Exceedances of Secondary Aerosol Formation from In-Use Natural Gas Heavy-Duty Vehicles Compared to Diesel Heavy-Duty Vehicles.

This work, for the first time, assessed the secondary aerosol formation from both in-use diesel and natural gas heavy-duty vehicles of different vocations when they were operated on a chassis dynamometer while the vehicles were exercised on different driving cycles. Testing was performed on natural gas vehicles equipped with three-way catalysts (TWCs) and diesel trucks equipped with diesel oxidation catalysts, diesel particulate filters, and selective catalytic reduction systems. Secondary aerosol was measured after introducing dilute exhaust into a 30 m3 environmental chamber. Particulate matter ranged from 0.18 to 0.53 mg/mile for the diesel vehicles vs 1.4-85 mg/mile for the natural gas vehicles, total particle number ranged from 4.01 × 1012 to 3.61 × 1013 for the diesel vehicles vs 5.68 × 1012-2.75 × 1015 for the natural gas vehicles, and nonmethane organic gas emissions ranged from 0.032 to 0.05 mg/mile for the diesel vehicles vs 0.012-1.35 mg/mile for the natural gas vehicles. Ammonia formation was favored in the TWC and was found in higher concentrations for the natural gas vehicles (ranged from ∼0 to 1.75 g/mile) than diesel vehicles (ranged from ∼0 to 0.4 g/mile), leading to substantial secondary ammonium nitrate formation (ranging from 8.5 to 98.8 mg/mile for the natural gas vehicles). For the diesel vehicles, one had a secondary ammonium nitrate of 18.5 mg/mile, while the other showed essentially no secondary ammonium nitrate formation. The advanced aftertreatment controls in diesel vehicles resulted in almost negligible secondary organic aerosol (SOA) formation (ranging from 0.046 to 2.04 mg/mile), while the natural gas vehicles led to elevated SOA formation that was likely sourced from the engine lubricating oil (ranging from 3.11 to 39.7 mg/mile). For two natural gas vehicles, the contribution of lightly oxidized lubricating oil in the primary organic aerosol was dominant (as shown in the mass spectra analysis), leading to enhanced SOA mass. Heavily oxidized lubricating oil was also observed to contribute to the SOA formation for other natural gas vehicles.

Variability in Aromatic Aerosol Yields under Very Low NOx Conditions at Different HO2/RO2 Regimes.

Current chemical transport models generally use a constant secondary organic aerosol (SOA) yield to represent SOA formation from aromatic compounds under low NOx conditions. However, a wide range of SOA yields (10 to 42%) from m-xylene under low NOx conditions is observed in this study. The chamber HO2/RO2 ratio is identified as a key factor explaining SOA yield variability: higher SOA yields are observed for runs with a higher HO2/RO2 ratio. The RO2 + RO2 pathway, which can be increasingly significant under low NOx and HO2/RO2 conditions, shows a lower SOA-forming potential compared to the RO2 + HO2 pathway. While the traditional low-NOx chamber experiments are commonly used to represent the RO2 + HO2 pathway, this study finds that the impacts of the RO2 + RO2 pathway cannot be ignored under certain conditions. We provide guidance on how to best control for these two pathways in conducting chamber experiments to best obtain SOA yield curves and quantify the contributions from each pathway. On the global scale, the chemical transport model GEOS-Chem is used to identify regions characterized by lower surface HO2/RO2 ratios, suggesting that the RO2 + RO2 pathway is more likely to prove significant to overall SOA yields in those regions. Current models generally do not consider the RO2 + RO2 impacts on aromatic SOA formation, but preliminary sensitivity tests with updated SOA yield parameters based on such a pathway suggest that without this consideration, some types of SOA may be overestimated in regions with lower HO2/RO2 ratios.

Catalyzed Gasoline Particulate Filters Reduce Secondary Organic Aerosol Production from Gasoline Direct Injection Vehicles.

