Characterizing Volatile Emissions and Combustion Byproducts from Aqueous Film-Forming Foams Using Online Chemical Ionization Mass Spectrometry.

Aqueous film-forming foams (AFFFs) are used in firefighting applications and often contain per- and polyfluoroalkyl substances (PFAS), which can detrimentally impact environmental and biological health. Incineration is a potential disposal method for AFFFs, which may produce secondary PFAS and other air pollutants. We used online chemical ionization mass spectrometry (CIMS) to measure volatile PFAS emissions from incinerating AFFF concentrate solutions. We quantified perfluorinated carboxylic acids (PFCAs) during the incineration of legacy and contemporary AFFFs. These included trifluoroacetic acid, which reached mg m-3 quantities in the incinerator exhaust. These PFCAs likely arose as products of incomplete combustion of AFFF fluorosurfactants with lower peak furnace temperatures yielding higher PFCA concentrations. We also detected other short-chain PFAS, and other novel chemical products in AFFF combustion emissions. The volatile headspace above AFFF solutions contained larger (C ≥ 8), less oxidized PFAS detected by CIMS. We identified neutral PFAS resembling fluorotelomer surfactants (e.g., fluorotelomer sulfonamide alkylbetaines and fluorotelomer thioether amido sulfonates) and fluorotelomer alcohols in contemporary AFFF headspaces. Directly comparing the distinct chemical spaces of AFFF volatile headspace and combustion byproducts as measured by CIMS provides insight toward the chemistry of PFAS during thermal treatment of AFFFs.

Characterization of PFAS air emissions from thermal application of fluoropolymer dispersions on fabrics.

During thermal processes utilized in affixing fluoropolymer coatings dispersion to fibers and fabrics, coating components are vaporized. It is suspected that per- and polyfluoroalkyl substances (PFAS) from the dispersions may undergo chemical transformations at the temperatures used, leading to additional emitted PFAS thermal byproducts. It is important to characterize these emissions to support evaluation of the resulting environmental and health impacts. In this study, a bench-scale system was built to simulate this industrial process via thermal application of dispersions to fiberglass utilizing relevant temperatures and residence times in sequential drying, baking, and sintering steps. Experiments were performed with two commercially available dispersions and a simple model mixture containing a single PFAS (6:2 fluorotelomer alcohol [6:2 FTOH]). Vapor-phase emissions were sampled and characterized by several off-line and real-time mass spectrometry techniques for targeted and nontargeted PFAS. Results indicate that multiple PFAS thermal transformation products and multiple nonhalogenated organic species were emitted from the exit of the high temperature third (sintering) furnace when 6:2 FTOH was the only PFAS present in the aqueous mixture. This finding supports the hypothesis that temperatures typical of these industrial furnaces may also induce chemical transformations within the fluorinated air emissions. Experiments using the two commercial fluoropolymer dispersions indicate air emissions of part-per-million by volume (ppmv) concentrations of heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether (Fluoroether E1), as well as other PFAS at operationally relevant temperatures. We suspect that E1 is a direct thermal decomposition product (via decarboxylation) of 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid (commonly referred to as HFPO-DA) present in the dispersions. Other thermal decomposition products, including the monomer, tetrafluoroethene, may originate from the PFAS used to stabilize the dispersion or from the polymer particles in suspension. This study represents the first researcher-built coating application simulator to report nontargeted PFAS emission characterization, real-time analyses, and the quantification of 30 volatile target PFAS.Implications: Thermal processes used to affix fluoropolymers to fabrics are believed to be a source of PFAS air emissions. These coating operations are used by many large and small manufacturers and typically do not currently require any air emissions control. This research designed and constructed a bench-scale system that simulates these processes and used several off-line and advanced real-time mass spectroscopy techniques to characterize PFAS air emissions from two commercial fluoropolymer dispersions. Further, as the compositions of commercial dispersions are largely unknown, a model three-component solution containing a single PFAS was used to characterize emissions of multiple PFAS thermal transformation products at operationally relevant conditions. This research shows that fluoropolymer fabric coating facilities can be sources of complex mixtures of PFAS air emissions that include volatile and semivolatile PFAS present in the dispersions, as well as PFAS byproducts formed by the thermal transformation of fluorocarbon and hydrocarbon species present in these dispersions.

Mutagenicity and carcinogenicity of combustion emissions are impacted more by combustor technology than by fuel composition: A brief review.

