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.

Abstract. Particle water and pH are predicted using meteorological observations (relative humidity (RH), temperature (T)), gas/particle composition, and thermodynamic modeling (ISORROPIA-II). A comprehensive uncertainty analysis is included, and the model is validated. We investigate mass concentrations of particle water and related particle pH for ambient fine-mode aerosols sampled in a relatively remote Alabama forest during the Southern Oxidant and Aerosol Study (SOAS) in summer and at various sites in the southeastern US during different seasons, as part of the Southeastern Center for Air Pollution and Epidemiology (SCAPE) study. Particle water and pH are closely linked; pH is a measure of the particle H+ aqueous concentration and depends on both the presence of ions and amount of particle liquid water. Levels of particle water, in turn, are determined through water uptake by both the ionic species and organic compounds. Thermodynamic calculations based on measured ion concentrations can predict both pH and liquid water but may be biased since contributions of organic species to liquid water are not considered. In this study, contributions of both the inorganic and organic fractions to aerosol liquid water were considered, and predictions were in good agreement with measured liquid water based on differences in ambient and dry light scattering coefficients (prediction vs. measurement: slope = 0.91, intercept = 0.5 μg m−3, R2 = 0.75). ISORROPIA-II predictions were confirmed by good agreement between predicted and measured ammonia concentrations (slope = 1.07, intercept = −0.12 μg m−3, R2 = 0.76). Based on this study, organic species on average contributed 35% to the total water, with a substantially higher contribution (50%) at night. However, not including contributions of organic water had a minor effect on pH (changes pH by 0.15 to 0.23 units), suggesting that predicted pH without consideration of organic water could be sufficient for the purposes of aqueous secondary organic aerosol (SOA) chemistry. The mean pH predicted in the Alabama forest (SOAS) was 0.94 ± 0.59 (median 0.93). pH diurnal trends followed liquid water and were driven mainly by variability in RH; during SOAS nighttime pH was near 1.5, while daytime pH was near 0.5. pH ranged from 0.5 to 2 in summer and 1 to 3 in the winter at other sites. The systematically low pH levels in the southeast may have important ramifications, such as significantly influencing acid-catalyzed reactions, gas–aerosol partitioning, and mobilization of redox metals and minerals. Particle ion balances or molar ratios, often used to infer pH, do not consider the dissociation state of individual ions or particle liquid water levels and do not correlate with particle pH.