The effects of photochemical aging on exhaust emissions from two light-duty vehicles with gasoline direct injection (GDI) engines equipped with and without catalyzed gasoline particle filters (GPFs) were investigated using a mobile environmental chamber. Both vehicles with and without the GPFs were exercised over the LA92 drive cycle using a chassis dynamometer. Diluted exhaust emissions from the entire LA92 cycle were introduced to the mobile chamber and subsequently photochemically reacted. It was found that the addition of catalyzed GPFs will significantly reduce tailpipe particulate emissions and also provide benefits in gaseous emissions, including nonmethane hydrocarbons (NMHC). Tailpipe emissions composition showed important changes with the use of GPFs by practically eliminating black carbon and increasing the fractional contribution of organic mass. Production of secondary organic aerosol (SOA) was reduced with GPF addition, but was also dependent on engine design which determined the amount of SOA precursors at the tailpipe. Our findings indicate that SOA production from GDI vehicles will be reduced with the application of catalyzed GPFs through the mitigation of reactive hydrocarbon precursors.

Gasoline Particulate Filters as an Effective Tool to Reduce Particulate and Polycyclic Aromatic Hydrocarbon Emissions from Gasoline Direct Injection (GDI) Vehicles: A Case Study with Two GDI Vehicles.

We assessed the gaseous, particulate, and genotoxic pollutants from two current technology gasoline direct injection vehicles when tested in their original configuration and with a catalyzed gasoline particulate filter (GPF). Testing was conducted over the LA92 and US06 Supplemental Federal Test Procedure (US06) driving cycles on typical California E10 fuel. The use of a GPF did not show any fuel economy and carbon dioxide (CO2) emission penalties, while the emissions of total hydrocarbons (THC), carbon monoxide (CO), and nitrogen oxides (NOx) were generally reduced. Our results showed dramatic reductions in particulate matter (PM) mass, black carbon, and total and solid particle number emissions with the use of GPFs for both vehicles over the LA92 and US06 cycles. Particle size distributions were primarily bimodal in nature, with accumulation mode particles dominating the distribution profile and their concentrations being higher during the cold-start period of the cycle. Polycyclic aromatic hydrocarbons (PAHs) and nitrated PAHs were quantified in both the vapor and particle phases of the PM, with the GPF-equipped vehicles practically eliminating most of these species in the exhaust. For the stock vehicles, 2-3 ring compounds and heavier 5-6 ring compounds were observed in the PM, whereas the vapor phase was dominated mostly by 2-3 ring aromatic compounds.

Particulate matter emissions and gaseous air toxic pollutants from commercial meat cooking operations.

This study assessed the effectiveness of three novel control technologies for particulate matter (PM) and volatile organic compound (VOC) removal from commercial meat cooking operations. All experiments were conducted using standardized procedures at University of California, Riverside's commercial test cooking facility. PM mass emissions collected using South Coast Air Quality Management District (SCAQMD) Method 5.1, as well as a dilution tunnel-based PM method showed statistically significantly reductions for each control technology when compared to baseline testing (i.e., without a catalyst). Overall, particle number emissions decreased with the use of control technologies, with the exception of control technology 2 (CT2), which is a grease removal technology based on boundary layer momentum transfer (BLMT) theory. Particle size distributions were unimodal with CT2 resulting in higher particle number populations at lower particle diameters. Organic carbon was the dominant PM component (>99%) for all experiments. Formaldehyde and acetaldehyde were the most abundant carbonyl compounds and showed reductions with the application of the control technologies. Some reductions in mono-aromatic VOCs were also observed with CT2 and the electrostatic precipitator (ESP) CT3 compared to the baseline testing.

Detailed Analysis of Criteria and Particle Emissions from a Very Large Crude Carrier Using a Novel ECA Fuel.

Ocean going vessels (OGVs) operating within emission control areas (ECA) are required to use fuels with ≤0.1 wt % sulfur. Up to now only distillate fuels could meet the sulfur limits. Recently refiners created a novel low-sulfur heavy-fuel oil (LSHFO) meeting the sulfur limits so questions were posed whether nitric oxide (NOx) and particulate matter (PM) emissions were the same for the two fuels. This project characterized criteria pollutants and undertook a detailed analysis of PM emissions from a very large crude oil carrier (VLCC) using a distillate ECA fuel (MGO) and novel LSHFO. Results showed emission factors of NOx were ∼5% higher with MGO than LSHFO. PM2.5 emission factors were ∼3 times higher with LSHFO than MGO, while both were below values reported by Lloyds, U.S. EPA and CARB. A detailed analysis of PM revealed it was >90% organic carbon (OC) for both fuels. Elemental carbon (EC) and soot measured with an AVL microsoot sensor (MSS) reflected black carbon. PM size distributions showed unimodal peaks for both MGO (20-30 nm) and LSHFO (30-50 nm). Particle number (PN) emissions were 28% and 17% higher with the PPS-M compared to the SMPS for LSHFO and MGO, respectively.

Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: Unified Method for Predicting Aerosol Composition and Formation.

Innovative secondary organic aerosol (SOA) composition analysis methods normalizing aerosol yield and chemical composition on an aromatic ring basis are developed and utilized to explore aerosol formation from oxidation of aromatic hydrocarbons. SOA yield and chemical composition are revisited using 15 years of University of California, Riverside/CE-CERT environmental chamber data on 17 aromatic hydrocarbons with HC:NO ranging from 11.1 to 171 ppbC:ppb. SOA yield is redefined in this work by normalizing the molecular weight of all aromatic precursors to the molecular weight of the aromatic ring [Formula: see text], where i is the aromatic hydrocarbon precursor. The yield normalization process demonstrates that the amount of aromatic rings present is a more significant driver of aerosol formation than the vapor pressure of the precursor aromatic. Yield normalization also provided a basis to evaluate isomer impacts on SOA formation. Further, SOA elemental composition is explored relative to the aromatic ring rather than on a classical mole basis. Generally, four oxygens per aromatic ring are observed in SOA, regardless of the alkyl substitutes attached to the ring. Besides the observed SOA oxygen to ring ratio (O/R ∼ 4), a hydrogen to ring ratio (H/R) of 6 + 2n is observed, where n is the number of nonaromatic carbons. Normalization of yield and composition to the aromatic ring clearly demonstrates the greater significance of aromatic ring carbons compared with alkyl carbon substituents in determining SOA formation and composition.

Temperature Effects on Secondary Organic Aerosol (SOA) from the Dark Ozonolysis and Photo-Oxidation of Isoprene.

Isoprene is globally the most ubiquitous nonmethane hydrocarbon. The biogenic emission is found in abundance and has a propensity for SOA formation in diverse climates. It is important to characterize isoprene SOA formation with varying reaction temperature. In this work, the effect of temperature on SOA formation, physical properties, and chemical nature is probed. Three experimental systems are probed for temperature effects on SOA formation from isoprene, NO + H2O2 photo-oxidation, H2O2 only photo-oxidation, and dark ozonolysis. These experiments show that isoprene readily forms SOA in unseeded chamber experiments, even during dark ozonolysis, and also reveal that temperature affects SOA yield, volatility, and density formed from isoprene. As temperature increases SOA yield is shown to generally decrease, particle density is shown to be stable (or increase slightly), and formed SOA is shown to be less volatile. Chemical characterization is shown to have a complex trend with both temperature and oxidant, but extensive chemical speciation are provided.

Effect of low-density polyethylene on smoke emissions from burning of simulated debris piles.

UNLABELLED: Low-density polyethylene (LDPE) plastic is used to keep piled debris from silvicultural activities--activities associated with development and care of forests--dry to enable efficient disposal by burning. The effects of inclusion of LDPE in this manner on smoke emissions are not well known. In a combustion laboratory experiment, 2-kg mixtures of LDPE and manzanita (Arctostaphylos sp.) wood containing 0, 0.25, and 2.5% LDPE by mass were burned. Gaseous and particulate emissions were sampled in real time during the entire flaming, mixed combustion phase--when the flaming and smoldering phases are present at the same time--and during a portion of the smoldering phase. Analysis of variance was used to test significance of modified combustion efficiency (MCE)--the ratio of concentrations of fire-integrated excess CO2 to CO2 plus CO--and LDPE content on measured individual compounds. MCE ranged between 0.983 and 0.993, indicating that combustion was primarily flaming; MCE was seldom significant as a covariate. Of the 195 compounds identified in the smoke emissions, only the emission factor (EF) of 3M-octane showed an increase with increasing LDPE content. Inclusion of LDPE had an effect on EFs of pyrene and fluoranthene, but no statistical evidence of a linear trend was found. Particulate emission factors showed a marginally significant linear relationship with MCE (0.05 < P-value < 0.10). Based on the results of the current and previous studies and literature reviews, the inclusion of small mass proportions of LDPE in piled silvicultural debris does not appear to change the emissions produced when low-moisture-content wood is burned. In general, combustion of wet piles results in lower MCEs and consequently higher levels of emissions. IMPLICATIONS: Current air quality regulations permit the use of burning to dispose of silvicultural piles; however, inclusion of low-density polyethyelene (LDPE) plastic in silvicultural piles can result in a designation of the pile as waste. Waste burning is not permitted in many areas, and there is also concern that inclusion of LDPE leads to toxic air emissions.

