Incident dementia and long-term exposure to constituents of fine particle air pollution: A national cohort study in the United States.

Growing evidence suggests that fine particulate matter (PM2.5) likely increases the risks of dementia, yet little is known about the relative contributions of different constituents. Here, we conducted a nationwide population-based cohort study (2000 to 2017) by integrating the Medicare Chronic Conditions Warehouse database and two independently sourced datasets of high-resolution PM2.5 major chemical composition, including black carbon (BC), organic matter (OM), nitrate (NO3-), sulfate (SO42-), ammonium (NH4+), and soil dust (DUST). To investigate the impact of long-term exposure to PM2.5 constituents on incident all-cause dementia and Alzheimer's disease (AD), hazard ratios for dementia and AD were estimated using Cox proportional hazards models, and penalized splines were used to evaluate potential nonlinear concentration-response (C-R) relationships. Results using two exposure datasets consistently indicated higher rates of incident dementia and AD for an increased exposure to PM2.5 and its major constituents. An interquartile range increase in PM2.5 mass was associated with a 6 to 7% increase in dementia incidence and a 9% increase in AD incidence. For different PM2.5 constituents, associations remained significant for BC, OM, SO42-, and NH4+ for both end points (even after adjustments of other constituents), among which BC and SO42- showed the strongest associations. All constituents had largely linear C-R relationships in the low exposure range, but most tailed off at higher exposure concentrations. Our findings suggest that long-term exposure to PM2.5 is significantly associated with higher rates of incident dementia and AD and that SO42-, BC, and OM related to traffic and fossil fuel combustion might drive the observed associations.

Oxidized and Unsaturated: Key Organic Aerosol Traits Associated with Cellular Reactive Oxygen Species Production in the Southeastern United States.

Exposure to ambient fine particulate matter (PM2.5) is associated with millions of premature deaths annually. Oxidative stress through overproduction of reactive oxygen species (ROS) is a possible mechanism for PM2.5-induced health effects. Organic aerosol (OA) is a dominant component of PM2.5 worldwide, yet its role in PM2.5 toxicity is poorly understood due to its chemical complexity. Here, through integrated cellular ROS measurements and detailed multi-instrument chemical characterization of PM in urban southeastern United States, we show that oxygenated OA (OOA), especially more-oxidized OOA, is the main OA type associated with cellular ROS production. We further reveal that highly unsaturated species containing carbon-oxygen double bonds and aromatic rings in OOA are major contributors to cellular ROS production. These results highlight the key chemical features of ambient OA driving its toxicity. As more-oxidized OOA is ubiquitous and abundant in the atmosphere, this emphasizes the need to understand its sources and chemical processing when formulating effective strategies to mitigate PM2.5 health impacts.

The Oxidative Potential of Fine Particulate Matter and Biological Perturbations in Human Plasma and Saliva Metabolome.

Particulate oxidative potential may comprise a key health-relevant parameter of particulate matter (PM) toxicity. To identify biological perturbations associated with particulate oxidative potential and examine the underlying molecular mechanisms, we recruited 54 participants from two dormitories near and far from a congested highway in Atlanta, GA. Fine particulate matter oxidative potential ("FPMOP") levels at the dormitories were measured using dithiothreitol assay. Plasma and saliva samples were collected from participants four times for longitudinal high-resolution metabolic profiling. We conducted metabolome-wide association studies to identify metabolic signals with FPMOP. Leukotriene metabolism and galactose metabolism were top pathways associated with ≥5 FPMOP-related indicators in plasma, while vitamin E metabolism and leukotriene metabolism were found associated with most FPMOP indicators in saliva. We observed different patterns of perturbed pathways significantly associated with water-soluble and -insoluble FPMOPs, respectively. We confirmed five metabolites directly associated with FPMOP, including hypoxanthine, histidine, pyruvate, lactate/glyceraldehyde, and azelaic acid, which were implications of perturbations in acute inflammation, nucleic acid damage and repair, and energy perturbation. The unique metabolic signals were specific to FPMOP, but not PM mass, providing initial indication that FPMOP might constitute a more sensitive, health-relevant measure for elucidating etiologies related to PM2.5 exposures.

