Sex-specific metabolic adaptations from in utero exposure to particulate matter derived from combustion of petrodiesel and biodiesel fuels.

Maternal exposure to particulate matter derived from diesel exhaust has been shown to cause metabolic dysregulation, neurological problems, and increased susceptibility to diabetes in the offspring. Diesel exhaust is a major source of air pollution and the use of biodiesel (BD) and its blends have been progressively increasing throughout the world; however, studies on the health impact of BD vs. petrodiesel combustion-generated exhaust have been controversial in part, due to differences in the chemical and physical nature of the associated particulate matter (PM). To explore the long-term impact of prenatal exposure, pregnant mice were exposed to PM generated by combustion of petrodiesel (B0) and a 20% soy BD blend (B20) by intratracheal instillation during embryonic days 9-17 and allowed to deliver. Offspring were then followed for 52 weeks. We found that mother's exposure to B0 and B20 PM manifested in striking sex-specific phenotypes with respect to metabolic adaptation, maintenance of glucose homeostasis, and medial hypothalamic glial cell makeup in the offspring. The data suggest PM exposure limited to a narrower critical developmental window may be compensated for by the mother and/or the fetus by altered metabolic programming in a marked sex-specific and fuel-derived PM-specific manner, leading to sex-specific risk for diseases related to environmental exposure later in life.

Ultrafine particles altered gut microbial population and metabolic profiles in a sex-specific manner in an obese mouse model.

Emerging evidence has highlighted the connection between exposure to air pollution and the increased risk of obesity, metabolic syndrome, and comorbidities. Given the recent interest in studying the effects of ultrafine particle (UFP) on the health of obese individuals, this study examined the effects of gastrointestinal UFP exposure on gut microbial composition and metabolic function using an in vivo murine model of obesity in both sexes. UFPs generated from light-duty diesel engine combustion of petrodiesel (B0) and a petrodiesel/biodiesel fuel blend (80:20 v/v, B20) were administered orally. Multi-omics approaches, including liquid chromatography-mass spectrometry (LC-MS) based targeted metabolomics and 16S rRNA gene sequence analysis, semi-quantitatively compared the effects of 10-day UFP exposures on obese C57B6 mouse gut microbial population, changes in diversity and community function compared to a phosphate buffer solution (PBS) control group. Our results show that sex-specific differences in the gut microbial population in response to UFP exposure can be observed, as UFPs appear to have a differential impact on several bacterial families in males and females. Meanwhile, the alteration of seventy-five metabolites from the gut microbial metabolome varied significantly (ANOVA p < 0.05) across the PBS control, B0, and B20 groups. Multivariate analyses revealed that the fuel-type specific disruption to the microbial metabolome was observed in both sexes, with stronger disruptive effects found in females in comparison to male obese mice. Metabolic signatures of bacterial cellular oxidative stress, such as the decreased concentration of nucleotides and lipids and increased concentrations of carbohydrate, energy, and vitamin metabolites were detected. Furthermore, blood metabolites from the obese mice were differentially affected by the fuel types used to generate the UFPs (B0 vs. B20).

Hybrid-electric passenger car energy utilization and emissions: Relationships for real-world driving conditions that account for road grade.

Past research showed on-road emissions patterns unique to hybrid electric vehicles (HEVs), indicating the need to account for them in emissions models as projected HEV sales increase over the coming decades. This work defines and characterizes a variable that quantifies HEV operating behavior to inform future development of new HEV emissions models based on current knowledge of conventional vehicle (CV) emissions patterns. Instantaneous hybridization factor (IHF), was quantified using on-road data collected from a 2010 Toyota Camry HEV. IHF is the ratio of electric system power to total system power and accounts for energy storage in the high voltage battery (IHF ranges from -1 to +1). Relationships between IHF and vehicle specific power (VSP), road type and road grade were examined. Negative VSP resulted in regenerative braking operation (IHF = -0.01 to -1) 90% of the time. IHF identified the VSP range where HEV operation was highly variable (VSP = -1 to 8 kW/ton) when driving at speeds below the ICE-off threshold (42 mph). VSP and IHF together account for 76-86% of the variability in HEV CO2 emissions in this study. CO2 model results using VSP computed with the measured real-world road grade (R2 = 0.86) gave improved fits over the no-grade VSP model (R2 = 0.69). This study establishes one framework for calculating the instantaneous HEV power split, confirms the need to include road grade in VSP for accurate modeling of vehicle emissions, and identified the need for significant improvements in on-board diagnostic (OBD) scantool measurement requirements for HEVs in three areas: (1) temporal resolution (sub-second to capture transient events such as ICE restarts); (2) simultaneous data logging capability for multiple controller area networks (i.e., engine and HEV parameters together); and (3) improved data precision.