Measuring in-use ship emissions with international and U.S. federal methods.

UNLABELLED: Regulatory agencies have shifted their emphasis from measuring emissions during certification cycles to measuring emissions during actual use. Emission measurements in this research were made from two different large ships at sea to compare the Simplified Measurement Method (SMM) compliant with the International Maritime Organization (IMO) NOx Technical Code to the Portable Emission Measurement Systems (PEMS) compliant with the US. Environmental Protection Agency (EPA) 40 Code of Federal Regulations (CFR) Part 1065 for on-road emission testing. Emissions of nitrogen oxides (NOx), carbon dioxide (CO2), and carbon monoxide (CO) were measured at load points specified by the International Organization for Standardization (ISO) to compare the two measurement methods. The average percentage errors calculated for PEMS measurements were 6.5%, 0.6%, and 357% for NOx, CO2, and CO, respectively. The NOx percentage error of 6.5% corresponds to a 0.22 to 1.11 g/kW-hr error in moving from Tier III (3.4 g/kW-hr) to Tier I (17.0 g/kW-hr) emission limits. Emission factors (EFs) of NOx and CO2 measured via SMM were comparable to other studies and regulatory agencies estimates. However EF(PM2.5) for this study was up to 26% higher than that currently used by regulatory agencies. The PM2.5 was comprised predominantly of hydrated sulfate (70-95%), followed by organic carbon (11-14%), ash (6-11%), and elemental carbon (0.4-0.8%). IMPLICATIONS: This research provides direct comparison between the International Maritime Organization and U.S. Environmental Protection Agency reference methods for quantifying in-use emissions from ships. This research provides correlations for NOx, CO2, and CO measured by a PEMS unit (certified by U.S. EPA for on-road testing) against IMO's Simplified Measurement Method for on-board certification. It substantiates the measurements of NOx by PEMS and quantifies measurement error. This study also provides in-use modal and overall weighted emission factors of gaseous (NOx, CO, CO2, total hydrocarbons [THC], and SO2) and particulate pollutants from the main engine of a container ship, which are helpful in the development of emission inventory.

Route of administration significantly affects particle deposition and cellular recruitment.

Lung exposures to dusts, pollutants, and other aerosol particulates are known to be associated with pulmonary diseases such as asthma and Chronic Obstructive Pulmonary Disease. These health impacts are attributed to the ability of aerosol components to induce pulmonary inflammation, which promotes tissue remodeling, including fibrosis, tissue degradation, and smooth muscle proliferation. Consequently, the distribution of these effects can have a significant impact on the physiologic function of the lung. In order to study the impact of distribution of inhaled particulates on lung pathogenesis, we compared the effect of different methods of particle delivery. By comparing intranasal versus aerosol delivery of fluorescent microspheres, we observed strikingly distinct patterns of particle deposition; intranasal delivery provided focused deposition concentrated on larger airways, while aerosol delivery showed unform deposition throughout the lung parenchyma. Recognizing that the impacts of inflammatory cells are contingent upon their recruitment and behavior, we postulate that these variations in distribution patterns can result in significant alterations in biological responses. To elucidate the relevance of these findings in terms of biological representation, we subsequently conducted an investigation into the responses elicited by the administration of endotoxin (bacterial Lipopolysaccharide, or LPS) in a transgenic neutrophil reporter mouse model. As with the microsphere results, patterns of recruited neutrophil inflammatory responses matched the delivery method; that is, despite the active migratory behavior of neutrophils, inflammatory histopathology patterns were either focused on large airways (intranasal administration) or diffusely throughout the parenchyma (aerosol). These results demonstrate the importance of modes of aerosol delivery as different patterns of inflammation and tissue remodeling will have distinct impacts on lung physiology.

Aerosolized aqueous dust extracts collected near a drying lake trigger acute neutrophilic pulmonary inflammation reminiscent of microbial innate immune ligands.