Studies during the past 50 years have characterized the carcinogenicity and mutagenicity of extractable organic material (EOM) of particulate matter (PM) in ambient air and from combustion emissions. We have summarized conclusions from these studies and present data supporting those conclusions for 50 combustion emissions, including carcinogenic potencies on mouse skin (papillomas/mouse/mg EOM), mutagenic potencies (revertants/µg EOM) in the Salmonella (Ames) mutagenicity assay, and mutagenicity emission factors (revertants/kg fuel or revertants/MJthermal ) in Salmonella. Mutagenic potencies of EOM from PM in ambient air and combustion emissions span 1-2 orders of magnitude, respectively. In contrast, the revertants/m3 span >5 orders of magnitude due to variable PM concentrations in ambient air. Carcinogenic potencies of EOM from combustion emissions on mouse skin and EOM-associated human lung cancer risk from those emissions both span ~3 orders of magnitude and are highly associated. The ubiquitous presence of polycyclic aromatic hydrocarbons (PAHs), nitroarenes, and aromatic amines results in mutagenic and carcinogenic potencies of PM that span only 1-3 orders of magnitude; most PM induces primarily G to T mutations. Mutagenicity emission factors of combustion emissions span 3-5 orders of magnitude and correlate with PAH emission factors (r > 0.9). Mutagenicity emission factors were largely a function of how material was burned (highly efficient modern combustors versus open burning) rather than what materials were burned. Combustion systems that minimize kinetic and mass-transfer limitations and promote complete oxidation also minimize the mutagenicity of their emissions. This fundamental engineering principle can inform environmental and public health assessments of combustion emissions.

Combustion of C1 and C2 PFAS: Kinetic modeling and experiments.

A combustion model, originally developed to simulate the destruction of chemical warfare agents, was modified to include C1-C3 fluorinated organic reactions and kinetics compiled by the National Institute of Standards and Technology (NIST). A simplified plug flow reactor version of this model was used to predict the destruction efficiency (DE) and formation of products of incomplete combustion (PICs) for three C1 and C2 per- and poly-fluorinated alkyl substances (PFAS) (CF4, CHF3, and C2F6) and compare predicted values to Fourier Transform Infrared spectroscopy (FTIR)-based measurements made from a pilot-scale EPA research combustor (40-64 kW, natural gas-fired, 20% excess air). PFAS were introduced through the flame, and at post-flame locations along a time-temperature profile allowing for simulation of direct flame and non-flame injection, and examination of the sensitivity of PFAS destruction on temperature and free radical flame chemistry. Results indicate that CF4 is particularly difficult to destroy with DEs ranging from ~60 to 95% when introduced through the flame at increasing furnace loads. Due to the presence of lower energy C-H and C-C bonds to initiate molecular dissociation reactions, CHF3 and C2F6 were easier to destroy, exhibiting DEs >99% even when introduced post-flame. However, these lower bond energies may also lead to the formation of CF2 and CF3 radicals at thermal conditions unable to fully de-fluorinate these species and formation of fluorinated PICs. DEs determined by the model agreed well with the measurements for CHF3 and C2F6 but overpredicted DEs at high temperatures and underpredicted DEs at low temperatures for CF4. However, high DEs do not necessarily mean absence of PICs, with both model predictions and limited FTIR measurements indicating the presence of similar fluorinated PICs in the combustion emissions. The FTIR was able to provide real-time emission measurements and additional model development may improve prediction of PFAS destruction and PIC formation.Implications: The widespread use of PFAS for over 70 years has led to their presence in multiple environmental matrixes including human tissues. While the chemical and thermal stability of PFAS are related to their desirable properties, this stability means that PFAS are very slow to degrade naturally and potentially difficult to destroy completely through thermal treatment processes often used for organic waste destruction. In this applied combustion study, model PFAS compounds were introduced to a pilot-scale EPA research furnace. Real-time FTIR measurements were performed of the injected compound and trace products of incomplete combustion (PICs) at operationally relevant conditions, and the results were successfully compared to kinetic model predictions of those same PFAS destruction efficiencies and trace gas-phase PIC constituents. This study represents a significant potential enhancement in available tools to support effective management of PFAS-containing wastes.

Low Temperature Thermal Treatment of Gas-Phase Fluorotelomer Alcohols by Calcium Oxide.