Source and Chemistry of Hydroxymethanesulfonate (HMS) in Fairbanks, Alaska.

Fairbanks, Alaska, is a subarctic city with fine particle (PM2.5) concentrations that exceed air quality regulations in winter due to weak dispersion caused by strong atmospheric inversions, local emissions, and the unique chemistry occurring under the cold and dark conditions. Here, we report on observations from the winters of 2020 and 2021, motivated by our pilot study that showed exceptionally high concentrations of fine particle hydroxymethanesulfonate (HMS) or related sulfur(IV) species (e.g., sulfite and bisulfite). We deployed online particle-into-liquid sampler-ion chromatography (PILS-IC) in conjunction with a suite of instruments to determine HMS precursors (HCHO, SO2) and aerosol composition in general, with the goal to characterize the sources and sinks of HMS in wintertime Fairbanks. PM2.5 HMS comprised a significant fraction of PM2.5 sulfur (26-41%) and overall PM2.5 mass concentration of 2.8-6.8% during pollution episodes, substantially higher than what has been observed in other regions, likely due to the exceptionally low temperatures. HMS peaked in January, with lower concentrations in December and February, resulting from changes in precursors and meteorological conditions. Strong correlations with inorganic sulfate and organic mass during pollution events suggest that HMS is linked to processes responsible for poor air quality episodes. These findings demonstrate unique aspects of air pollution formation in cold and humid atmospheres.

Low-Molecular-Weight Carboxylic Acids in the Southeastern U.S.: Formation, Partitioning, and Implications for Organic Aerosol Aging.

While carboxylic acids are important components in both particle and gas phases in the atmosphere, their sources and partitioning are not fully understood. In this study, we present real-time measurements of both particle- and gas-phase concentrations for five of the most common and abundant low-molecular-weight carboxylic acids (LMWCA) in a rural region in the southeastern U.S. in Fall 2016. Through comparison with secondary organic aerosol (SOA) tracers, we find that isoprene was the most important local precursor for all five LMWCA but via different pathways. We propose that monocarboxylic acids (formic and acetic acids) were mainly formed through gas-phase photochemical reactions, while dicarboxylic acids (oxalic, malonic, and succinic acids) were predominantly from aqueous processing. Unexpectedly high concentrations of particle-phase formic and acetic acids (in the form of formate and acetate, respectively) were observed and likely the components of long-range transport organic aerosol (OA), decoupled from their gas-phase counterparts. In addition, an extraordinarily strong correlation (R2 = 0.90) was observed between a particulate LMWCA and aged SOA, which we tentatively attribute to boundary layer dynamics.

Chemical feedbacks weaken the wintertime response of particulate sulfate and nitrate to emissions reductions over the eastern United States.

Sulfate ([Formula: see text]) and nitrate ([Formula: see text]) account for half of the fine particulate matter mass over the eastern United States. Their wintertime concentrations have changed little in the past decade despite considerable precursor emissions reductions. The reasons for this have remained unclear because detailed observations to constrain the wintertime gas-particle chemical system have been lacking. We use extensive airborne observations over the eastern United States from the 2015 Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) campaign; ground-based observations; and the GEOS-Chem chemical transport model to determine the controls on winter [Formula: see text] and [Formula: see text] GEOS-Chem reproduces observed [Formula: see text]-[Formula: see text]-[Formula: see text] particulate concentrations (2.45 µg [Formula: see text]) and composition ([Formula: see text]: 47%; [Formula: see text]: 32%; [Formula: see text]: 21%) during WINTER. Only 18% of [Formula: see text] emissions were regionally oxidized to [Formula: see text] during WINTER, limited by low [H2O2] and [OH]. Relatively acidic fine particulates (pH∼1.3) allow 45% of nitrate to partition to the particle phase. Using GEOS-Chem, we examine the impact of the 58% decrease in winter [Formula: see text] emissions from 2007 to 2015 and find that the H2O2 limitation on [Formula: see text] oxidation weakened, which increased the fraction of [Formula: see text] emissions oxidizing to [Formula: see text] Simultaneously, NOx emissions decreased by 35%, but the modeled [Formula: see text] particle fraction increased as fine particle acidity decreased. These feedbacks resulted in a 40% decrease of modeled [[Formula: see text]] and no change in [[Formula: see text]], as observed. Wintertime [[Formula: see text]] and [[Formula: see text]] are expected to change slowly between 2015 and 2023, unless [Formula: see text] and NOx emissions decrease faster in the future than in the recent past.

