Hydrocarbon emissions speciation in diesel and biodiesel exhausts

Diesel engine emissions are composed of a long list of organic compounds, ranging from C₂ to C₁₂₊, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic.The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed.Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed.The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.     

Surface ozone background in the United States: Canadian and Mexican pollution influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.     

Spatiotemporal modelling of ozone distribution in the State of California

This paper is concerned with the spatiotemporal mapping of monthly 8-h average ozone (O₃) concentrations over California during a 15-years period. The basic methodology of our analysis is based on the spatiotemporal random field (S/TRF) theory. We use a S/TRF decomposition model with a dominant seasonal O₃ component that may change significantly from site to site. O₃ seasonal patterns are estimated and separated from stochastic fluctuations. By means of Bayesian Maximum Entropy (BME) analysis, physically meaningful and sufficiently detailed space–time maps of the seasonal O₃ patterns are generated across space and time. During the summer and winter months the seasonal O₃ concentration maps exhibit clear and progressively changing geographical patterns over time, suggesting the existence of relationships in accordance with the typical physiographic and climatologic features of California. BME mapping accuracy can be superior to that of other techniques commonly used by EPA; its framework can rigorously assimilate useful data sources that were previously unaccounted for; the generated maps offer valuable assessments of the spatiotemporal O₃ patterns that can be helpful in the identification of physical mechanisms and their interrelations, the design of human exposure and population health models, and in risk assessment. As they focus on the seasonal patterns, the maps are not contingent on short-time and locally prevalent weather conditions, which are of no interest in a global and non-forecasting framework. Moreover, the maps offer valuable insight about the space–time O₃ concentration patterns and are, thus, helpful for disentangling the influence of explanatory factors or even for identifying some influential ones that could have been otherwise overlooked.     

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.     

Molecular characterization of denitrifying bacteria isolated from the anoxic reactor of a modified DEPHANOX plant performing enhanced biological phosphorus removal

Enhanced Biological Phosphorus Removal (EBPR) under anoxic conditions was achieved using a Biological Nutrient Removal (BNR) system based on a modification of the DEPHANOX configuration. Double-probe Fluorescence in Situ Hybridization (FISH) revealed that Polyphosphate Accumulating Organisms (PAOs) comprised 12.3 +/- 3.2% of the total bacterial population in the modified DEPHANOX plant. The growing bacterial population on blood agar and Casitone Glycerol Yeast Autolysate agar (CGYA) medium was 16.7 +/- 0.9 x 10(5) and 3.0 +/- 0.6 x 10(5) colony forming units (cfu) mL(-1) activated sludge, respectively. A total of 121 bacterial isolates were characterized according to their denitrification ability, with 26 bacterial strains being capable of reducing nitrate to gas. All denitrifying isolates were placed within the alpha-, beta-, and gamma-subdivisions of Proteobacteria and the family Flavobacteriaceae. Furthermore, a novel denitrifying bacterium within the genus Pseudomonas was identified. This is the first report on the isolation and molecular characterization of denitrifying bacteria from EBPR sludge using a DEPHANOX-type plant.     

Effect of diurnal changes in VOC source strengths on performances of receptor models

Introduction

The effect of diurnal changes in strengths of volatile organic compound (VOC) sources on the performances of positive matrix factorization (PMF) and principal component analysis (PCA) was investigated using ambient measurement results that were taken during daytime and nighttime hours between March 24 and May 14, 2011, within Davutpasa Campus of Yildiz Technical University (Istanbul, Turkey).

Methods

Forty-five VOC species, ranging from C₅ to C₁₁ in volatility, were measured in the samples, 40 of which are included in the analyses. Ambient samples were grouped as daytime, nighttime, and all day datasets, and both PMF and PCA were applied to each dataset. A total of six source groups were extracted from each dataset: solvent use, general industrial paint use, gasoline and diesel vehicle exhausts, and biogenic as well as evaporative emissions. Estimated source contributions showed great diurnal variations.

Results

The results suggested that extraction of possible sources by PCA depends greatly on the number of samples and the strength of the sources, while PMF produced stable results regardless of number of samples and source strengths.

Conclusion

Although PMF was unable to resolve gasoline vehicle and evaporative emissions, it was found to be successful in explaining diurnal fluctuations in source strengths, while the performance of PCA depends on the strength of emission source.     

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.     

Toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles

This study evaluates the toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles after 168 h of exposure. The LC(50) of deltamethrin and λ-cyhalothrin at 168 h was calculated as the μg of active ingredient per liter (μg AI/L). According to these values, the LC(50) was 6.26 and 3.94 μg AI/L for deltamethrin and λ-cyhalothrin, respectively. Several enzymes were studied for early signs of intoxication following exposure to the pesticides for 24 h. Glutathione-S-transferase,carboxylesterase, and lactate dehydrogenase were inhibited by λ-cyhalothrin, and both pesticides inhibited acid phosphatase and aspartate aminotransferase. In contrast, acetylcholinesterase was activated by deltamethrin. The results suggest that X. laevis is sensitive to the pyrethroids that were tested, and the enzyme responses suggest that they are potential biomarkers for evaluating the toxic effect of pyrethroids on amphibians in environmental conditions.     

Optimization of photo-Fenton process parameters on carbofuran degradation using central composite design

Carbofuran, one of the most toxic and biorefractory carbamate compounds, is widely used in insecticides in Taiwan (9-18% of total insecticides production per year). In the present study, a central composite design experiment was used to study the effect of photo-Fenton treatment on carbofuran solution and to optimize the process variables such as carbofuran concentration (1-100 mg L(-1)), H(2)O(2) dosage rate (0.25-6 mg L(-1) min(-1)) and Fe(3+) dosage (1-50 mg L(-1)), which influenced the efficiency of carbofuran degradation and mineralization. The results indicated that all the variables investigated in this study had significant roles in the degradation and mineralization of carbofuran in solution. The carbofuran degradation and mineralization efficiencies were increased with increase in H(2)O(2) dosage rate and Fe(3+) dosage, and with decrease in carbofuran concentration. Furthermore, optimum values of both H(2)O(2) dosage rate and Fe(3+) dosage were found to shift to higher values as carbofuran concentration increased. Based on the model obtained in this study, optimum H(2)O(2) dosage rate and Fe(3+) dosage were found to be 4 mg L(-1) min(-1) and 20 mg L(-1), respectively, for 51 mg L(-1) of carbofuran concentration. Under these conditions, carbofuran was completely removed within 30 min and coupled with 78% mineralization at the end of experiment.