Given the extent to which per- and polyfluoroalkyl substances (PFAS) are used in commercial and industrial applications, the need to evaluate treatment options that reduce environmental emissions and human and ecological exposures of PFAS is becoming more necessary. One specific chemical class of PFAS, fluorotelomer alcohols (FTOHs), have vapor pressures such that a significant fraction is expected to be present in the gas-phase even at ambient temperatures. FTOHs are used in a variety of PFAS applications, including synthesis and material coatings. Using two complementary mass spectrometric methods, the use of calcium oxide (CaO) was examined as a low temperature and potentially low-cost thermal treatment media for removal and destruction of four gas-phase FTOHs of varying molecular weights. This was accomplished by assessing the removal/destruction efficiency of the FTOHs and the formation of fluorinated byproducts as a function of treatment temperature (200 - 800 °C) in the presence of CaO compared to thermal-only destruction. During the treatment process, there is evidence that other PFAS compounds are produced at low temperatures (200 - 600 °C) as the primary FTOH partially degrades. At temperatures above 600 °C, thermal treatment with CaO prevented the formation or removed nearly all these secondary products.

Mutagenicity emission factors of canola oil and waste vegetable oil biodiesel: Comparison to soy biodiesel.

Canola (or rapeseed) oil and waste vegetable oil (WVO) are used commonly to make biodiesel fuels composed completely from these oils (B100) or as blends with petroleum diesel (B0). However, no studies have reported the mutagenic potencies of the particulate matter with diameter ≤2.5 µm (PM2.5) or the mutagenicity emission factors, such as revertants/MJthermal (rev/MJth) for these biodiesel emissions. Using strains TA98 and TA100 with the Salmonella (Ames) mutagenicity assay, we determined these metrics for organic extracts of PM2.5 of emissions from biodiesel containing 5% soy oil (soy B5); 5, 20, 50, and 100% canola (canola B5, B20, B50, B100), and 100% waste vegetable oil (WVO B100). The mutagenic potencies (rev/mg PM2.5) of the canola B100 and WVO B100 emissions were generally greater than those of B0, whereas the mutagenicity emission factors (rev/MJth, rev/kg fuel, and rev/m3) were less, reflecting the lower PM emissions of the biodiesels relative to B0. Nearly all the rev/mg PM2.5 and rev/MJth values were greater in TA98 with S9 than without S9, indicating a relatively greater role for polycyclic aromatic hydrocarbons, which require S9, than nitroarenes, which do not. In TA100 -S9, the rev/mg PM2.5 and rev/MJth for the biodiesels were generally ≥ to those of B0, indicating that most of these biodiesels produced more direct-acting, base-substitution mutagenic activity than did B0. For B100 biodiesels and petroleum diesel, the rev/MJth in TA98 + S9 ranked: petroleum diesel > canola > WVO > soy. The diesel emissions generally had rev/MJth values orders of magnitude higher than those of large utility-scale combustors (natural gas, coal, oil, or wood) but orders of magnitude lower than those of inefficient open burning (e.g., residential wood fireplaces). These comparative data of the potential health effects of a variety of biodiesel fuels will help inform the life-cycle assessment and use of biodiesel fuels.

Mutagenicity and oxidative damage induced by an organic extract of the particulate emissions from a simulation of the deepwater horizon surface oil burns.

Emissions from oil fires associated with the "Deepwater Horizon" explosion and oil discharge that began on April 20, 2010 in the Gulf of Mexico were analyzed chemically to only a limited extent at the time but were shown to induce oxidative damage in vitro and in mice. To extend this work, we burned oil floating on sea water and performed extensive chemical analyses of the emissions (Gullett et al., Marine Pollut Bull, in press, ). Here, we examine the ability of a dichloromethane extract of the particulate material with an aerodynamic size ≤ 2.5 µm (PM2.5 ) from those emissions to induce oxidative damage in human lung cells in vitro and mutagenicity in 6 strains of Salmonella. The extract had a percentage of extractable organic material (EOM) of 7.0% and increased expression of the heme oxygenase (HMOX1) gene in BEAS-2B cells after exposure for 4 hr at 20 µg of EOM/ml. However, the extract did not alter mitochondrial respiration rate as measured by extracellular flux analysis. The extract was most mutagenic in TA100 +S9, indicative of a role for polycyclic aromatic hydrocarbons (PAHs), reflective of the high concentrations of PAHs in the emissions (1 g/kg of oil consumed). The extract had a mutagenicity emission factor of 1.8 ± 0.1 × 105 revertants/megajoulethermal in TA98 +S9, which was greater than that of diesel exhaust and within an order of magnitude of open burning of wood and plastic. Thus, organics from PM2.5 of burning oil can induce oxidative responses in human airway epithelial cells and are highly mutagenic. Environ. Mol. Mutagen. 58:162-171, 2017. © 2017 Wiley Periodicals, Inc.