Monoterpenes are the largest source of summertime organic aerosol in the southeastern United States.

The chemical complexity of atmospheric organic aerosol (OA) has caused substantial uncertainties in understanding its origins and environmental impacts. Here, we provide constraints on OA origins through compositional characterization with molecular-level details. Our results suggest that secondary OA (SOA) from monoterpene oxidation accounts for approximately half of summertime fine OA in Centreville, AL, a forested area in the southeastern United States influenced by anthropogenic pollution. We find that different chemical processes involving nitrogen oxides, during days and nights, play a central role in determining the mass of monoterpene SOA produced. These findings elucidate the strong anthropogenic-biogenic interaction affecting ambient aerosol in the southeastern United States and point out the importance of reducing anthropogenic emissions, especially under a changing climate, where biogenic emissions will likely keep increasing.

Fine Particle Iron in Soils and Road Dust Is Modulated by Coal-Fired Power Plant Sulfur.

Transition metal ions, such as water-soluble iron (WS-Fe), are toxic components of fine particles (PM2.5). In Atlanta, from 1998 to 2013, a previous study found that WS-Fe was the PM2.5 species most associated with adverse cardiovascular outcomes. We examined this data set to investigate the sources of WS-Fe and the effects of air quality regulations on ambient levels of WS-Fe. We find that insoluble forms of iron in mineral and road dust combined with sulfate from coal-fired electrical generating units were converted into soluble forms by sulfate-driven acid dissolution. Sulfate produced both the highly acidic aerosol (summer pH 1.5-2) and liquid water required for the aqueous phase acid dissolution, but variability in WS-Fe was mainly driven by particle liquid water. These processes were more pronounced in summer when particles were most acidic, whereas in winter the relative importance of WS-Fe from combustion emissions increased. Although WS-Fe constituted a minute fraction of PM2.5 mass (0.15%), the WS-Fe-PM2.5 mass correlation was high (r = 0.67) and may be explained by these formation routes, which, in part, could account for observed associations between PM2.5 mass and adverse health seen in past studies. Similar processes are expected in many regions, implying that these unexpected benefits from coal-burning reduction may be widespread.

Global Measurements of Brown Carbon and Estimated Direct Radiative Effects.

Brown carbon (BrC) is an organic aerosol material that preferentially absorbs light of shorter wavelengths. Global-scale radiative impacts of BrC have been difficult to assess due to the lack of BrC observational data. To address this, aerosol filters were continuously collected with near pole-to-pole latitudinal coverage over the Pacific and Atlantic basins in three seasons as part of the Atmospheric Tomography Mission. BrC chromophores in filter extracts were measured. We find that globally, BrC was highly spatially heterogeneous, mostly detected in air masses that had been transported from regions of extensive biomass burning. We calculate the average direct radiative effect due to BrC absorption accounted for approximately 7% to 48% of the top of the atmosphere clear-sky instantaneous forcing by all absorbing carbonaceous aerosols in the remote atmosphere, indicating that BrC from biomass burning is an important component of the global radiative balance.

Oxidative Potential of Particulate Matter and Generation of Reactive Oxygen Species in Epithelial Lining Fluid.

