Hydrocarbon emission fingerprints from contemporary vehicle/engine technologies with conventional and new fuels

The present paper presents results from the analysis of 29 individual C₂–C₉ hydrocarbons (HCs) specified in the European Commission Ozone Directive. The 29 HCs are measured in exhaust from common, contemporary vehicle/engine/fuel technologies for which very little or no data is available in the literature. The obtained HC emission fingerprints are compared with fingerprints deriving from technologies that are being phased out in Europe. Based on the total of 138 emission tests, thirteen type-specific fingerprints are extracted (Mean ± SD percentage contributions from individual HCs to the total mass of the 29 HCs), essential for receptor modelling source apportionment. The different types represent exhaust from Euro3 and Euro4 light-duty (LD) diesel and petrol-vehicles, Euro3 heavy-duty (HD) diesel exhaust, and exhaust from 2-stroke preEuro, Euro1 and Euro2 mopeds. The fuels comprise liquefied petroleum gas, petrol/ethanol blends (0–85% ethanol), and mineral diesel in various blends (0–100%) with fatty acid methyl esters, rapeseed methyl esters palm oil methyl esters, soybean oil methyl or sunflower oil methyl esters. Type-specific tracer compounds (markers) are identified for the various vehicle/engine/fuel technologies.An important finding is an insignificant effect on the HC fingerprints of varying the test driving cycle, indicating that combining HC fingerprints from different emission studies for receptor modelling purposes would be a robust approach.The obtained results are discussed in the context of atmospheric ozone formation and health implications from emissions (mg km^?1 for LD and mopeds and mg kW h^?1 for HD, all normalised to fuel consumption: mg dm^?3 fuel) of the harmful HCs, benzene and 1,3-butadiene.Another important finding is a strong linear correlation of the regulated “total” hydrocarbon emissions (tot-HC) with the ozone formation potential of the 29 HCs (ΣPO₃ = (1.66 ± 0.04) × tot-RH; r² = 0.93). Tot-HC is routinely monitored in emission control laboratories, whereas C₂–C₉ are not. The revealed strong correlations broadens the usability of data from vehicle emission control laboratories and facilitates the comparison of the ozone formation potential of HCs in exhaust from of old and new vehicle/engine/fuel technologies.     

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).     

Evaluation of synthetic adsorbents for cleanup of herbicide-laden wastewater

Small-and large-scale farm operators and applicators urgently need user-friendly and cost-effective on-site methods to treat dilute-formulated herbicide-laden wastewater (i.e., rinsate). In this study, we investigated solvent-regenerable synthetic adsorbents, Ambersorb® 563 adsorbent, Ambersorb 572 adsorbent, and Ambersorb 575 adsorbent, as alternatives to activated carbon (Filtrasorb ® 400) for cleanup of water containing Dual 8E (a.i., metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide]) or Banvel 4L (a.i., dicamba [3,6-dichloro-2-methoxybenzoic acid]). Batch-type adsorption experiments were conducted to compare adsorptive capacities of the various adsorbents. Adsorption maxima, obtained from adsorption isotherms, indicated that of the Ambersorb adsorbents tested, Ambersorb 572 adsorbent generally exhibited the highest adsorptive capacities for the herbicides tested and was comparable to Filtrasorb 400. Solvent (methanol) regenerability studies demonstrated that herbicide was readily recovered from Ambersorb 572 adsorbent and Filtrasorb 400. In general, metolachlor was more readily recoverable than dicamba. In fixed-bed column studies, Ambersorb 572 adsorbent exhibited twice the adsorptive capacity of Filtrasorb 400. Fixed-bed columns were more effective in removing metolachlor from herbicide containing water regardless of the adsorbent used. Multicycling of Ambersorb 572 adsorbent resulted in 30% loss of adsorptive capacity for dicamba as Banvel 4L and no loss of adsorptive capacity for metolachlor as Dual 8E. Working capacity was reached after three adsorption-regeneration cycles. Fixed-bed columns packed with solvent-regenerable adsorbents may prove useful as part of an on-site wastewater disposal system.     

BENEFITS AND LAND USE CHANGE CONNECTED WITH A FLOOD CONTROL PROJECT1

ABSTRACT: This study examines agricultural land use change in the flood plain of the Iowa River as a result of building the Coralville Dam. Estimates of land use change and the benefits realized from the project are compared to the original project study benefits estimated by the Corps of Engineers. An analysis of the factors affecting land use change is carried out through a regression model to determine those variables that explain observed land use change.     

Prediction of polychlorinated dibenzofuran congener distribution from gas-phase phenol condensation pathways

A model for predicting the distribution of dibenzofuran and polychlorinated dibenzofuran (PCDF) congeners from a distribution of phenols was developed. The model is based on a simplified chemical mechanism. Relative rate constants and reaction order with respect to phenol precursors were derived from experimental results using single phenols and equal molar mixtures of up to four phenols. For validation, experiments were performed at three temperatures using a distribution of phenol and 19 chlorinated phenols as measured in municipal waste incinerator exhaust gas. Comparison of experimental measurements and model predictions for PCDF isomer distributions and homologue pattern shows agreement within measurement uncertainty. The R-squared correlation coefficient exceeds 0.9 for all PCDF isomer distributions and the distribution of PCDF homologues. These results demonstrate that the distribution of dibenzofuran and the 135 PCDF congeners from gas-phase condensation of phenol and chlorinated phenols can be predicted from measurement of the distribution of phenol and the 19 chlorinated phenol congeners.     

The fate of 14C-diazinon in compost, compost-amended soil, and uptake by earthworms

A process for disposing of pesticide rinsates using sorption onto organic matter followed by composting is being evaluated. As a part of this evaluation process, we have studied the bioavailability of composted delta-2-14C-diazinon and its degradation products to earthworms (Eisenia foetida Savigny) in 30 and 60 d compost amended soil. After 60 d of composting there was considerable degradation of diazinon (95%) and a corresponding increase in the primary hydrolysis product, 2-isopropyl-4-methyl-6-hydroxypyrimidine (IMHP) as determined by high performance thin layer chromatography (HPTLC). Approximately 50% of the radioactivity became incorporated into the non-extractable fractions associated with composted organic matter with no measurable amounts of 14CO2 produced during the 60-day composting period. Following addition of the composted materials to soil, diazinon leading to 50% mortality after 14 d of exposure; continued to slowly degrade and become increasingly sorbed/entrapped within the soil-compost matrix. Soil amended with 30-d composted diazinon was toxic to earthworms whereas, no mortality was observed in those earthworms exposed to the 60-d composted diazinon. However, earthworms exposed to 30-d and 60-d composted diazinon were found to have similar levels of radioactivity in their tissues. The majority of the radioactivity in earthworms exposed 60-d composted diazinon was either unextractably bound within the earthworm tissue or was not acetone soluble. Most of the radioactivity that could be extracted with acetone was not separated by the two HPTLC methods we used. This study demonstrates that composting high concentrations of diazinon can greatly reduce toxicity and the amount of diazinon that is bioavailable to a representative soil macroinvertebrate (E. foetida).