BACKGROUND: A high incidence of asthma is prevalent among residents near the Salton Sea, a large inland terminal lake in southern California. This arid region has high levels of ambient particulate matter (PM); yet while high PM levels are often associated with asthma in many environments, it is possible that the rapidly retreating lake, and exposed playa or lakebed, may contribute components with a specific role in promoting asthma symptoms. OBJECTIVES: Our hypothesis is that asthma may be higher in residents closest to the Salton Sea due to chronic exposures to playa dust. Playa emissions may be concentrating dissolved material from the lake, with microbial components capable of inducing pulmonary innate immune responses. To test this hypothesis, we used a mouse model of aerosol exposures to assess the effects of playa dust. METHODS: From dust collected around the Salton Sea region, aqueous extracts were used to generate aerosols, which were injected into an environmental chamber for mouse exposure studies. We compared the effects of exposure to Salton Sea aerosols, as well as to known immunostimulatory reference materials. Acute 48-h and chronic 7-day exposures were compared, with lungs analyzed for inflammatory cell recruitment and gene expression. RESULTS: Dust from sites nearest to the Salton Sea triggered lung neutrophil inflammation that was stronger at 48-h but reduced at 7-days. This acute inflammatory profile and kinetics resembled the response to innate immune ligands LTA and LPS while distinct from the classic allergic response to Alternaria. CONCLUSION: Lung inflammatory responses to Salton Sea dusts are similar to acute innate immune responses, raising the possibility that microbial components are entrained in the dust, promoting inflammation. This effect highlights the health risks at drying terminal lakes from inflammatory components in dust emissions from exposed lakebed.

Overview of ICARUS-A Curated, Open Access, Online Repository for Atmospheric Simulation Chamber Data.

Atmospheric simulation chambers continue to be indispensable tools for research in the atmospheric sciences. Insights from chamber studies are integrated into atmospheric chemical transport models, which are used for science-informed policy decisions. However, a centralized data management and access infrastructure for their scientific products had not been available in the United States and many parts of the world. ICARUS (Integrated Chamber Atmospheric data Repository for Unified Science) is an open access, searchable, web-based infrastructure for storing, sharing, discovering, and utilizing atmospheric chamber data [https://icarus.ucdavis.edu]. ICARUS has two parts: a data intake portal and a search and discovery portal. Data in ICARUS are curated, uniform, interactive, indexed on popular search engines, mirrored by other repositories, version-tracked, vocabulary-controlled, and citable. ICARUS hosts both legacy data and new data in compliance with open access data mandates. Targeted data discovery is available based on key experimental parameters, including organic reactants and mixtures that are managed using the PubChem chemical database, oxidant information, nitrogen oxide (NOx) content, alkylperoxy radical (RO2) fate, seed particle information, environmental conditions, and reaction categories. A discipline-specific repository such as ICARUS with high amounts of metadata works to support the evaluation and revision of atmospheric model mechanisms, intercomparison of data and models, and the development of new model frameworks that can have more predictive power in the current and future atmosphere. The open accessibility and interactive nature of ICARUS data may also be useful for teaching, data mining, and training machine learning models.

Greenhouse gas and criteria emission benefits through reduction of vessel speed at sea.

Reducing emissions from ocean-going vessels (OGVs) as they sail near populated areas is a widely recognized goal, and Vessel Speed Reduction (VSR) is one of several strategies that is being adopted by regulators and port authorities. The goal of this research was to measure the emission benefits associated with greenhouse gas and criteria pollutants by operating OGVs at reduced speed. Emissions were measured from one Panamax and one post-Panamax class container vessels as their vessel speed was reduced from cruise to 15 knots or below. VSR to 12 knots yielded carbon dioxide (CO(2)) and nitrogen oxides (NO(x)) emissions reductions (in kg/nautical mile (kg/nmi)) of approximately 61% and 56%, respectively, as compared to vessel cruise speed. The mass emission rate (kg/nmi) of PM(2.5) was reduced by 69% with VSR to 12 knots alone and by ~97% when coupled with the use of the marine gas oil (MGO) with 0.00065% sulfur content. Emissions data from vessels while operating at sea are scarce and measurements from this research demonstrated that tidal current is a significant parameter affecting emission factors (EFs) at lower engine loads. Emissions factors at ≤20% loads calculated by methodology adopted by regulatory agencies were found to underestimate PM(2.5) and NO(x) by 72% and 51%, respectively, when compared to EFs measured in this study. Total pollutant emitted (TPE) in the emission control area (ECA) was calculated, and emission benefits were estimated as the VSR zone increased from 24 to 200 nmi. TPE(CO2) and TPE(PM2.5) estimated for large container vessels showed benefits for CO(2) (2-26%) and PM(2.5) (4-57%) on reducing speeds from 15 to 12 knots, whereas TPE(CO2) and TPE(PM2.5) for small and medium container vessels were similar at 15 and 12 knots.