Reactive oxygen species (ROS) play a central role in adverse health effects of atmospheric particulate matter (PM). Respiratory deposition can lead to the formation of ROS in the epithelial lining fluid due to redox reactions of PM components with lung antioxidants. As direct quantification of ROS is challenging, PM oxidative potential is more commonly measured using antioxidant surrogates including dithiothreitol and ascorbic acid, assuming that the decay of surrogates corresponds to ROS formation. However, this assumption has not yet been validated and the lack of ROS quantification in the respiratory tract causes major limitations in evaluating PM impacts on oxidative stress. By combining field measurements of size-segregated chemical composition, a human respiratory tract model, and kinetic modeling, we quantified production rates and concentrations of different types of ROS in different regions of the epithelial lining fluid by considering particle-size-dependent respiratory deposition. The extrathoracic region is found to have higher ROS concentrations compared to the bronchial and alveolar regions. Although H2O2 and O2- production is governed by Fe and Cu ions, OH radicals are mainly generated by organic compounds and Fenton-like reactions of metal ions. In winter when affected by biomass burning, model comparisons suggest that humic-like substances (HULIS) contribute to ROS formation substantially. We found that PM oxidative potential is a good indicator of the chemical production of H2O2 and O2- but does not represent OH generation. These results provide rationale and limitations of the use of oxidative potential as an indicator of PM toxicity in epidemiological and toxicological studies.

Effects of Atmospheric Processing on the Oxidative Potential of Biomass Burning Organic Aerosols.

Oxidative potential (OP), which is the ability of certain components in atmospheric particles to generate reactive oxidative species (ROS) and deplete antioxidants in vivo, is a prevailing toxicological mechanism underlying the adverse health effects associated with exposure to ambient aerosols. While previous studies have identified the high OP of fresh biomass burning organic aerosols (BBOA), it remains unclear how it evolves throughout atmospheric transport. Using the dithiothreitol (DTT) assay as a measure of OP, a combination of field observations and laboratory experiments is used to determine how atmospheric aging transforms the intrinsic OP (OPmassDTT) of BBOA. For ambient BBOA collected during the fire seasons in Greece, OPmassDTT was observed to increase by a factor of 2.1 ± 0.9 for samples of atmospheric ages up to 68 h. Laboratory experiments indicate that aqueous photochemical aging (aging by UVB and UVA photolysis; as well as OH oxidation), as well as aging by ozone and atmospheric dilution can transform the OPmassDTT of the water-soluble fraction of wood smoke within 2 days of atmospheric transport. The results from this work suggest that the air quality impacts of biomass burning emissions can extend beyond regions near fire sites and should be accounted for.

Review of Acellular Assays of Ambient Particulate Matter Oxidative Potential: Methods and Relationships with Composition, Sources, and Health Effects.

Oxidative stress is a potential mechanism of action for particulate matter (PM) toxicity and can occur when the body's antioxidant capacity cannot counteract or detoxify harmful effects of reactive oxygen species (ROS) due to an excess presence of ROS. ROS are introduced to the body via inhalation of PM with these species present on and/or within the particles (particle-bound ROS) and/or through catalytic generation of ROS in vivo after inhaling redox-active PM species (oxidative potential, OP). The recent development of acellular OP measurement techniques has led to a surge in research across the globe. In this review, particle-bound ROS techniques are discussed briefly while OP measurements are the focus due to an increasing number of epidemiologic studies using OP measurements showing associations with adverse health effects in some studies. The most common OP measurement techniques, including the dithiothreitol assay, glutathione assay, and ascorbic acid assay, are discussed along with evidence for utility of OP measurements in epidemiologic studies and PM characteristics that drive different responses between assay types (such as species composition, emission source, and photochemistry). Overall, most OP assays respond to metals like copper than can be found in emission sources like vehicles. Some OP assays respond to organics, especially photochemically aged organics, from sources like biomass burning. Select OP measurements have significant associations with certain cardiorespiratory end points, such as asthma, congestive heart disease, and lung cancer. In fact, multiple studies have found that exposure to OP measured using the dithiothreitol and glutathione assays drives higher risk ratios for certain cardiorespiratory outcomes than PM mass, suggesting OP measurements may be integrating the health-relevant fraction of PM and will be useful tools for future health analyses. The compositional impacts, including species and emission sources, on OP could have serious implications for health-relevant PM exposure. Though more work is needed, OP assays show promise for health studies as they integrate the impacts of PM species and properties on catalytic redox reactions into one measurement, and current work highlights the importance of metals, organic carbon, vehicles, and biomass burning emissions to PM exposures that could impact health.