Particulate Formation from a Copper Oxide-Based Oxygen Carrier in Chemical Looping Combustion for CO2 Capture.

Attrition behavior and particle loss of a copper oxide-based oxygen carrier from a methane chemical looping combustion (CLC) process was investigated in a fluidized bed reactor. The aerodynamic diameters of most elutriated particulates, after passing through a horizontal settling duct, range between 2 and 5 µm. A notable number of submicrometer particulates are also identified. Oxygen carrier attrition was observed to lead to increased CuO loss resulting from the chemical looping reactions, i.e., Cu is enriched in small particles generated primarily from fragmentation in the size range of 10-75 µm. Cyclic reduction and oxidation reactions in CLC have been determined to weaken the oxygen carrier particles, resulting in increased particulate emission rates when compared to those of oxygen carriers without redox reactions. The generation rate for particulates <10 µm was found to decrease with progressive cycles over as-prepared oxygen carrier particles and then reach a steady state. The surface of the oxygen carrier is also found to be coarsened due to a Kirkendall effect, which also explains the enrichment of Cu on particle surfaces and in small particles.

Soot, organics, and ultrafine ash from air- and oxy-fired coal combustion.

Pulverized bituminous coal was burned in a 10W externally heated entrained flow furnace under air-combustion and three oxy-combustion inlet oxygen conditions (28, 32, and 36%). Experiments were designed to produce flames with practically relevant stoichiometric ratios (SR=1.2-1.4) and constant residence times (2.3s). Size-classified fly ash samples were collected, and measurements focused on the soot, elemental carbon (EC), and organic carbon (OC) composition of the total and ultrafine (<0.6µm) fly ash. Results indicate that although the total fly ash carbon, as measured by loss on ignition, was always acceptably low (<2%) with all three oxycombustion conditions lower than air-combustion, the ultrafine fly ash for both air-fired and oxy-fired combustion conditions consists primarily of carbonaceous material (50-95%). Carbonaceous components on particles <0.6µm measured by a thermal optical method showed that large fractions (52-93%) consisted of OC rather than EC, as expected. This observation was supported by thermogravimetric analysis indicating that for the air, 28% oxy, and 32% oxy conditions, 14-71% of this material may be OC volatilizing between 100 and 550°C with the remaining 29-86% being EC/soot. However, for the 36% oxy condition, OC may comprise over 90% of the ultrafine carbon with a much smaller EC/soot contribution. These data were interpreted by considering the effects of oxy-combustion on flame attachment, ignition delay, and soot oxidation of a bituminous coal, and the effects of these processes on OC and EC emissions. Flame aerodynamics and inlet oxidant composition may influence emissions of organic hazardous air pollutants (HAPs) from a bituminous coal. During oxy-coal combustion, judicious control of inlet oxygen concentration and placement may be used to minimize organic HAP and soot emissions.

Mutagenicity and Pollutant Emission Factors of Solid-Fuel Cookstoves: Comparison with Other Combustion Sources.