Comparing the impact of ultrafine particles from petrodiesel and biodiesel combustion to bacterial metabolism by targeted HPLC-MS/MS metabolic profiling.

Alterations of gut bacterial metabolism play an important role in their host metabolism, and can result in diseases such as obesity and diabetes. While many factors were discovered influencing the gut bacterial metabolism, exposure to ultrafine particles (UFPs) from engine combustions were recently proposed to be a potential risk factor for the perturbation of gut bacterial metabolism, and consequentially to obesity and diabetes development. This study focused on evaluation of how UFPs from diesel engine combustions impact gut bacterial metabolism. We hypothesize that UFPs from different type of diesel (petrodiesel vs. biodiesel) will both impact bacterial metabolism, and the degree of impact is also diesel type-dependent. Targeted metabolic profiling of 221 metabolites were applied to three model gut bacteria in vitro, Streptococcus salivarius, Lactobacillus acidophilus and Lactobacillus fermentum. UFPs from two types of fuels, petrodiesel (B0) and a biodiesel blend (B20: 20% soy biodiesel/80% B0 by volume), were exposed to the bacteria and their metabolic changes were compared. For each bacterial strain, metabolites with significantly changed abundance were observed in both perturbations, and all three strains have increased number of altered metabolites detected from B20 UFPs perturbation in comparison to B0 UFPs. Multivariate statistical analysis further confirmed that the metabolic profiles were clearly different between testing groups. Metabolic pathway analyses also demonstrated several important metabolic pathways, including pathways involves amino acids biosynthesis and sugar metabolism, were significantly impacted by UFPs exposure.

Hybrid-Electric Passenger Car Carbon Dioxide and Fuel Consumption Benefits Based on Real-World Driving.

Hybrid-electric vehicles (HEVs) have lower fuel consumption and carbon dioxide (CO2) emissions than conventional vehicles (CVs), on average, based on laboratory tests, but there is a paucity of real-world, on-road HEV emissions and performance data needed to assess energy use and emissions associated with real-world driving, including the effects of road grade. This need is especially great as the electrification of the passenger vehicle fleet (from HEVs to PHEVs to BEVs) increases in response to climate and energy concerns. We compared tailpipe CO2 emissions and fuel consumption of an HEV passenger car to a CV of the same make and model during real-world, on-the-road network driving to quantify the in-use benefit of one popular full HEV technology. Using vehicle specific power (VSP) assignments that account for measured road grade, the mean CV/HEV ratios of CO2 tailpipe emissions or fuel consumption defined the corresponding HEV "benefit" factor for each VSP class (1 kW/ton resolution). Averaging over all VSP classes for driving in all seasons, including temperatures from -13 to +35 °C in relatively steep (-13.2 to +11.5% grade), hilly terrain, mean (±SD) CO2 emission benefit factors were 4.5 ± 3.6, 2.5 ± 1.7, and 1.4 ± 0.5 for city, exurban/suburban arterial and highway driving, respectively. Benefit factor magnitude corresponded to the frequency of electric-drive-only (EDO) operation, which was modeled as a logarithmic function of VSP. A combined model explained 95% of the variance in HEV benefit for city, 75% for arterial and 57% for highway driving. Benefit factors consistently exceeded 2 for VSP classes with greater than 50% EDO (i.e., only city and arterial driving). The reported HEV benefits account for real-world road grade that is often neglected in regulatory emissions and fuel economy tests. Fuel use HEV benefit factors were 1.3 and 2 for the regulatory highway (HWFET) and city (FTP) cycles, respectively, 18% and 31% higher than the EPA adjusted fuel economy values. This study establishes the significant need for high-resolution vehicle activity and road grade data in transportation data sets to accurately forecast future petroleum and GHG emissions savings from hybridization of the passenger vehicle fleet.

Petrodiesel and Waste Grease Biodiesel (B20) Emission Particles at a Rural Recycling Center: Characterization and Effects on Lung Epithelial Cells and Macrophages.

