Examining the temperature dependence of ethanol (E85) versus gasoline emissions on air pollution with a largely-explicit chemical mechanism

The increased use of ethanol in transportation fuels warrants an investigation of its consequences. An important component of such an investigation is the temperature dependence of ethanol and gasoline exhaust chemistry. We use the Master Chemical Mechanism (MCM, version 3.1, LEEDS University) with the SMVGEAR II chemical ordinary differential solver to provide the speed necessary to simulate complex chemistry to examine such effects. The MCM has over 13,500 organic reactions and 4600 species. SMVGEAR II is a sparse-matrix Gear solver that reduces the computation time significantly while maintaining any specified accuracy. Although we use a box model for this study, we determine and demonstrate in a separate study that the speed of the MCM with SMVGEAR II allows the MCM to be modeled in 3-dimensions. We also verified the accuracy of the model in comparison with smog chamber data. We then use the model with species-resolved tailpipe emissions data for E85 (15% gasoline, 85% ethanol fuel blend) and gasoline vehicles to compare the impact of each on nitrogen oxides, organic gases, and ozone as a function of ambient temperature and background concentrations, using Los Angeles in 2020 as a base case. We use two different emissions sets – one is a compilation of exhaust and evaporative data taken near 24 °C and the other from exhaust data taken at ?7 °C – to determine how atmospheric chemistry and emissions are affected by temperature. We include diurnal effects by examining two day scenarios. We find that, accounting for chemistry and dilution alone, the average ozone concentrations through the range of temperatures tested are higher with E85 than with gasoline by ～7 part per billion volume (ppbv) at higher temperatures (summer conditions) to ～39 ppbv at low temperatures and low sunlight (winter conditions) for an area with a high nitrogen oxide (NOx) to non-methane organic gas (NMOG) ratio. The results suggest that E85's effect on health through ozone formation becomes increasingly more significant relative to gasoline at colder temperatures due to the change in exhaust emission composition at lower temperatures. Acetaldehyde and formaldehyde concentrations are also much higher with E85 at cold temperatures, which is a concern because both are considered to be carcinogens. These could have implications for wintertime use of E85. Peroxy acetyl nitrate (PAN), another air pollutant of concern, increases with E85 by 0.3–8 ppbv. The sensitivity of the results to box size, initial background concentrations, background emissions, and water vapor were also examined.     

Behaviour and dynamics of di-ammonium phosphate in bauxite processing residue sand in Western Australia—II. Phosphorus fractions and availability

Background, aim and scope  

Australia is the largest producer of bauxite in the world, with an annual output of approximately 62 million metric dry tons in 2007. For every tonne of alumina, about 2 tonnes of highly alkaline and highly saline bauxite-processing residue are produced. In Western Australia, Alcoa World Alumina, Australia (Alcoa) produces approximately 15 MT of residue annually from its refineries (Kwinana, Pinjarra and Wagerup). The bauxite-processing residue sand (BRS) fraction represents the primary material for rehabilitating Alcoa’s residue disposal areas (RDAs). However, the inherently hostile characteristics (high alkalinity, high salinity and poor nutrient availability) of BRS pose severe limitations for establishing sustainable plant cover systems. Alcoa currently applies 2.7 t ha⁻¹ of di-ammonium phosphate ((NH₄)₂HPO₄; DAP)-based fertiliser as a part of rehabilitation of the outer residue sand embankments of its RDAs. Limited information on the behaviour of the dominant components of this inorganic fertiliser in highly alkaline BRS is currently available, despite the known effects of pH on ammonium (NH₄) and phosphorus (P) behaviour. The aim of this study was to quantify the effects of pH on NH₃ volatilisation and residual nitrogen (N) in BRS following DAP applications.     

Efficacy of forming biofilms by <Emphasis Type="Italic">Pseudomonas migulae</Emphasis> AN-1 toward in situ bioremediation of aniline-contaminated aquifer by groundwater circulation wells

The formation and activity of aniline-degrading biofilms developed by the psychrotrophic Pseudomonas migulae AN-1 were studied for the in situ remediation of contaminated aquifer using in-well bioreactor of groundwater circulating wells (GCWs). Biofilms grown in mineral salt medium with aniline exhibited tolerance to high concentrations of aniline. In aniline degradation rate, AN-1 biofilms exhibited slight differences compared with planktonic cells. The effectiveness and bio-implication of AN-1 biofilms in GCWs were investigated to treat aniline-contaminated aquifer. The results demonstrate that AN-1 biofilms survived the GCWs treatment process with high aniline-degrading efficiency. This system provides a novel environmentally friendly technology for the in situ bioremediation of low-volatile contaminants.     