BACKGROUND: Emissions from solid fuels used for cooking cause ~4 million premature deaths per year. Advanced solid-fuel cookstoves are a potential solution, but they should be assessed by appropriate performance indicators, including biological effects. OBJECTIVE: We evaluated two categories of solid-fuel cookstoves for eight pollutant and four mutagenicity emission factors, correlated the mutagenicity emission factors, and compared them to those of other combustion emissions. METHODS: We burned red oak in a 3-stone fire (TSF), a natural-draft stove (NDS), and a forced-draft stove (FDS), and we combusted propane as a liquified petroleum gas control fuel. We determined emission factors based on useful energy (megajoules delivered, MJd) for carbon monoxide, nitrogen oxides (NOx), black carbon, methane, total hydrocarbons, 32 polycyclic aromatic hydrocarbons, PM2.5, levoglucosan (a wood-smoke marker), and mutagenicity in Salmonella. RESULTS: With the exception of NOx, the emission factors per MJd were highly correlated (r ≥ 0.97); the correlation for NOx with the other emission factors was 0.58-0.76. Excluding NOx, the NDS and FDS reduced the emission factors an average of 68 and 92%, respectively, relative to the TSF. Nevertheless, the mutagenicity emission factor based on fuel energy used (MJthermal) for the most efficient stove (FDS) was between those of a large diesel bus engine and a small diesel generator. CONCLUSIONS: Both mutagenicity and pollutant emission factors may be informative for characterizing cookstove performance. However, mutagenicity emission factors may be especially useful for characterizing potential health effects and should be evaluated in relation to health outcomes in future research. An FDS operated as intended by the manufacturer is safer than a TSF, but without adequate ventilation, it will still result in poor indoor air quality. CITATION: Mutlu E, Warren SH, Ebersviller SM, Kooter IM, Schmid JE, Dye JA, Linak WP, Gilmour MI, Jetter JJ, Higuchi M, DeMarini DM. 2016. Mutagenicity and pollutant emission factors of solid-fuel cookstoves: comparison with other combustion sources. Environ Health Perspect 124:974-982; http://dx.doi.org/10.1289/ehp.1509852.

Generation and characterization of diesel engine combustion emissions from petroleum diesel and soybean biodiesel fuels and application for inhalation exposure studies.

Biodiesel made from the transesterification of plant- and animal-derived oils is an important alternative fuel source for diesel engines. Although numerous studies have reported health effects associated with petroleum diesel emissions, information on biodiesel emissions are more limited. To this end, a program at the U.S. EPA assessed health effects of biodiesel emissions in rodent inhalation models. Commercially obtained soybean biodiesel (B100) and a 20% blend with petroleum diesel (B20) were compared to pure petroleum diesel (B0). Rats and mice were exposed independently for 4 h/day, 5 days/week for up to 6 weeks. Exposures were controlled by dilution air to obtain low (50 µg/m(3)), medium (150 µg/m(3)) and high (500 µg/m(3)) diesel particulate mass (PM) concentrations, and compared to filtered air. This article provides details on facilities, fuels, operating conditions, emission factors and physico-chemical characteristics of the emissions used for inhalation exposures and in vitro studies. Initial engine exhaust PM concentrations for the B100 fuel (19.7 ± 0.7 mg/m(3)) were 30% lower than those of the B0 fuel (28.0 ± 1.5 mg/m(3)). When emissions were diluted with air to control equivalent PM mass concentrations, B0 exposures had higher CO and slightly lower NO concentrations than B100. Organic/elemental carbon ratios and oxygenated methyl esters and organic acids were higher for the B100 than B0. Both the B0 and B100 fuels produced unimodal-accumulation mode particle-size distributions, with B0 producing lower concentrations of slightly larger particles. Subsequent papers in this series will describe the effects of these atmospheres on cardiopulmonary responses and in vitro genotoxicity studies.

Health effects of soy-biodiesel emissions: bioassay-directed fractionation for mutagenicity.

CONTEXT: Soy biodiesel is the predominant biodiesel in the USA, but there is little understanding of the classes of chemicals responsible for the mutagenicity of its emissions. OBJECTIVE: We determined some of the chemical classes responsible for the mutagenicity of the particulate matter (PM) of the emissions from petroleum diesel (B0) and biodiesel containing increasing concentrations of soy methyl esters (B20, B50, and B100). MATERIALS AND METHODS: We subjected organic extracts of the PM to bioassay-directed fractionation by sequential elution on silica gel with solvents of increasing polarity to produce four fractions per fuel. We injected these onto high performance liquid chromatography to produce 62 sub-fractions per fraction based on chemical polarity and evaluated all fractions and sub-fractions for mutagenicity in Salmonella. We correlated the results with the concentrations of 32 polycyclic aromatic hydrocarbons (PAHs) in the fractions. RESULTS: The mutagenicity-emission factors of the fractions generally decreased with increasing concentrations of soy in the fuel. Despite the different chemical compositions of the fuels, the extractable organics of all four emissions had similar features: ∼60% of the mass was nonpolar, non-mutagenic compounds; most of the PAHs were polar; and most of the mutagenicity was due to weakly polar and polar compounds. Some of the mutagenicity of B20 was due to highly polar compounds. CONCLUSIONS: The PM from soy biodiesel emissions was less mutagenic than that from petroleum diesel, and this reduction was associated with reduced concentrations of various weakly polar, polar, and highly polar mutagens, including PAHs, aromatic amines, nitroarenes, and oxy-PAHs.