Benefits of two mitigation strategies for container vessels: cleaner engines and cleaner fuels.

Emissions from ocean-going vessels (OGVs) are a significant health concern for people near port communities. This paper reports the emission benefits for two mitigation strategies, cleaner engines and cleaner fuels, for a 2010 container vessel. In-use emissions were measured following International Organization for Standardization (ISO) protocols. The overall in-use nitrogen oxide (NO(x)) emission factor was 16.1 ± 0.1 gkW(-1) h(-1), lower than the Tier 1 certification (17 gkW(-1) h(-1)) and significantly lower than the benchmark value of 18.7 gkW(-1) h(-1) commonly used for estimating emission inventories. The in-use particulate matter (PM(2.5)) emission was 1.42 ± 0.04 gkW(-1) h(-1) for heavy fuel oil (HFO) containing 2.51 wt % sulfur. Unimodal (∼30 nm) and bimodal (∼35 nm; ∼75 nm) particle number size distributions (NSDs) were observed when the vessel operated on marine gas oil (MGO) and HFO, respectively. First-time emission measurements during fuel switching (required 24 nautical miles from coastline) showed that concentrations of sulfur dioxide (SO(2)) and particle NSD took ∼55 min to reach steady-state when switching from MGO to HFO and ∼84 min in the opposite direction. Therefore, if OGVs commence fuel change at the regulated boundary, then vessels can travel up to 90% of the distance to the port before steady-state values are re-established. The transient behavior follows a classic, nonlinear mixing function driven by the amount of fuel in day tank and the fuel consumption rate. Hence, to achieve the maximum benefits from a fuel change regulation, fuel switch boundary should be further increased to provide the intended benefits for the people living near the ports.

Allergic inflammation in the human lower respiratory tract affected by exposure to diesel exhaust.

To improve understanding of human health risks from exposure to diesel exhaust particles (DEP*), we tested whether immunologic effects previously observed in the human nose also occur in the lower airways. Our overall hypothesis was that cell influx and production of cytokines, chemokines, immunoglobulin E (IgE), and other mediators, which would be measurable in sputum and blood, occur in people with asthma after realistic controlled exposures to diesel exhaust (DE). In Phase 1 we tested for direct effects of DE in subjects with clinically undifferentiated mild asthma. In Phase 2 we tested whether DE exposure would exacerbate response to inhaled cat allergen in subjects with both asthma and cat sensitivity. The exposure facility was a controlled-environment chamber supplied with DE from an idling medium-duty truck with ultra-low-sulfur fuel and no catalytic converter. We exposed volunteers for 2 hours with intermittent exercise to exhaust with DEP mass concentration near 100 microg/m3. Exposures to nitrogen dioxide (NO2) near 0.35 ppm (similar to its concentration in DE) and to filtered air (FA) served as controls. Blood was drawn before exposure on day 1 and again the next morning (day 2). Sputum was induced only on day 2. Bronchial reactivity was measured -1 hour after exposure ended. Supplementary endpoints included measures of blood coagulation status, cardiopulmonary physiology, and symptoms. Each phase employed 15 subjects with asthma; 3 subjects participated in both phases. In Phase 1, airway reactivity was measured with inhaled methacholine; in Phase 2, with inhaled cat allergen. We found little biologic response to DE exposure compared with exposure to control atmospheres. In Phase 1, interleukin 4 (IL-4) in sputum showed an estimated 1.7-fold increase attributable to DE exposure, which was close to statistical significance; airway resistance increased modestly but significantly on day 2 after DE exposure; and nonspecific symptom scores increased significantly during DE exposure. In Phase 2, indicators of airway inflammation in sputum showed a possibly meaningful response: polymorphonuclear leukocytes (PMNs) and eosinophils increased after DE exposure, whereas macrophages decreased. IgE in sputum and the bronchoconstrictive response to cat allergen varied significantly between atmospheres, but not in patterns consistent with our primary hypothesis. Symptom score changes relatable to DE exposure were smaller than those in Phase 1 and not statistically significant. Controlled exposures, lasting 2 hours with intermittent exercise, to diluted DE at a particle mass concentration of 100 microg/m3 did not evoke clear and consistent lower-airway or systemic immunologic or inflammatory responses in mildly asthmatic subjects, with or without accompanying challenge with cat allergen. Likewise, these DE exposures did not significantly increase nonspecific or allergen-specific bronchial reactivity. A few isolated statistically significant or near-significant changes were observed during and after DE exposure, including increases in nonspecific symptoms (e.g., headache, nausea) suggestive of subtle, rapid-onset systemic effects. It is possible the lower respiratory tract is more resistant than the nose to adjuvant effects of diesel particles on allergic inflammation, so that no meaningful effects occur under exposure conditions like these. Alternatively, the experimental conditions may have been near a threshold for finding effects. That is, important lower respiratory effects may occur but may be detectable experimentally with slightly higher DEP concentrations, longer exposures, more invasive testing (e.g., bronchoalveolar lavage), or more susceptible subjects. However, ethical and practical barriers to such experiments are considerable.

