Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

Assessment of non-occupational exposure to polycyclic aromatic hydrocarbons through personal air sampling and urinary biomonitoring

Non-occupational inhalation and ingestion exposure to polycyclic aromatic hydrocarbons (PAHs) has been studied in 8 non-smoking volunteers through personal air sampling and urinary biomonitoring. The study period was divided into 4 segments (2 days/segment), including weekdays with regular commute and weekends with limited traffic related exposures; each segment had a high or low PAH diet. Personal air samples were collected continuously from the subjects while at home, at work, and while commuting to and from work. All urine excretions were collected as individual samples during the study. In personal air samples, 28 PAHs were measured, and in urine samples 9 mono-hydroxylated metabolites (OH-PAHs) from 4 parent PAHs (naphthalene, fluorene, phenanthrene and pyrene) were measured. Naphthalene was found at higher concentrations in air samples collected at the subjects' residences, whereas PAHs with four or more aromatic rings were found at higher levels in samples taken while commuting. Urinary OH-PAH biomarker levels increased following reported high inhalation and/or dietary exposure. On days with a low PAH diet, the total amount of inhaled naphthalene during each 24-hour period was well correlated with the amount of excreted naphthols, as was, to a lesser extent, fluorene with its urinary metabolites. During days with a high dietary intake, only naphthalene was significantly correlated with its excreted metabolite. These findings suggest that this group of non-occupational subjects were exposed to naphthalene primarily through indoor air inhalation, and exposed to other PAHs such as pyrene mainly through ingestion.     

The Value of Better Information on Technology R&D Programs in Response to Climate Change

Expert elicitations are a promising method for determining how R&D investments are likely to have an impact on technological advance in climate change energy technologies. But, expert elicitations are time consuming and resource intensive. Thus, we investigate the value of the information gained in expert elicitations. More specifically, given baseline elicitations from one study, we estimate the expected value of better information (EVBI) from revisiting and improving these assessments. We find that the EVBI is very large in comparison with the cost of performing expert elicitations. We also find that EVBI is higher on technologies with larger budgets and with net values that are not too high or too low.     

Land application of tylosin and chlortetracycline swine manure: Impacts to soil nutrients and soil microbial community structure

The land application of aged chortetracycle (CTC) and tylosin-containing swine manure was investigated to determine associated impacts to soil microbial respiration, nutrient (phosphorus, ammonium, nitrate) cycling, and soil microbial community structure under laboratory conditions. Two silty clay loam soils common to southeastern South Dakota were used. Aerobic soil respiration results using batch reactors containing a soil-manure mixture showed that interactions between soil, native soil microbial populations, and antimicrobials influenced CO₂ generation. The aged tylosin treatment resulted in the greatest degree of CO₂ inhibition, while the aged CTC treatment was similar to the no-antimicrobial treatment. For soil columns in which manure was applied at a one-time agronomic loading rate, there was no significant difference in soil-P behavior between either aged CTC or tylosin and the no-antimicrobial treatment. For soil-nitrogen (ammonium and nitrate), the aged CTC treatment resulted in rapid ammonium accumulation at the deeper 40cm soil column depth, while nitrate production was minimal. The aged CTC treatment microbial community structure was different than the no-antimicrobial treatment, where amines/amide and carbohydrate chemical guilds utilization profile were low. The aged tylosin treatment also resulted in ammonium accumulation at 40 cm column depth, however nitrate accumulation also occurred concurrently at 10 cm. The microbial community structure for the aged tylosin was also significantly different than the no-antimicrobial treatment, with a higher degree of amines/amides and carbohydrate chemical guild utilization compared to the no-antimicrobial treatment. Study results suggest that land application of CTC and tylosin-containing manure appears to fundamentally change microbial-mediated nitrogen behavior within soil A horizons.     

Inter-Laboratory Comparison of Air Particulate Monitoring Data

ABSTRACT

This paper compares three analytical methods that are often used to analyze composition of atmospheric aerosol: Ion Chromatography (IC), Proton Induced X-ray Emission (PIXE), and X-Ray Fluorescence (XRF). Three monitoring studies are discussed: (1) a comparison of air particulate data collected by several independent sampler/ analytical technique suites run by different laboratories; (2) a study involving two identical samplers and a single suite of analytical techniques; and (3) analysis of identical aerosol samples by two different techniques (XRF vs. PIXE). While the XRF versus PIXE project shows a very good agreement for most elements, the first interlaboratory study demonstrates the “real-life” noise introduced into the final data set by various sampling complications and different collection characteristics of the samplers used. The XRF versus PIXE study also revealed an unexplained deviation in measured sulphur concentrations for very lightly loaded samples. In the five-sampler comparison, two data sets provided by IC were approximately 20% lower than the three data sets obtained by PIXE and XRF. When two identical IMPROVE-compat-ible samplers were used and samples were subjected to similar procedures and the same analytical techniques, the variability between the two air concentration data sets significantly decreased.     