Chemical Composition and Toxicity of Particles Emitted from a Consumer-Level 3D Printer Using Various Materials.

Consumer-level 3D printers emit ultrafine and fine particles, though little is known about their chemical composition or potential toxicity. We report chemical characteristics of the particles in comparison to raw filaments and assessments of particle toxicity. Particles emitted from polylactic acid (PLA) appeared to be largely composed of the bulk filament material with mass spectra similar to the PLA monomer spectra. Acrylonitrile butadiene styrene (ABS), extruded at a higher temperature than PLA, emitted vastly more particles and their composition differed from that of the bulk filament, suggesting that trace additives may control particle formation. In vitro cellular assays and in vivo mice exposure all showed toxic responses when exposed to PLA and ABS-emitted particles, where PLA-emitted particles elicited higher response levels than ABS-emitted particles at comparable mass doses. A chemical assay widely used in ambient air-quality studies showed that particles from various filament materials had comparable particle oxidative potentials, slightly lower than those of ambient particulate matter (PM2.5). However, particle emissions from ABS filaments are likely more detrimental when considering overall exposure due to much higher emissions. Our results suggest that 3D printer particle emissions are not benign and exposures should be minimized.

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets.

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

Linked Response of Aerosol Acidity and Ammonia to SO2 and NO x Emissions Reductions in the United States.

Large reductions of sulfur and nitrogen oxide emissions in the United States have led to considerable improvements in air quality, though recent analyses in the Southeastern United States have shown little response of aerosol pH to these reductions. This study examines the effects of reduced emissions on the trend of aerosol acidity in fine particulate matter (PM2.5), at a nationwide scale, using ambient concentration data from three monitoring networks-the Ammonia Monitoring Network (AMoN), the Clean Air Status and Trends network (CASTNET) and the Southeastern Aerosol Research and Characterization Network (SEARCH), in conjunction with thermodynamic (ISORROPIA-II) and chemical transport (CMAQ) model results. Sulfate and ammonium experienced similar and significant decreases with little change in pH, neutralization ratio ( f = [NH4+]/2[SO42-] + [NO3-]), or nitrate. Oak Grove, MS was the only SEARCH site showing statistically significant pH changes in the Southeast region where small increases in pH (0.003-0.09 pH units/year) were observed. Of the five regions characterized using CASTNET/AMoN data, only California exhibited a statistically significant, albeit small pH increase of +0.04 pH units/year. Furthermore, statistically insignificant (α = 0.05) changes in ammonia were observed in response to emission and PM2.5 speciation changes. CMAQ simulation results had similar responses, showing steady ammonia levels and generally low pH, with little change from 2001 to 2011.

Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States.

Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43-70% of total measured organic aerosol (29-49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic-biogenic interactions and consequently improve air quality and climate simulations.

Changes in Light Absorptivity of Molecular Weight Separated Brown Carbon Due to Photolytic Aging.

Brown carbon (BrC) consists of those organic compounds in atmospheric aerosols that absorb solar radiation and may play an important role in planetary radiative forcing and climate. However, little is known about the production and loss mechanisms of BrC in the atmosphere. Here, we study how the light absorptivity of BrC from wood smoke and secondary BrC generated from the reaction of ammonium sulfate with methylglyoxal changes under photolytic aging by UVA radiation in the aqueous phase. Owing to its chemical complexity, BrC is separated by molecular weight using size exclusion chromatography, and the response of each molecular weight fraction to aging is studied. Photolytic aging induced significant changes in the light absorptivity of BrC for all molecular weight fractions; secondary BrC was rapidly photoblenched, whereas for wood smoke BrC, both photoenhancement and photobleaching were observed. Initially, large biomass burning BrC molecules were rapidly photoenhanced, followed by slow photolysis. As a result, large BrC molecules dominated the total light absorption of aged biomass burning BrC. These experimental results further support earlier observations that large molecular weight BrC compounds from biomass burning can be relatively long-lived components in atmospheric aerosols, thus more likely to have larger impacts on aerosol radiative forcing and could serve as biomass burning tracers.