Abstract. We deployed a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) to characterize the chemical composition of submicron non-refractory particulate matter (NR-PM$_{1}$) in the southeastern USA. Measurements were performed in both rural and urban sites in the greater Atlanta area, Georgia (GA), and Centreville, Alabama (AL), for approximately 1 year as part of Southeastern Center for Air Pollution and Epidemiology study (SCAPE) and Southern Oxidant and Aerosol Study (SOAS). Organic aerosol (OA) accounts for more than half of NR-PM1 mass concentration regardless of sampling sites and seasons. Positive matrix factorization (PMF) analysis of HR-ToF-AMS measurements identified various OA sources, depending on location and season. Hydrocarbon-like OA (HOA) and cooking OA (COA) have important, but not dominant, contributions to total OA in urban sites (i.e., 21–38 % of total OA depending on site and season). Biomass burning OA (BBOA) concentration shows a distinct seasonal variation with a larger enhancement in winter than summer. We find a good correlation between BBOA and brown carbon, indicating biomass burning is an important source for brown carbon, although an additional, unidentified brown carbon source is likely present at the rural Yorkville site. Isoprene-derived OA factor (isoprene-OA) is only deconvolved in warmer months and contributes 18–36 % of total OA. The presence of isoprene-OA factor in urban sites is more likely from local production in the presence of NOx than transport from rural sites. More-oxidized and less-oxidized oxygenated organic aerosol (MO-OOA and LO-OOA, respectively) are dominant fractions (47–79 %) of OA in all sites. MO-OOA correlates well with ozone in summer but not in winter, indicating MO-OOA sources may vary with seasons. LO-OOA, which reaches a daily maximum at night, correlates better with estimated nitrate functionality from organic nitrates than total nitrates. Based on the HR-ToF-AMS measurements, we estimate that the nitrate functionality from organic nitrates contributes 63–100 % to the total measured nitrates in summer. Furthermore, the contribution of organic nitrates to total OA is estimated to be 5–12 % in summer, suggesting that organic nitrates are important components in the ambient aerosol in the southeastern USA. The spatial distribution of OA is investigated by comparing simultaneous HR-ToF-AMS measurements with ACSM measurements at two different sampling sites. OA is found to be spatially homogeneous in summer due possibly to stagnant air mass and a dominant amount of regional secondary organic aerosol (SOA) in the southeastern USA. The homogeneity is less in winter, which is likely due to spatial variation of primary emissions. We observe that the seasonality of OA concentration shows a clear urban/rural contrast. While OA exhibits weak seasonal variation in the urban sites, its concentration is higher in summer than winter for rural sites. This observation from our year-long measurements is consistent with 14 years of organic carbon (OC) data from the SouthEastern Aerosol Research and Characterization (SEARCH) network. The comparison between short-term measurements with advanced instruments and long-term measurements of basic air quality indicators not only tests the robustness of the short-term measurements but also provides insights in interpreting long-term measurements. We find that OA factors resolved from PMF analysis on HR-ToF-AMS measurements have distinctly different diurnal variations. The compensation of OA factors with different diurnal trends is one possible reason for the repeatedly observed, relatively flat OA diurnal profile in the southeastern USA. In addition, analysis of long-term measurements shows that the correlation between OC and sulfate is substantially stronger in summer than winter. This seasonality could be partly due to the effects of sulfate on isoprene SOA formation as revealed by the short-term intensive measurements.

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 gasparticle 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. O rganic nitrates (ONs; ON = RONO 2 + RO 2 NO 2 ) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NO x = NO + NO 2 ). ONs formed from isoprene oxidation alone are responsible for the export of 8-30% of anthropogenic NO x out of the US continental boundary layer (1, 2). Regional NO x budgets and tropospheric ozone (O 3 ) production are, therefore, particularly sensitive to uncertainties in the yields and fates of ON (3-6). The yields implemented in modeling studies are determined from laboratory experiments, in which only a few of the first generation gaseous ONs or the total gas-phase ONs and particle-phase organic nitrates (pONs) have been quantified, whereas production of highly functionalized ONs capable of strongly partitioning to the particle phase have been inferred (7-11) or directly measured in the gas phase (12). Addition of a nitrate (-ONO 2 ) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5-3 orders of magnitude (13). Thus, ON formation can enhance particle-phase partitioning of semivolatile species in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) growth (8). However, highly time-resolved measurements of speciated ON in the particle phase have been lacking.We use a recently developed high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) using iodide-adduct ionization (14) with a filter inlet for gases and aerosols (FIGAERO) (15) that allows alternating in situ measurements of the molecular SignificanceWe present online field observations of the speciated molecular composition of organic nitrates in ambient atmospheric particles utilizing recently developed high-resolution MS-based instrumentation. We find that never-before-identified low-volatility organi...

We show for the first time quantitative online measurements of five nitrated phenol (NP) compounds in ambient air (nitrophenol C6H5NO3, methylnitrophenol C7H7NO3, nitrocatechol C6H5NO4, methylnitrocatechol C7H7NO4, and dinitrophenol C6H4N2O5) measured with a micro-orifice volatilization impactor (MOVI) high-resolution chemical ionization mass spectrometer in Detling, United Kingdom during January-February, 2012. NPs absorb radiation in the near-ultraviolet (UV) range of the electromagnetic spectrum and thus are potential components of poorly characterized light-absorbing organic matter ("brown carbon") which can affect the climate and air quality. Total NP concentrations varied between less than 1 and 98 ng m(-3), with a mean value of 20 ng m(-3). We conclude that NPs measured in Detling have a significant contribution from biomass burning with an estimated emission factor of 0.2 ng (ppb CO)(-1). Particle light absorption measurements by a seven-wavelength aethalometer in the near-UV (370 nm) and literature values of molecular absorption cross sections are used to estimate the contribution of NP to wood burning brown carbon UV light absorption. We show that these five NPs are potentially important contributors to absorption at 370 nm measured by an aethalometer and account for 4 ± 2% of UV light absorption by brown carbon. They can thus affect atmospheric radiative transfer and photochemistry and with that climate and air quality.