Diesel engine emissions are an important source of ultrafine particulate matter (PM) in both ambient air and many occupational settings. Biodiesel is a popular, 'green' alternative to petroleum diesel fuel, but little is known about the impact of 'real world' biodiesel combustion on workplace PM concentrations and particle characteristics including size, morphology, and composition; or on biological responses. The objectives of the present work were to characterize PM workplace concentrations and tailpipe emissions produced by the combustion of commercially purchased low sulfur petrodiesel and a waste grease B20 blend (20% biodiesel/80% petrodiesel by volume) in heavy duty diesel (HDD) nonroad equipment operating in a 'real world' rural recycling center. Furthermore, we assessed the in vitro responses of cell lines representing human lung epithelial cells (BEAS-2B) and macrophages (THP-1) after 24 h of exposure to these real-world particles. Compared to petroleum diesel, use of B20 in HDD equipment resulted in lower mass concentrations of PM2.5, PM<0.25 (particle diameter less than 2.5 and 0.25 micrometer, respectively), and elemental carbon. Transmission electron analysis of PM showed that primary particle size and morphology were similar between fuel types. Metals composition analysis revealed differences between fuels, with higher Fe, Al, V, and Se measured during B20 use, and higher As, Cd, Cu, Mn, Ni and Pb concentrations measured during petrodiesel use. In vitro responses varied between fuels but data supported that waste grease B20 particles elicited inflammatory responses in human macrophages and lung epithelial cells comparable to petrodiesel particles. However, the effects were more pronounced with B20 than petrodiesel at the same mass concentration. Since the primary particle size and morphology were similar between fuels, it is likely that the differential results seen in the in vitro assays points to differences in the composition of the PM. Future research should focus on the organic carbon and metals speciation and potential impact of real world particles on reactive oxygen species generation and mechanisms for differences in the cellular inflammatory responses.

Soy biodiesel and petrodiesel emissions differ in size, chemical composition and stimulation of inflammatory responses in cells and animals.

Debate about the biological effects of biodiesel exhaust emissions exists due to variation in methods of exhaust generation and biological models used to assess responses. Because studies in cells do not necessarily reflect the integrated response of a whole animal, experiments were conducted in two human cell lines representing bronchial epithelial cells and macrophages and female mice using identical particle suspensions of raw exhaust generated by a Volkswagen light-duty diesel engine using petrodiesel (B0) and a biodiesel blend (B20: 20% soy biodiesel/80% B0 by volume). Tailpipe particle emissions measurement showed B0 generated two times more particle mass, larger ultrafine particle number distribution modes, and particles of more nonpolar organic composition than the B20 fuel. Biological assays (inflammatory mediators, oxidative stress biomarkers) demonstrated that particulate matter (PM) generated by combustion of the two fuels induced different responses in in vitro and in vivo models. Concentrations of inflammatory mediators (Interleukin-6, IL-6; Interferon-gamma-induced Protein 10, IP-10; Granulocyte-stimulating factor, G-CSF) in the medium of B20-treated cells and in bronchoalveolar lavage fluid of mice exposed to B20 were ∼20-30% higher than control or B0 PM, suggesting that addition of biodiesel to diesel fuels will reduce PM emissions but not necessarily adverse health outcomes.

Mechanized and natural soil-to-air transfer of trifluralin and prometryn from a cotton field in Las Cruces, New Mexico.

