similar time intervals during the experiments and bacterial concentrations were measured by the plate count method. Cumulative numbers of the leached bacteria, filtration coefficient (lambda(f)), and relative adsorption index (S(R)) were calculated. The preferential pathways and stable structure of the SCL facilitated the rapid transport and early appearance of the bacteria in the effluent. The LS filtered more bacteria when compared with the SCL. The effluent contamination of poultry manure-treated columns was greater than the cow manure- and sewage sludge-treated ones. The difference between cow manure and sewage sludge was negligible. The lambda(f) and S(R) values for E. coli and total bacteria were greater in the LS than in the SCL. This indicates a predominant role for the physical pore-obstruction filtration mechanisms as present in the poorly structured LS vs. the retention at adsorptive sites (chemical filtration) more likely in the better structured SCL. While the results confirmed the significant role of soil structure and preferential (macroporous) pathways, manure type was proven to have a major role in determining the maximum penetration risk of bacteria by governing filtration of bacteria. Thus while the numbers of bacteria in waste may be of significance for shallow aquifers, the type of waste may determine the risk for microbial contamination of deep aquifers.     

Evaluating the efficacy of wood shreds for mitigating erosion

An erosion control product made by shredding on-site woody materials was evaluated for mitigating erosion through a series of rainfall simulations. Tests were conducted on bare soil and soil with 30, 50, and 70% cover on a coarse and a fine-grained soil. Results indicated that the wood product known as wood shreds reduced runoff and soil loss from both soil types. Erosion mitigation ranged from 60 to nearly 100% depending on the soil type and amount of concentrated flow and wood shred cover. Wood shreds appear to be a viable alternative to agricultural straw. A wood shred cover of 50% appears optimal, but the appropriate coverage rate will depend on the amount of expected concentrated flow and soil type.     

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.