Black carbon (BC) and light-absorbing organic carbon (brown carbon, BrC) play key roles in warming the atmosphere, but the magnitude of their effects remains highly uncertain. Theoretical modelling and laboratory experiments demonstrate that coatings on BC can enhance BC's light absorption, therefore many climate models simply assume enhanced BC absorption by a factor of ∼1.5. However, recent field observations show negligible absorption enhancement, implying models may overestimate BC's warming. Here we report direct evidence of substantial field-measured BC absorption enhancement, with the magnitude strongly depending on BC coating amount. Increases in BC coating result from a combination of changing sources and photochemical aging processes. When the influence of BrC is accounted for, observationally constrained model calculations of the BC absorption enhancement can be reconciled with the observations. We conclude that the influence of coatings on BC absorption should be treated as a source and regionally specific parameter in climate models.

We compare the relative toxicity of various organic aerosol (OA) components identified by an aerosol mass spectrometer (AMS) based on their ability to generate reactive oxygen species (ROS). Ambient fine aerosols were collected from urban (three in Atlanta, GA and one in Birmingham, AL) and rural (Yorkville, GA and Centerville, AL) sites in the Southeastern United States. The ROS generating capability of the water-soluble fraction of the particles was measured by the dithiothreitol (DTT) assay. Water-soluble PM extracts were further separated into the hydrophobic and hydrophilic fractions using a C-18 column, and both fractions were analyzed for DTT activity and water-soluble metals. Organic aerosol composition was measured at selected sites using a high-resolution time-of-flight AMS. Positive matrix factorization of the AMS spectra resolved the organic aerosol into isoprene-derived OA (Isop_OA), hydrocarbon-like OA (HOA), less-oxidized oxygenated OA, (LO-OOA), more-oxidized OOA (MO-OOA), cooking OA (COA), and biomass burning OA (BBOA). The association of the DTT activity of water-soluble PM2.5 (WS_DTT) with these factors was investigated by linear regression techniques. BBOA and MO-OOA were most consistently linked with WS_DTT, with intrinsic water-soluble activities of 151 ± 20 and 36 ± 22 pmol/min/μg, respectively. Although less toxic, MO-OOA was most widespread, contributing to WS_DTT activity at all sites and during all seasons. WS_DTT activity was least associated with biogenic secondary organic aerosol. The OA components contributing to WS_DTT were humic-like substances (HULIS), which are abundantly emitted in biomass burning (BBOA) and include highly oxidized OA from multiple sources (MO-OOA). Overall, OA contributed approximately 60% to the WS_DTT activity, with the remaining probably from water-soluble metals, which were mostly associated with the hydrophilic WS_DTT fraction.

Brown carbon aerosol consists of light-absorbing organic particulate matter with wavelength-dependent absorption. Aerosol optical extinction, absorption, size distributions, and chemical composition were measured in rural Alabama during summer 2013. The field site was well located to examine sources of brown carbon aerosol, with influence by high biogenic organic aerosol concentrations, pollution from two nearby cities, and biomass burning aerosol. We report the optical closure between measured dry aerosol extinction at 365 nm and calculated extinction from composition and size distribution, showing agreement within experiment uncertainties. We find that aerosol optical extinction is dominated by scattering, with single-scattering albedo values of 0.94 ± 0.02. Black carbon aerosol accounts for 91 ± 9% of the total carbonaceous aerosol absorption at 365 nm, while organic aerosol accounts for 9 ± 9%. The majority of brown carbon aerosol mass is associated with biomass burning, with smaller contributions from biogenically derived secondary organic aerosol.