Diurnal and Weekday Variations in the Source Contributions of Ozone Precursors in California’s South Coast Air Basin

Abstract

For at least 30 years, ozone (O₃) levels on weekends in parts of California’s South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O₃ precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NO_x) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O₃ formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NO_x associated with black carbon (BC) to NO_x associated with carbon monoxide (CO) were approximately 1.25 ± 0.22 during weekdays and 0.76 ± 0.07 and 0.52 ± 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NO_x emissions from diesel exhaust can be a major factor causing lower NO_x mixing ratios and higher NMHC/NO_x ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NO_x ratios on weekend mornings.     

Comparison of the MOVES2010a,MOBILE6.2, and EMFAC2007 mobile source emission models with on-road traffic tunnel and remote sensing measurements

The Desert Research Institute conducted an on-road mobile source emission study at a traffic tunnel in Van Nuys, California, in August 2010 to measure fleet-averaged, fuel-based emission factors. The study also included remote sensing device (RSD) measurements by the University of Denver of 13,000 vehicles near the tunnel. The tunnel and RSD fleet-averaged emission factors were compared in blind fashion with the corresponding modeled factors calculated by ENVIRON International Corporation using U.S. Environmental Protection Agency's (EPA's) MOVES2010a (Motor Vehicle Emissions Simulator) and MOBILE6.2 mobile source emission models, and California Air Resources Board's (CARB's) EMFAC2007 (EMission FACtors) emission model. With some exceptions, the fleet-averaged tunnel, RSD, and modeled carbon monoxide (CO) and oxide of nitrogen (NO_x) emission factors were in reasonable agreement (±25%). The nonmethane hydrocarbon (NMHC) emission factors (specifically the running evaporative emissions) predicted by MOVES were insensitive to ambient temperature as compared with the tunnel measurements and the MOBILE- and EMFAC-predicted emission factors, resulting in underestimation of the measured NMHC/NO_x ratios at higher ambient temperatures. Although predicted NMHC/NO_x ratios are in good agreement with the measured ratios during cooler sampling periods, the measured NMHC/NO_x ratios are 3.1, 1.7, and 1.4 times higher than those predicted by the MOVES, MOBILE, and EMFAC models, respectively, during high-temperature periods. Although the MOVES NO_x emission factors were generally higher than the measured factors, most differences were not significant considering the variations in the modeled factors using alternative vehicle operating cycles to represent the driving conditions in the tunnel. The three models predicted large differences in NO_x and particle emissions and in the relative contributions of diesel and gasoline vehicles to total NO_x and particulate carbon (TC) emissions in the tunnel.

Implications: Although advances have been made to mobile source emission models over the past two decades, the evidence that mobile source emissions of carbon monoxide and hydrocarbons in urban areas were underestimated by as much as a factor of 2–3 in past inventories underscores the need for on-going verification of emission inventories. Results suggest that there is an overall increase in motor vehicle NMHC emissions on hot days that is not fully accounted for by the emission models. Hot temperatures and concomitant higher ratios of NMHC emissions relative to NO_x both contribute to more rapid and efficient formation of ozone. Also, the ability of EPA's MOVES model to simulate varying vehicle operating modes places increased importance on the choice of operating modes to evaluate project-level emissions.     

Multiplex biotoxin surface plasmon resonance method for marine biotoxins in algal and seawater samples

A multiplex surface plasmon resonance (SPR) biosensor method for the detection of paralytic shellfish poisoning (PSP) toxins, okadaic acid (and analogues) and domoic acid was developed. This method was compared to enzyme-linked immunosorbent assay (ELISA) methods. Seawater samples (n?=?256) from around Europe were collected by the consortia of an EU project MIcroarrays for the Detection of Toxic Algae (MIDTAL) and evaluated using each method. A simple sample preparation procedure was developed which involved lysing and releasing the toxins from the algal cells with glass beads followed by centrifugation and filtering the extract before testing for marine biotoxins by both multi-SPR and ELISA. Method detection limits based on IC₂₀ values for PSP, okadaic acid and domoic acid toxins were 0.82, 0.36 and 1.66 ng/ml, respectively, for the prototype multiplex SPR biosensor. Evaluation by SPR for seawater samples has shown that 47, 59 and 61 % of total seawater samples tested positive (result greater than the IC₂₀) for PSP, okadaic acid (and analogues) and domoic acid toxins, respectively. Toxic samples were received mainly from Spain and Ireland. This work has demonstrated the potential of multiplex analysis for marine biotoxins in algal and seawater samples with results available for 24 samples within a 7 h period for three groups of key marine biotoxins. Multiplex immunological methods could therefore be used as early warning monitoring tools for a variety of marine biotoxins in seawater samples.