Chemical Characterization of Water-Soluble Organic Aerosol in Contrasting Rural and Urban Environments in the Southeastern United States.

We developed a novel system for direct and online characterization of water-solubility of organic aerosol (OA) by coupling a Particle Into Liquid Sampler (PILS) to a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). We showed that approximately 88% and 77% of OA are water-soluble in rural Centreville, Alabama and urban Atlanta, Georgia, respectively. The water-solubility of OA factors, resolved with Positive Matrix Factorization analysis of AMS data, is directly investigated for the first time. Above 80% of isoprene-derived OA is water-soluble and its water-soluble fraction has the least variability among all OA factors. This is consistent with that the majority of this factor represents OA formed through the aqueous-phase reaction of isoprene epoxydiols. More-oxidized oxygenated OA is dominantly water-soluble, consistent with this factor representing highly oxidized compounds. Less-oxidized oxygenated OA has the lowest water-solubility among all secondary OA factors, which agrees with the hypothesis that this factor in the southeastern U.S. includes contributions from organic nitrates. While hydrocarbon-like OA is largely water-insoluble, biomass burning OA and cooking OA have the largest range of water-soluble fraction. This study on the water-solubility of OA factors provides insights for interpretation of OA factors and improves understanding of the complex OA sources in the atmosphere.

Highly Acidic Ambient Particles, Soluble Metals, and Oxidative Potential: A Link between Sulfate and Aerosol Toxicity.

Soluble transition metals in particulate matter (PM) can generate reactive oxygen species in vivo by redox cycling, leading to oxidative stress and adverse health effects. Most metals, such as those from roadway traffic, are emitted in an insoluble form, but must be soluble for redox cycling. Here we present the mechanism of metals dissolution by highly acidic sulfate aerosol and the effect on particle oxidative potential (OP) through analysis of size distributions. Size-segregated ambient PM were collected from a road-side and representative urban site in Atlanta, GA. Elemental and organic carbon, ions, total and water-soluble metals, and water-soluble OP were measured. Particle pH was determined with a thermodynamic model using measured ionic species. Sulfate was spatially uniform and found mainly in the fine mode, whereas total metals and mineral dust cations were highest at the road-side site and in the coarse mode, resulting in a fine mode pH < 2 and near neutral coarse mode. Soluble metals and OP peaked at the intersection of these modes demonstrating that sulfate plays a key role in producing highly acidic fine aerosols capable of dissolving primary transition metals that contribute to aerosol OP. Sulfate-driven metals dissolution may account for sulfate-health associations reported in past studies.

Ambient Size Distributions and Lung Deposition of Aerosol Dithiothreitol-Measured Oxidative Potential: Contrast between Soluble and Insoluble Particles.

Ambient particulate matter may upset redox homeostasis, leading to oxidative stress and adverse health effects. Size distributions of water-insoluble and water-soluble OPDTT (dithiothreitol assay, measure of oxidative potential per air volume) are reported for a roadside site and an urban site. The average water-insoluble fractions were 23% and 51%, and 37% and 39%, for fine and coarse modes at the roadside and urban sites, respectively, measured during different periods. Water-soluble OPDTT was unimodal, peaked near 1-2.5 µm due to contributions from fine-mode organic components plus coarse-mode transition metal ions. In contrast, water-insoluble OPDTT was bimodal, with both fine and coarse modes. The main chemical components that drive both fractions appear to be the same, except that for water-insoluble OPDTT the compounds were absorbed on surfaces of soot and non-tailpipe traffic dust. They were largely externally mixed and deposited in different regions in the respiratory system, transition metal ions predominately in the upper regions and organic species, such as quinones, deeper in the lung. Although OPDTT per mass (toxicity) was highest for ultrafine particles, estimated lung deposition was mainly from accumulation and coarse particles. Contrasts in the phases of these forms of OPDTT deposited in the respiratory system may have differing health impacts.