Aging of secondary organic aerosol from alpha-pinene ozonolysis: roles of hydroxyl and nitrate radicals.

UNLABELLED: This work investigates the oxidative aging of preformed secondary organic aerosol (SOA) derived from alpha-pinene ozonolysis (-100 ppb(v) hydrocarbon [HC(x)] with excess of O3) within the University of California-Riverside Center for Environmental Research and Technology environmental chamber that occurs after introduction of additional hydroxyl (OH) and nitrate (NO3) radicals. Simultaneous measurements of SOA volume concentration, hygroscopicity, particle density, and elemental chemical composition (C:O:H) reveal increased particle wall-loss-corrected SOA formation (1.5%, 7.5%, and 15.1%), increase in oxygen-to-carbon ratio (O/C; 15.6%, 8.7%, and 8.7%), and hydrophilicity (4.2%, 7.4%, and 1.4%) after addition of NO (ultraviolet [UV] on), H2O2 (UV(on)), and N2O5 (dark), respectively. The processing observed as an increase in O/C and hydrophilicity is attributed to OH and NO3 reactions with first-generation vapor products and UV photolysis. The rate of increase in O/C appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) on a day time scale even at the raised chamber radical concentrations. The additional processing with UV irradiation without addition of NO, H2O2, or N2O5 is observed, adding 5.5% wall-loss-corrected volume. The photolysis-only processing is attributed to additional OH generated from photolysis of the nitrous acid (HONO) offgasing from chamber walls. This finding indicates that OH and NO3 radicals can further alter the chemical composition of SOA from alpha-pinene ozonolysis, which is proved to consist of first-generation products. IMPLICATIONS: Secondary organic aerosol (SOA) may undergo aging processes once formed in the atmosphere, thereby altering the physicochemical and toxic properties of aerosol. This study discusses SOA aging of a major biogenic volatile organic compound (VOC; alpha-pinene) after it initially forms SOA. Aging of the alpha-pinene ozonolysis system by OH (through NO or H2O2 injection), NO3 (through N2O5 injection), and photolysis is observed. Although the reaction rate appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) level of oxygenation on a 1-day scale, it is important that SOA aging be considered in ambient air quality models. Aging in this study is attributed to further oxidation of gas-phase oxidation products of alpha-pinene ozonolysis.

The impact of hydrogenated vegetable oil (HVO) on the formation of secondary organic aerosol (SOA) from in-use heavy-duty diesel vehicles.