Two pre-emergence herbicides (trifluralin and prometryn) were applied on a cotton field in Las Cruces, New Mexico, and their atmospheric particle and gas-phase concentrations were measured during mechanized soil preparation and natural wind erosion sampling events before and after herbicide application. Air sampling was conducted using samplers mounted at various heights from the ground and at various locations on the field. During mechanized soil management with a disk harrow, sampling occurred at two distances from the tractor ("near-source", 4 m downwind and "far-source", 20-100 m from the disking tractor). Natural background (no disking) sampling events occurred during daytime and at night. Both herbicides were quantifiable for all postapplication sampling events, including background sampling that occurred 8, 38, and 40 days after herbicide application. Average concentrations in both the gas and particle phases ranged from about 10 to 350 ng/m(3). Averaging by event type, mean total prometryn concentrations were 2 (night background) to 8 (near-source) times higher than the corresponding trifluralin concentrations. Prometryn/trifluralin ratios were higher in airborne samples than in soil, indicative of trifluralin losses during daytime sampling, possibly via atmospheric reactions. Prometryn particle phase mass fractions were generally higher than those for trifluralin for all sampling events, consistent with Kair/soil-oc partition coefficients, and particle-phase mass fractions were higher for near-source disking and daytime background sampling compared to far-source and nighttime. Daytime natural background prometryn concentrations could be as high as those measured during disking, and background samples showed significant relationships to meteorological parameters (air temperature, relative humidity, and dewpoint). Mechanical disturbance by tilling operations reduced the ability to predict airborne herbicide concentrations on the basis of meteorological conditions. Prometryn concentrations were higher for larger particle sizes (Dp > 1.8 µm), while no clear patterns with particle size were observed for trifluralin. Trifluralin concentrations in the smallest size bin (PM0.18) were 2-50 times higher than prometryn for the three disking events where an impactor was used, indicating the importance of measuring size-resolved herbicide distributions in future studies.

Relative effects of surfactants and humidity on soil/air desorption of chloroacetanilide and dinitroaniline herbicides.

Herbicides are typically applied as formulation mixtures in order to ensure uniform application and improve biocide performance, but little is known about the effects of formulated surfactants on herbicide exchange between soil and the atmosphere. Desorption experiments were performed for seven herbicides from the chloroacetanilide and dinitroaniline families with model anionic-nonionic surfactant mixtures under a range of relative humidity (RH) conditions (3-66%) on two soils. Enhanced desorption of herbicides from soil to the gas phase was observed asthe concentration of surfactant mixture or the RH increased. Multiple linear regression models developed to summarize the soil/air desorption behavior of these herbicides revealed that surfactant concentration, relative humidity, and herbicide properties (i.e., K(H), K(OA)) all have significant contributions to herbicide desorption. However, the ANOVA results indicated that surfactant concentration only accounted for 1.4% of the variance in desorption, RH accounted for 40-60%, and herbicide properties, logK(H) or logK(OA), accounted for 20-40%. The study results predict that less than a 20% increase (study range 1.5-21.0%) in surfactant concentration could double the atmospheric losses of herbicide from their soil application sites, and about a 60% increase in ambient RH (3-66%) elevated the losses by 10-40 times.

Variability of particle number emissions from diesel and hybrid diesel-electric buses in real driving conditions.

A linear mixed model was developed to quantify the variability of particle number emissions from transit buses tested in real-world driving conditions. Two conventional diesel buses and two hybrid diesel-electric buses were tested throughout 2004 under different aftertreatments, fuels, drivers, and bus routes. The mixed model controlled the confounding influence of factors inherent to on-board testing. Statistical tests showed that particle number emissions varied significantly according to the after treatment, bus route, driver, bus type, and daily temperature, with only minor variability attributable to differences between fuel types. The daily setup and operation of the sampling equipment (electrical low pressure impactor) and mini-dilution system contributed to 30-84% of the total random variability of particle measurements among tests with diesel oxidation catalysts. By controlling for the sampling day variability, the model better defined the differences in particle emissions among bus routes. In contrast, the low particle number emissions measured with diesel particle filters (decreased by over 99%) did not vary according to operating conditions or bus type but did vary substantially with ambient temperature.

Near-field dust exposure from cotton field tilling and harvesting.

The frequency and intensities of dust exposures in and near farm fields, which potentially contribute to high intensity human exposure events, are undocumented due to the transient nature of local dust plumes and the difficulties of making accurate concentration measurements. The objective of this study is to measure near-field spatial concentrations of the dust plumes emitted during tilling and harvesting of an irrigated cotton field outside of Las Cruces, NM (soil class: fine-loamy, mixed, superactive, thermic Typic Calciargid). A comparison of remote lidar measurements of plumes emitted from cotton field operations with in situ samplers shows a strong agreement between the two techniques: r2 = 0.79 for total suspended particulates (TSP) and r2 = 0.61 for particulate matter with diameter less than or equal to 10 microm (PM10). Plume movement was dependent on the short-term wind field and atmospheric stability. Horizontal spread rate of the plumes, determined from lidar measured Gaussian dispersion parameters, was less than expected by a factor of 7. Thus, in-plume downwind concentrations were higher than expected. Vertical dispersion was dependent on the rise of "cells" of warm air convecting off the soil surface. On a windy day, discing the field showed TSP and PM10 concentrations at the source itself of up to 176 microg m(-3) and 120 microg m(-3), respectively. These resulted in in-plume peak TSP concentrations of about 1.22 microg m(-3) at 10 m downwind and 0.33 microg m(-3) at 100 m downwind. The measured concentrations highlight a potential exposure risk to people in and around farming operations.