Health effects of soy-biodiesel emissions: mutagenicity-emission factors.

CONTEXT: Soy biodiesel is the predominant biodiesel fuel used in the USA, but only a few, frequently conflicting studies have examined the potential health effects of its emissions. OBJECTIVE: We combusted petroleum diesel (B0) and fuels with increasing percentages of soy methyl esters (B20, B50 and B100) and determined the mutagenicity-emission factors expressed as revertants/megajoule of thermal energy consumed (rev/MJ(th)). MATERIALS AND METHODS: We combusted each fuel in replicate in a small (4.3-kW) diesel engine without emission controls at a constant load, extracted organics from the particles with dichloromethane, determined the percentage of extractable organic material (EOM), and evaluated these extracts for mutagenicity in 16 strains/S9 combinations of Salmonella. RESULTS: Mutagenic potencies of the EOM did not differ significantly between replicate experiments for B0 and B100 but did for B20 and B50. B0 had the highest rev/MJ(th), and those of B20 and B100 were 50% and ∼85% lower, respectively, in strains that detect mutagenicity due to polycyclic aromatic hydrocarbons (PAHs), nitroarenes, aromatic amines or oxidative mutagens. For all strains, the rev/MJ(th) decreased with increasing biodiesel in the fuel. The emission factor for the 16 EPA Priority PAHs correlated strongly (r(2 )= 0.69) with the mutagenicity-emission factor in strain TA100 + S9, which detects PAHs. CONCLUSIONS: Under a constant load, soy-biodiesel emissions were 50-85% less mutagenic than those of petroleum diesel. Without additional emission controls, petroleum and biodiesel fuels had mutagenicity-emission factors between those of large utility-scale combustors (e.g. natural gas, coal, or oil) and inefficient open-burning (e.g. residential wood fireplaces).

Characterization of Size-Fractionated Airborne Particles Inside an Electronic Waste Recycling Facility and Acute Toxicity Testing in Mice.

Disposal of electronic waste (e-waste) in landfills, incinerators, or at rudimentary recycling sites can lead to the release of toxic chemicals into the environment and increased health risks. Developing e-waste recycling technologies at commercial facilities can reduce the release of toxic chemicals and efficiently recover valuable materials. While these e-waste operations represent a vast improvement over previous approaches, little is known about environmental releases, workplace exposures, and potential health impacts. In this study, airborne particulate matter (PM) was measured at various locations within a modern U.S.-based e-waste recycling facility that utilized mechanical processing. In addition, composite size fractionated PM (coarse, fine and ultrafine) samples were collected, extracted, chemically analyzed, and given by oropharyngeal aspiration to mice or cultured with lung slices for lung toxicity tests. Indoor total PM concentrations measured during the study ranged from 220 to 1200 µg/m(3). In general, the coarse PM (2.5-10 µm) was 3-4 times more abundant than fine/ultrafine PM (<2.5 µm). The coarse PM contained higher levels of Ni, Pb, and Zn (up to 6.8 times) compared to the fine (0.1-2.5 µm) and ultrafine (<0.1 µm) PM. Compared to coarse PM measurements from a regional near-roadway study, Pb and Ni were enriched 170 and 20 times, respectively, in the indoor PM, with other significant enrichments (>10 times) observed for Zn and Sb, modest enrichments (>5 times) for Cu and Sr, and minor enrichments (>2 times) for Cr, Cd, Mn, Ca, Fe, and Ba. Negligible enrichment (<2 times) or depletion (<1 time) were observed for Al, Mg, Ti, Si, and V. The coarse PM fraction elicited significant pro-inflammatory responses in the mouse lung at 24 h postexposure compared to the fine and ultrafine PM, and similar toxicity outcomes were observed in the lung slice model. We conclude that exposure to coarse PM from the facility caused substantial inflammation in the mouse lung and enrichment of these metals compared to levels normally present in the ambient PM could be of potential health concern.

Inhaled diesel emissions generated with cerium oxide nanoparticle fuel additive induce adverse pulmonary and systemic effects.

Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe results in greater adverse pulmonary effects compared with DE. Male Sprague Dawley rats were exposed to filtered air, DE, or DECe for 5 h/day for 2 days. N-acetyl glucosaminidase activity was increased in bronchial alveolar lavage fluid (BALF) of rats exposed to DECe but not DE. There were also marginal but insignificant increases in several other lung injury biomarkers in both exposure groups (DECe > DE for all). To further characterize DECe toxicity, rats in a second study were exposed to filtered air or DECe for 5 h/day for 2 days or 4 weeks. Tissue analysis indicated a concentration- and time-dependent accumulation of lung and liver cerium followed by a delayed clearance. The gas-phase and high concentration of DECe increased lung inflammation at the 2-day time point, indicating that gas-phase components, in addition to particles, contribute to pulmonary toxicity. This effect was reduced at 4 weeks except for a sustained increase in BALF γ-glutamyl transferase activity. Histopathology and transmission electron microscopy revealed increased alveolar septa thickness due to edema and increased numbers of pigmented macrophages after DECe exposure. Collectively, these findings indicate that DECe induces more adverse pulmonary effects on a mass basis than DE. In addition, lung accumulation of cerium, systemic translocation to the liver, and delayed clearance are added concerns to existing health effects of DECe.

Bioassay-directed fractionation and sub-fractionation for mutagenicity and chemical analysis of diesel exhaust particles.

Several types of diesel exhaust particles (DEPs) have been used for toxicology studies, including a high-organic automobile DEP (A-DEP) from Japan, and a low-organic forklift DEP developed by the National Institute of Standards and Technology (N-DEP). However, these DEPs were not characterized extensively for chemical composition or sub-fractionated and tested extensively for mutagenicity. We collected a compressor-generated DEP (C-DEP) and characterized it by conducting bioassay-directed fractionation of the extractable organics in Salmonella and correlating the results by hierarchical clustering with the concentrations of 32 polycyclic aromatic hydrocarbons (PAHs). Relative to A- and N-DEP, the mutagenic potency of C-DEP was intermediate in TA100 +S9 (PAH mutagenicity) but was lowest in TA98 -S9 (nitroarene mutagenicity). More than 50% of the mass of the extractable organics of C-DEP eluted in the nonpolar Fraction 1, and only ∼20% eluted in the moderately polar Fractions 2 and 3. However, most of the mutagenicity eluted in Fractions 2 and 3, similar to A-DEP but different from N-DEP. HPLC-derived mutagrams of 62 sub-fractions per fraction confirmed that most of the mutagenicity was due to moderately polar compounds. The diagnostic strains identified a strong role for PAHs, nitroarenes, aromatic amines, and oxy-PAHs in the mutagenicity of C-DEP. Hierarchical clustering confirmed the importance of oxy-PAHs but not that of nitroarenes. To our knowledge this is the first use of hierarchical clustering to correlate chemical composition with the mutagenicity of a complex mixture. The chemical analysis and mutagenicity of C-DEP described here makes C-DEP suitable for additional toxicological studies.

Biokinetically-based in vitro cardiotoxicity of residual oil fly ash: hazard identification and mechanisms of injury.

Epidemiological studies have associated air pollution particulate matter (PM) exposure with adverse cardiovascular effects. Identification of causal PM sources is critically needed to support regulatory decisions to protect public health. This research examines the in vitro cardiotoxicity of bioavailable constituents of residual oil fly ash (ROFA) employing in vivo, biokinetically-based, concentrations determined from their pulmonary deposition. Pulmonary deposition of ROFA led to a rapid increase in plasma vanadium (V) levels that were prolonged in hypertensive animals without systemic inflammation. ROFA cardiotoxicity was evaluated using neonatal rat cardiomyocyte (RCM) cultures exposed to particle-free leachates of ROFA (ROFA-L) at levels present in exposed rat plasma. Cardiotoxicity was observed at low levels (3.13 µg/mL) of ROFA-L 24 h post-exposure. Dimethylthiourea (28 mM) inhibited ROFA-L-induced cytotoxicity at high (25-12.5 µg/mL) doses, suggesting that oxidative stress is responsible at high ROFA-L doses. Cardiotoxicity could not be reproduced using a V + Ni + Fe mixture or a ROFA-L depleted of these metals, suggesting that ROFA-L cardiotoxicity requires the full complement of bioavailable constituents. Susceptibility of RCMs to ROFA-L-induced cytotoxicity was increased following tyrosine phosphorylation inhibition, suggesting that phosphotyrosine signaling pathways play a critical role in regulating ROFA-L-induced cardiotoxicity. These data demonstrate that bioavailable constituents of ROFA are capable of direct adverse cardiac effects.