This manuscript contains an assessment of tailpipe emissions and secondary aerosol formation from two in-use heavy-duty diesel vehicles (HDDVs) with different aftertreatment systems when operated with ultra-low sulfur diesel (ULSD) and hydrogenated vegetable oil (HVO) operated on a chassis dynamometer. Secondary aerosol formation was characterized from the HDDVs' diluted exhaust collected and photochemically aged in a 30 m3 mobile atmospheric chamber. Primary nitrogen oxide (NOx) and particulate matter (PM) emissions were reduced for both vehicles operating on HVO compared to ULSD. For the vehicles with no selective catalytic reduction (SCR) system, secondary aerosol production was ~2 times higher for ULSD compared to HVO. The composition of primary aerosol was exclusively organic for the vehicle with no SCR system regardless of fuel type. The composition of secondary aerosol with HVO was primarily organic for the vehicle equipped with diesel particulate filter (DPF)/SCR system; however, when the same vehicle was tested with ULSD, the composition was ~20% organic (80% ammonium nitrate). The results reported here revealed that the in-use vehicle with no-SCR had a non-functioning DPF leading to dramatic increases in secondary aerosol formation when compared to the DPF/SCR vehicle. The high-resolution mass spectra analysis showed that the POA of HVO combustion contained relatively lower portion of CH class compounds (or higher CHO class compounds) compared to ULSD under the similar conditions, which can be rationalized by the higher cetane number of HVO. Substantial growth of oxidized organic aerosol (such as m/z 44 peak) were observed after 5 h of photochemical oxidation, consistent with aged organic aerosols present in the atmosphere. The C4H9+ fragment at m/z 57 peak was used as a tracer to calculate evolution of secondary organic aerosol formation.

Quantifying in-use PM measurements for heavy duty diesel vehicles.

Heavy duty emissions regulations have recently expanded from the laboratory to include in-use requirements. This paradigm shift to in-use testing has forced the development of portable emissions measurement systems (PEMS) for particulate matter (PM). These PM measurements are not trivial for laboratory work, and are even more complex for in-use testing. This study evaluates five PM PEMS in comparison to UCR's mobile reference laboratory under in-use conditions. Three on-highway, heavy-duty trucks were selected to provide PM emissions levels from 0.1 to 0.0003 g/hp-h, with varying compositions of elemental carbon (EC), organic carbon (OC), and sulfate. The on-road driving courses included segments near sea level, at elevations up to 1500 m, and coastal and desert regions. The photoacoustic measurement PEMS performed best for the non-after treatment system (ATS)-equipped engine, where the PM was mostly EC, with a linear regression slope of 0.91 and an R(2) of 0.95. The PEMS did not perform as well for the 2007 modified ATS equipped engines. The best performing PEMS showed a slope of 0.16 for the ATS-equipped engine with predominantly sulfate emissions and 0.89 for the ATS-equipped engine with predominantly OC emissions, with the next best slope at 0.45 for the predominantly OC engine.

Real-time gaseous, PM and ultrafine particle emissions from a modern marine engine operating on biodiesel.

Emissions from harbor-craft significantly affect air quality in populated regions near ports and inland waterways. This research measured regulated and unregulated emissions from an in-use EPA Tier 2 marine propulsion engine on a ferry operating in a bay following standard methods. A special effort was made to monitor continuously both the total Particulate Mass (PM) mass emissions and the real-time Particle Size Distribution (PSD). The engine was operated following the loads in ISO 8178-4 E3 cycle for comparison with the certification standards and across biodiesel blends. Real-time measurements were also made during a typical cruise in the bay. Results showed the in-use nitrogen oxide (NOx) and PM(2.5) emission factors were within the not to exceed standard for Tier 2 marine engines. Comparing across fuels we observed the following: a) no statistically significant change in NO(x) emissions with biodiesel blends (B20, B50); b) ∼ 16% and ∼ 25% reduction of PM(2.5) mass emissions with B20 and B50 respectively; c) a larger organic carbon (OC) to elemental carbon (EC) ratio and organic mass (OM) to OC ratio with B50 compared to B20 and B0; d) a significant number of ultrafine nuclei and a smaller mass mean diameter with increasing blend-levels of biodiesel. The real-time monitoring of gaseous and particulate emissions during a typical cruise in the San Francisco Bay (in-use cycle) revealed important effects of ocean/bay currents on emissions: NO(x) and CO(2) increased 3-fold; PM(2.5) mass increased 6-fold; and ultrafine particles disappeared due to the effect of bay currents. This finding has implications on the use of certification values instead of actual in-use emission values when developing inventories. Emission factors for some volatile organic compounds (VOCs), carbonyls, and poly aromatic hydrocarbons (PAHs) are reported as supplemental data.