Effects of relative humidity on chloroacetanilide and dinitroaniline herbicide desorption from agricultural PM2.5 on quartz fiber filters.

This study quantified the release of seven relatively polar preemergence herbicides to the gas phase from soil-generated PM2.5-loaded quartz fiber filters (QFFs) and bare QFF as a function of relative humidity (RH). A 48-hour desorption fraction, F48, was defined to evaluate the relative desorption behavior of herbicides from two families, chloroacetanilide (alachlor, butachlor, metolachlor, and propachlor) and dinitroaniline (pendimethalin, prodiamine, and trifluralin) using temperature- (8 degrees C) and humidity- (10-64% RH) controlled air at a flow rate of 4 L/min. With increasing RH, an increase in F48 by a factor of 2-8 was observed for all herbicides, except metolachlor and butachlor, which showed significantly strong sorption to both sorbents. The conjugate carbonyl oxygen and amide nitrogen in the chloroacetanilide structure enables stronger specific interactions with the sorbents, leading to lower desorption compared to the dinitroaniline herbicides. Desorption of chloroacetanilides decreased in the order propachlor > alachlor > metolachlor approximately butachlor, and desorption of dinitroanilines decreased in the order trifluralin > pendimethalin > prodiamine. These orders are consistent with the different substituents in the herbicide molecules for each family and their relative tendencies to coordinate with surface moieties as indicated by electron-donating capacity. Henry's law constant and Abraham's H-acceptor parameter were found to be useful empirical parameters for describing the F48 desorption behavior for all seven herbicides.

Lidar characterization of crystalline silica generation and transport from a sand and gravel plant.

Light detection and ranging (Lidar) remote sensing two-dimensional vertical and horizontal scans collected downwind of a sand and gravel plant were used to evaluate the generation and transport of geologic fugitive dust emitted by quarry operations. The lidar data give unsurpassed spatial resolution of the emitted dust, but lack quantitative particulate matter (PM) mass concentration data. Estimates of the airborne PM10 and crystalline silica concentrations were determined using linear relationships between point monitor PM10 and quartz content data with the lidar backscatter signal collected from the point monitor location. Lidar vertical profiles at different distances downwind from the plant were used to quantify the PM10 and quartz horizontal fluxes at 2-m vertical resolution as well as off-site emission factors. Emission factors on the order of 65-110 kg of PM10 (10-30 kg quartz) per daily truck activity or 2-4 kg/t product shipped (0.5-1 kg quartz/t) were quantified for this facility. The lidar results identify numerous elevated plumes at heights >30 m and maximum plume heights of 100 m that cannot be practically sampled by conventional point sampler arrays. The PM10 and quartz mass flux was greatest at 10-25 m height and decreased with distance from the main operation. Measures of facility activity were useful for explaining differences in mass flux and emission rates between days. The study results highlight the capabilities of lidar remote sensing for determining the spatial distribution of fugitive dust emitted by area sources with intermittent and spatially diverse dust generation rates.

Herbicide sorption to fine particulate matter suspended downwind of agricultural operations: field and laboratory investigations.

