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.     

The importance of auditory-visual interaction in the construction of ‘tranquil space’

In a world of sensory overload, it is becoming increasingly important to provide environments that enable us to recover our sense of well being. Such restorative (‘tranquil’) environments need to comprise sufficient sensory stimulation to keep us engaged, whilst at the same time providing opportunity for reflection and relaxation. One essential aspect in safeguarding existing, or developing new ‘tranquil space’, is understanding the optimum relationship between the soundscape and the visual composition of a location. This research represents a first step in understanding the effects of audio-visual interaction on the perception of tranquillity and identifies how the interpretation of acoustic information is an integral part of this process. By using uni and bi-modal auditory-visual stimuli in a two stage experimental strategy, it has been possible to measure the key components of the tranquillity construct. The findings of this work should be of particular interest to those charged with landscape management, such as National Park Authorities, Regional Councils, and other agencies concerned with providing and maintaining public amenity.     

Sulfur Dioxide Fumigation of Soybeans: Effect on Yield

In order to determine the influence of SO₂ fumigation of soybean plants on yield, a three-year experiment was conducted on 485 plois of soybeans. Single fumigations of S0₂ were applied at 10 different stages of growth in 1968-69 and 7 stages of growth in 1970. A linear relationship was found to exist beiween the percent of leaf area destroyed and ihe percent crop loss with a significant regression coefficient of b = —0.659, or iwo-thirds of one percent crop loss for each percent of area destroyed. No definite significant stage-of-growth effect was found and no treatment effects were significant for the early stages of growth from the 3-leaf to the 15-leaf stage, nor was there any loss in yield without visible leaf injury.     

A Combined Ca(OH)2/NH3 Flue Gas Desulfurization Process for High Sulfur Coal: Results of a Pilot Plant Study

The removal of SO₂ with atomization of a slaked lime slurry and supplemental injection of gaseous NH₃ were tested in a conventional spray dryer/baghouse system for SO₂ concentrations of 2000 ppm and 3000 ppm and a 30° F approach to saturation. Results at 3000 ppm of SO₂ showed an average SO₂ removal efficiency of 90.3 percent at a combined stoichiometric ratio of 0.95-1.10 and an average overall sorbent utilization of 91.6 percent. The overall molal ratio of NH₃/SO₂ reaction was found to be 2:1 under the test conditions Particle size analyses, and EP toxicity tests were conducted on the products of the reactions.     

An Environmental Decision-Making Tool for Evaluating Ground-Level Ozone-Related Health Effects

Abstract

A computer model called the Ozone Risk Assessment Model (ORAM) was developed to evaluate the health effects caused by ground-level ozone (O₃) exposure. ORAM was coupled with the U.S. Environmental Protection Agency’s (EPA) Third-Generation Community Multiscale Air Quality model (Models-3/CMAQ), the state-of-the-art air quality model that predicts O₃ concentration and allows the examination of various scenarios in which emission rates of O₃ precursors (basically, oxides of nitrogen [NO_x] and volatile organic compounds) are varied. The principal analyses in ORAM are exposure model performance evaluation, health-effects calculations (expected number of respiratory hospital admissions), economic valuation, and sensitivity and uncertainty analysis through a Monte Carlo simulation. As a demonstration of the system, ORAM was applied to the eastern Tennessee region, and the entire O₃ season was simulated for a base case (typical emissions) and three different emission scenarios. The results indicated that a synergism occurs when reductions in NO_x emissions from mobile and point sources were applied simultaneously. A 12.9% reduction in asthma hospital admissions is expected when both mobile and point source NO_x emissions are reduced (50 and 70%, respectively) versus a 5.8% reduction caused by mobile source and a 3.5% reduction caused by point sources when these emission sources are reduced individually.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Application of a combined measurement and modeling method to quantify windblown dust emissions from the exposed playa at Mono Lake, California

Particulate matter < or =10 microm (PM10) emissions due to wind erosion can vary dramatically with changing surface conditions. Crust formation, mechanical disturbance, soil texture, moisture, and chemical content of the soil can affect the amount of dust emitted during a wind event. A refined method of quantifying windblown dust emissions was applied at Mono Lake, CA, to account for changing surface conditions. This method used a combination of real-time sand flux monitoring, ambient PM10 monitoring, and dispersion modeling to estimate dust emissions and their downwind impact. The method identified periods with high emissions and periods when the surface was stable (no sand flux), even though winds may have been high. A network of 25 Cox sand catchers (CSCs) was used to measure the mass of saltating particles to estimate sand flux rates across a 2-km2 area. Two electronic sensors (Sensits) were used to time-resolve the CSC sand mass to estimate hourly sand flux rates, and a perimeter tapered element oscillating microbalance (TEOM) monitor measured hourly PM10 concentrations. Hourly sand flux rates were related by dispersion modeling to hourly PM10 concentrations to back-calculate the ratio of vertical PM10 flux to horizontal sand flux (K-factors). Geometric mean K-factor values (K(f)) were found to change seasonally, ranging from 1.3 x 10(-5) to 5.1 x 10(-5) for sand flux measured at 15 cm above the surface (q15). Hourly PM10 emissions, F, were calculated by applying seasonal K-factors to sand flux measurements (F = K(f) x q15). The maximum hourly PM10 emission rate from the study area was 76 g/m2 x hr (10-m wind speed = 23.5 m/sec). Maximum daily PM10 emissions were estimated at 450 g/m2 x day, and annual emissions at 1095 g/m2 x yr. Hourly PM10 emissions were used by the U.S. Environmental Protection Agency (EPA) guideline AERMOD dispersion model to estimate downwind ambient impacts. Model predictions compared well with monitor concentrations, with hourly PM10 ranging from 16 to over 60,000 microg/m3 (slope = 0.89, R2 = 0.77).     