Residue determination and dissipation of ioxynil octanoate in maize and soil

A simple and efficient residue analysis method for direct determination of ioxynil octanoate in maize and soil was developed and validated with High Performance Liquid Chromatography-Ultra Violet (HPLC-UV). The samples were extracted with mixtures of acetonitrile and deionized water followed by Solid Phase Extraction (SPE) to remove co-extractives prior to analysis by HPLC-UV. The recoveries of ioxynil octanoate extracted from maize and soil samples ranged from 86 %-104 % and 84 %-96 %, respectively, with relative standard deviation (RSD) less than 7.84% and sensitivity of 0.01 mg kg(-1). The method was applied to determine the residue of ioxynil octanoate in maize and soil samples from experimental field. Data had shown that the dissipation rate in soil was described as pseudo-first-order kinetics and the half-life (t(1/2)) was less than 1.78 days. No ioxynil octanoate residue (<0.01 mg kg(-1)) was detected in maize at harvest time withholding period of 60 days after treatments of the pesticide. Direct confirmation of the analytes in field trial samples was realized by Liquid Chromatography-Mass Spectrometry (LC-MS).     

Experimental investigation and modelling of tritium washout by precipitation in the area of the nuclear power plant of Paks, Hungary

Tritium occurs in nature in trace amounts, but its concentration is changing due to natural and artificial sources. Studies focusing on natural tritium have to take into account the effect of artificial sources. Also, the impact of tritium is an important issue in environmental protection, e.g. in connection with the emissions from nuclear power plants. The present work focuses on the rain washout of tritium emitted from the Paks nuclear power plant in Hungary. Rainwater collectors were placed around the plant and after a period of precipitation, rainwater was collected and analysed for tritium content. Samples were analysed using low-level liquid scintillation counting, with some also subject to the more accurate ³He ingrowth method. The results clearly show the trace of the tritium plume emitted from the plant; however, values are only about one order of magnitude higher than environmental background levels. A washout model was devised to estimate the distribution of tritium around the plant. The model gives slightly higher concentrations than those measured in the field, but in general the agreement is satisfactory. The modelled values demonstrate that the effect of the plant on rainwater tritium levels is negligible over a distance of some kilometres.     

Cu fractions, mobility and bioavailability in soil-wheat system after Cu-enriched livestock manure applications

Fertilization of crops with livestock manure (LM) is a common waste disposal option, but repeated application of LM containing high concentrations of heavy metals such as Cu could lead to crop toxicity and environmental risk. To examine the Cu availability and uptake by wheat in a Mollisol affected by Cu-enriched LM, pot experiments were conducted. LM (376 mg kg⁻¹ Cu originally) was spiked with different concentrations of Cu (0, 100, 200, 400, 600 and 800 mg kg⁻¹ soil, added as CuSO₄) to simulate soil Cu contamination by LM application. The results indicated that Cu was predominately distributed in organic bound fraction, while the most drastic increase was found in reducible fraction. Acid-extractable fraction played a more important role than other fractions in controlling the mobility and bioavailability of Cu. DTPA-extractable Cu may overestimate the Cu bioavailability since DTPA solution could extract soluble and part of stable forms. The application of LM at 1% level significantly decline the Cu mobility, but that at 3% level exhibited the opposite effect.Although the quantities of Cu in wheat was very low compared with the accumulation in soil, Cu concentrations in roots increased evidently from 12 to 533 mg kg⁻¹ and that in aerial parts were in a narrow range from 12.1 to 32.7 mg kg⁻¹, indicating the more sensitivity of roots to the Cu toxicity. The Cu concentrations in grains after 3% manure application did not approach the threshold for Cu toxicity (<20 mg kg⁻¹) even at higher Cu addition rates.     