Tillage-induced erosion of herbicides bound to airborne soil particles has not been quantified as a mechanism for offsite herbicide transport. This study quantifies the release of two preemergent herbicides, metolachlor and pendimethalin, to the atmosphere as gas- and particle-phase species during soil incorporation operations. Fine particulate matter (PM2.5) and gas-phase samples were collected at three sampling heights during herbicide disking into the soil in Davis, CA, in May 2000 and May 2001 using filter/PUF sampling. Quartz fiber filters (QFFs) were used in May 2000, and Teflon membrane filters (TMFs) were used in May 2001. The field data were combined with laboratory filter/PUF partitioning experiments to account for adsorption to the filter surfaces and quantify the mass of PM2.5-bound herbicides in the field samples. Laboratory results indicate a significant adsorption of metolachlor, but not pendimethalin, to the quartz filter surfaces. Metolachlor partitioning to PM2.5 collected on TMF filters resulted in corrected PM2.5 field partition coefficient values, Kp,corr = Cp/Cg, of approximately 10(-3.5) m3/microg, indicating its preference for the gas phase. Pendimethalin exhibited more semivolatile behavior,with Kp,corr values that ranged from 10(-3) to 10(-1) m3/ microg and increased with sampling height and distance downwind of the operation. An increase in pendimethalin enrichment at a height of 5 m suggests winnowing of finer, more sorptive soil components with corresponding higher transport potential. Pendimethalin was enriched in the PM2.5 samples by up to a factor of 250 compared to the field soil, indicating thatfurther research on the processes controlling the generation of PM-bound herbicides during agricultural operations is warranted to enable prediction of off-site mass fluxes by this mechanism.

Uncertainty in particle number modal analysis during transient operation of compressed natural gas, diesel, and trap-equipped diesel transit buses.

The relationships between transient vehicle operation and ultrafine particle emissions are not well-known, especially for low-emission alternative bus technologies such as compressed natural gas (CNG) and diesel buses equipped with particulate filters/traps (TRAP). In this study, real-time particle number concentrations measured on a nominal 5 s average basis using an electrical low pressure impactor (ELPI) for these two bus technologies are compared to that of a baseline catalyst-equipped diesel bus operated on ultralow sulfur fuel (BASE) using dynamometer testing. Particle emissions were consistently 2 orders of magnitude lower for the CNG and TRAP compared to BASE on all driving cycles. Time-resolved total particle numbers were examined in terms of sampling factors identified as affecting the ability of ELPI to quantify the particulate matter number emissions for low-emitting vehicles such as CNG and TRAP as a function of vehicle driving mode. Key factors were instrument sensitivity and dilution ratio, alignment of particle and vehicle operating data, sampling train background particles, and cycle-to-cycle variability due to vehicle, engine, after-treatment, or driver behavior. In-cycle variability on the central business district (CBD) cycle was highest for the TRAP configuration, but this could not be attributed to the ELPI sensitivity issues observed for TRAP-IDLE measurements. Elevated TRAP emissions coincided with low exhaust temperature, suggesting on-road real-world particulate filter performance can be evaluated by monitoring exhaust temperature. Nonunique particle emission maps indicate that measures other than vehicle speed and acceleration are necessary to model disaggregated real-time particle emissions. Further testing on a wide variety of test cycles is needed to evaluate the relative importance of the time history of vehicle operation and the hysteresis of the sampling train/dilution tunnel on ultrafine particle emissions. Future studies should monitor particle emissions with high-resolution real-time instruments and account for the operating regime of the vehicle using time-series analysis to develop predictive number emissions models.

Roadside particle number distributions and relationships between number concentrations, meteorology, and traffic along a northern California freeway.

Particle number distributions were measured simultaneously upwind and downwind of a suburban-agricultural freeway to determine relationships with traffic and meteorological parameters. Average traffic volumes were 6330 vehicles/hr with 10% heavy-duty vehicles, and volumes were higher in July than November. Most downwind particle number distributions were bimodal, with a primary mode at approximately 10-25 nm, indicating that newly formed particles were sampled. Total downwind 6-237 nm particle number concentrations (Ntot) ranged from 9.3 x 10(3) to 2.5 x 10(5) cm(-3), with higher daily average concentrations in November compared with July. Ntot correlated with wind speed, temperature, and relative humidity. Upwind photochemically initiated nucleation likely led to elevated background nanoparticle concentrations in July, as evidenced by increasing upwind distribution modal diameter with increasing temperature and a strong correlation between upwind Ntot and solar radiation. Also in summer, Ntot showed stronger correlation with heavy-duty vehicle volumes than wind speed, temperature, and relative humidity. These results indicate the importance of measuring background particle size distributions simultaneously with roadside distributions. There may be a minimum vehicle volume from which useful real-world vehicle particle number distributions can be measured at roadside, even when collecting samples within 10 m of the traveled lanes.

Airborne respirable silica near a sand and gravel facility in central California: XRD and elemental analysis to distinguish source and background quartz.