Identifying natural and anthropogenic sources of metals in urban and rural soils using GIS-based data,PCA, and spatial interpolation

Determining sources of neurotoxic metals in rural and urban soils is important for mitigating human exposure. Surface soil from four areas with significant clusters of mental retardation and developmental delay (MR/DD) in children, and one control site were analyzed for nine metals and characterized by soil type, climate, ecological region, land use and industrial facilities using readily available GIS-based data. Kriging, principal component analysis (PCA) and cluster analysis (CA) were used to identify commonalities of metal distribution. Three MR/DD areas (one rural and two urban) had similar soil types and significantly higher soil metal concentrations. PCA and CA results suggested that Ba, Be and Mn were consistently from natural sources; Pb and Hg from anthropogenic sources; and As, Cr, Cu, and Ni from both sources. Arsenic had low commonality estimates, was highly associated with a third PCA factor, and had a complex distribution, complicating mitigation strategies to minimize concentrations and exposures.     

Evaluation of ion exchange resins for the removal of dissolved organic matter from biologically treated paper mill effluent

In this study, the efficiency of six ion exchange resins to reduce the dissolved organic matter (DOM) from a biologically treated newsprint mill effluent was evaluated and the dominant removal mechanism of residual organics was established using advanced organic characterisations techniques. Among the resins screened, TAN1 possessed favourable Freundlich parameters, high resin capacity and solute affinity, closely followed by Marathon MSA and Marathon WBA. The removal efficiency of colour and lignin residuals was generally good for the anion exchange resins, greater than 50% and 75% respectively. In terms of the DOM fractions removal measured through liquid chromatography–organic carbon and nitrogen detector (LC–OCND), the resins mainly targeted the removal of humic and fulvic acids of molecular weight ranging between 500 and 1000 g mol^?1, the portion expected to contribute the most to the aromaticity of the effluent. For the anion exchange resins, physical adsorption operated along with ion exchange mechanism assisting to remove neutral and transphilic acid fractions of DOM. The column studies confirmed TAN1 being the best of those screened, exhibited the longest mass transfer zone and maximum treatable volume of effluent. The treatable effluent volume with 50% reduction in dissolved organic carbon (DOC) was 4.8 L for TAN1 followed by Marathon MSA – 3.6 L, Marathon 11 – 2.0 L, 21K-XLT – 1.5 L and Marathon WBA – 1.2 L. The cation exchange resin G26 was not effective in DOM removal as the maximum DOC removal obtained was only 27%. The resin capacity could not be completely restored for any of the resins; however, a maximum restoration up to 74% and 93% was achieved for TAN1 and Marathon WBA resins. While this feasibility study indicates the potential option of using ion exchange resins for the reclamation of paper mill effluent, the need for improving the regeneration protocols to restore the resin efficiency is also identified. Similarly, care should be taken while employing LC–OCND for characterising resin-treated effluents, as the resin degradation is expected to contribute some organic carbon moieties misleading the actual performance of resin.     

Evaluation of Vegetation Near Coal-burning Power Plants in Southwestern Pennsylvania. II. Ozone Injury on Foliage of Hybrid Poplar

The objective of this study was to determine if the incidence or severity of foliar injury induced by regional, ambient ozone was influenced by local emissions from a complex of coal-burning power plants in southwestern Pennsylvania. Plantings of an ozonesensitive hybrid poplar clone {Populus maximowizii x trichocarpa, clone NE 388) were established in 1972 at various distances and directions from the power plants. Foliar injury caused by ambient ozone was evaluated annually from 1973 to 1990 in early to mid- August. Data are presented for the 12-year period, 1979 to 1990 inclusive, for which the most complete data sets were available. Injury from ambient ozone varied spatially and temporally, but with little relationship to power plant location. There was an apparent negative relationship between emission trends and ozone-induced symptoms, but only for one power plant. The correlation between annual mean levels of ozone-induced stipple and frequency of days (per year) with a 1-hr ozone maximum exceeding 0.04 ppm was weak, but significant. Ozone-induced bifacial necrosis was not observed on the foliage of the hybrid poplar during the drought year of 1988 in spite of record high levels of ozone; however, ozoneinduced stipple was observed.