Formation of toxic species and precursors of PCDD/F in thermal decomposition of alpha-cypermethrin

This article examines the thermal decomposition of alpha-cypermethrin, one of the most common pyrethroid pesticides. The objective was to identify its decomposition pathways and to gain an understanding into the formation of toxic species in the environment, including those that may behave in combustion systems, especially in fires in the environment, as precursors for PCDD/F (polychlorinated dibenzo-p-dioxins and dibenzofurans). The experiments were conducted under non-oxidative conditions using a tubular reactor housed in a three-zone heating furnace and operated with a dilute stream of alpha-cypermethrin in 99.999% nitrogen. The condensable products were identified and quantitated, after being collected in a cold solvent trap and in an activated charcoal cartridge. The study revealed the formation of pollutants including precursors of toxic PCDD/F such as diphenyl ether and phenol. It was also found that the decomposition of alpha-cypermethrin involved parallel pathways of an unusual vinylcyclopropane rearrangement-cum-aromatisation reaction transforming alpha-cypermethrin and a rupture of the C(O)OC(CN) linkage. The former is similar to that occurring in the decomposition of permethrin pesticide, whereas the latter constitutes a newly discovered channel for the formation of pollutants. Density functional theory (DFT) calculations allowed us to attribute the occurrence of the second pathway to the effect of the cyanide group in significantly weakening the OC bond.     

Nitrogen concentrations in mosses indicate the spatial distribution of atmospheric nitrogen deposition in Europe

In 2005/6, nearly 3000 moss samples from (semi-)natural location across 16 European countries were collected for nitrogen analysis. The lowest total nitrogen concentrations in mosses (<0.8%) were observed in northern Finland and northern UK. The highest concentrations (≥1.6%) were found in parts of Belgium, France, Germany, Slovakia, Slovenia and Bulgaria. The asymptotic relationship between the nitrogen concentrations in mosses and EMEP modelled nitrogen deposition (averaged per 50 km × 50 km grid) across Europe showed less scatter when there were at least five moss sampling sites per grid. Factors potentially contributing to the scatter are discussed. In Switzerland, a strong (r² = 0.91) linear relationship was found between the total nitrogen concentration in mosses and measured site-specific bulk nitrogen deposition rates. The total nitrogen concentrations in mosses complement deposition measurements, helping to identify areas in Europe at risk from high nitrogen deposition at a high spatial resolution.     

Analysis of surface and aerosol polarized reflectance for aerosol retrievals from polarized remote sensing in PRD urban region

A precise estimate of polarization induced by surface is crucial for polarized remote sensing dedicated to monitoring aerosol properties over urban area. The accurate knowledge of interaction between surface and aerosol polarized reflectance is essential for accurately achieving aerosol properties. In order to study surface and aerosol polarized reflectance for aerosol retrievals over urban area, a new airborne directional polarimetric camera (DPC) with high spatial resolution (4 m at 4000 m a.g.l) was developed. The surface polarized reflectance over distinct surface covers of urban area (forest, shrub, and soil) were studied using DPC measurements during a field campaign in the Pearl River Delta (PRD), China. The large variations were found in surface polarized reflectance of distinct urban covers due to surface type variability. For all surface types, the empirical BPDF model cannot describe accurately surface polarized reflectance at all possible illumination and observation geometries. From the quantitatively study of relationship between surface and aerosol polarized contribution to DPC measurements, we show that the polarized contributions of aerosol, which optical properties were defined by ground-based measurements, are much larger than the polarized contribution of surface, and found that the polarized contribution of surface covers increases with decreasing NDVI. The effect of polarization accuracy of measurements on aerosol retrieval was also investigated using DPC measurements, and found that 0.1% polarization accuracy of measurements can be neglected when AOD is retrieved using polarized measurements. Based on the information of effects of polarized reflectance differences between distinct surface covers and polarization accuracy of polarized measurements on retrieved aerosols over urban area, we found that the accuracy of aerosol retrieval over forest covers is higher than other surface types using polarized remote sensing.     

酸碱改性对氧化铁脱硫剂脱硫性能影响的研究

通过酸碱改性制备了酸式和碱式2种不同表面性质的常温氧化铁脱硫剂,并采用FT-IR技术对其表面酸碱性质和净化硫化氢废气活性进行了研究.结果表明,表面酸碱件质不同的脱硫剂其脱硫反应行为也不同,在脱硫过程中硫化氢氧化生成的硫酸及亚硫酸会影响脱硫剂的表面酸碱性质,造成酸式脱硫剂的表面酸性更强,从而抑制了硫化氢分子在酸式脱硫剂表...