Role of oxidative stress on diesel-enhanced influenza infection in mice.

Numerous studies have shown that air pollutants, including diesel exhaust (DE), reduce host defenses, resulting in decreased resistance to respiratory infections. This study sought to determine if DE exposure could affect the severity of an ongoing influenza infection in mice, and examine if this could be modulated with antioxidants. BALB/c mice were treated by oropharyngeal aspiration with 50 plaque forming units of influenza A/HongKong/8/68 and immediately exposed to air or 0.5 mg/m3 DE (4 hrs/day, 14 days). Mice were necropsied on days 1, 4, 8 and 14 post-infection and lungs were assessed for virus titers, lung inflammation, immune cytokine expression and pulmonary responsiveness (PR) to inhaled methacholine. Exposure to DE during the course of infection caused an increase in viral titers at days 4 and 8 post-infection, which was associated with increased neutrophils and protein in the BAL, and an early increase in PR. Increased virus load was not caused by decreased interferon levels, since IFN-ß levels were enhanced in these mice. Expression and production of IL-4 was significantly increased on day 1 and 4 p.i. while expression of the Th1 cytokines, IFN-γ and IL-12p40 was decreased. Treatment with the antioxidant N-acetylcysteine did not affect diesel-enhanced virus titers but blocked the DE-induced changes in cytokine profiles and lung inflammation. We conclude that exposure to DE during an influenza infection polarizes the local immune responses to an IL-4 dominated profile in association with increased viral disease, and some aspects of this effect can be reversed with antioxidants.

Effects of prenatal diesel exhaust inhalation on pulmonary inflammation and development of specific immune responses.

There is increasing evidence that exposure to air pollutants during pregnancy can result in a number of deleterious effects including low birth weight and the incidence of allergic asthma. To investigate the in utero effects of DE exposure, timed pregnant BALB/c mice were exposed to 0, 0.8 or 3.1 mg/m(3) of DE during gestation days (GD) 9 to GD 18. The number of successful pregnancies was 15/20 in the air controls and 10/20 in each of the diesel exposures. Immune function in the 6-week-old offspring as determined by development of delayed type hypersensitivity (DTH) reactions to bovine serum albumin (BSA), antibody titers to injected sheep red blood cells (SRBC), splenic T cells expressing CD45(+)CD3(+)CD8(+) and CD3(+)CD25(+), and mRNA expression of TNF-alpha, TLR2, SP-A, TGF-beta and Foxp3 in the lung were not affected by prenatal DE exposure. On the other hand, lung TLR4 mRNA expression, the number of neutrophils in the bronchoalveolar lavage fluid (BALF) and splenic T cells expressing CD45(+)CD3(+)CD4(+) and CD4(+)CD25(+) were differentially affected depending on the DE concentration and gender. When additional groups of mice were sensitized and challenged via the respiratory tract with ovalbumin to induce allergic airway inflammation, female mice had higher protein levels in the BALF compared to males and this was reduced by prenatal exposure to either concentration of DE. No other changes in allergen-induced immunity, lung function or severity of inflammation were noted. Collectively, the results show that in utero exposure to DE altered some baseline inflammatory indices in the lung in a gender-specific manner, but had no effect on development of specific immune responses to experimental antigens, or the severity of allergic lung inflammation.

Electrophilic and redox properties of diesel exhaust particles.

The adverse health effects of air pollutants have been associated with their redox and electrophilic properties. Although the specific chemical species involved in these effects are not known, the characterization of their general physical and chemical properties is important to our understanding of the mechanisms by which they cause health problems. This manuscript describes results of a study examining the partition properties of these activities in aqueous and organic media. The water and dichloromethane (DCM) solubility of redox active and electrophilic constituents of seven diesel exhaust particle (DEP) samples were determined with assays developed earlier in this laboratory. The constituents exhibiting redox activity, which included both metals and nonmetal species, were associated with the particles in the aqueous suspensions. Portions of the redox active compounds were also DCM-soluble. In contrast, the electrophilic constituents included both water-soluble and DCM-soluble species. The role of quinones or quinone-like compounds in redox and electrophilic activities of the DCM-soluble constituents was assessed by reductive acetylation, a procedure that inactivates quinones. The results from this experiment indicated that most of the activities in the organic extract were associated with quinone-like substances. The partition properties of the reactive species are important in exposure assessment since the toxicokinetics of particles and solutes are quite distinct.