Despite the potential toxicity of respirable quartz to humans, little is known about the transport of airborne quartz from sources to receptors and how to distinguish anthropogenically generated quartz from natural background in a receptor sample. Airborne quartz emissions near a sand and gravel facility were determined using PM10 and PM2.5 filter samples collected at four downwind sites (D1: 22 m, D2: 62 m, D3: 259 m, and D4: 745 m from the facility) as well as one upwind site (U1: 1495 m) during summer sampling. X-ray diffraction was used to determine quartz concentration and elemental composition was analyzed using PIXE, XRF, PESA, and HIPS techniques. Elemental composition of the PM samples was used to determine the X-ray mass absorption coefficients that are essential for accurate quartz quantification by XRD. Elemental composition was found to be a useful tool to distinguish source and background crystalline silica. Both PM10 and PM2.5 samples collected at the D1, D2, and D3 sites contained more Si, Al, and Fe and less H, Na, and S, compared to those at the U1 site, whereas site D4 sample compositions were similar to those at the U1 site. A composite variable, SOIL/(H+Na+S), where SOIL = 2.20Al + 2.49Si + 1.63Ca + 1.94Ti + 2.42Fe, was used to distinguish source materials from background. Average dry season quartz concentrations in replicate PM10 samples were 4.6 +/- 0.9) microg m(-3) at U1, 60.6 (+/- 5.4) microg m(3) at D1, 62.4 (+/- 3.6) at D2, 32.6 (+/- 2.1) microg m(-3) at D3, and 9.41 (+/- 0.9) microg m(-3) at D4. The mass fraction of quartz was the highest at the D1 site and decreased with increasing distance from the facility. The mass of PM2.5 samples was too low to determine quartz concentrations. These results identify the facility as the main source of quartz and other silicate minerals downwind of the plant and that the air quality of the most remote sampling site, located approximately 750 m downwind, was still impacted by the facility's activity.

Ultrafine PM emissions from natural gas, oxidation-catalyst diesel, and particle-trap diesel heavy-duty transit buses.

This paper addresses how current technologies effective for reducing PM emissions of heavy-duty engines may affect the physical characteristics of the particles emitted. Three in-use transit bus configurations were compared in terms of submicron particle size distributions using simultaneous SMPS measurements under two dilution conditions, a minidiluter and the legislated constant volume sampler (CVS). The compressed natural gas (CNG)-fueled and diesel particulate filter (DPF)-equipped diesel configurations are two "green" alternatives to conventional diesel engines. The CNG bus in this study did not have an oxidation catalyst whereas the diesel configurations (with and without particulate filter) employed catalysts. The DPF was a continuously regenerating trap (CRT). Particle size distributions were collected between 6 and 237 nm using 2-minute SMPS scans during idle and 55 mph steady-state cruise operation. Average particle size distributions collected during idle operation of the diesel baseline bus operating on ultralow sulfur fuel showed evidence for nanoparticle growth under CVS dilution conditions relative to the minidiluter. The CRT effectively reduced both accumulation and nuclei mode concentrations by factors of 10-100 except under CVS dilution conditions where nuclei mode concentrations were measured during 55 mph steady-state cruise that exceeded baseline diesel concentrations. The CVS data suggest some variability in trap performance. The CNG bus had accumulation mode concentrations 10-100x lower than the diesel baseline but often displayed large nuclei modes, especially under CVS dilution conditions. Partly this may be explained by the lack of an oxidation catalyst on the CNG, but differences between the minidiluter and CVS size distributions suggest that dilution ratio, temperature-related wall interactions, and differences in tunnel background between the diluters contributed to creating nanoparticle concentrations that sometimes exceeded diesel baseline concentrations when driving under load. The results do not support use of CVS dilution methodology for ultrafine particle sampling, and, despite attention to collection of tunnel blanks in this study, results indicate that a protocol needs to be determined and prescribed for taking into account tunnel blank "emissions" to obtain meaningful comparisons between different technologies. Of critical importance is determining how temperature differences between tunnel blank and test cycle sampling compare in terms of background particle numbers. Total particle number concentrations for the minidiluter sampling point were not significantly different for the two alternative technologies when considering all the steady-cycle data collected. Concentrations ranged from 0.8 to 3 x 10(6) for the baseline bus operating on ultralow sulfur fuel, from 0.5 to 9 x 10(4) for the diesel bus equipped with the CRT filter, and from 1 to 8 x 10(4) particles/cc for the CNG bus.