Jason C. Schroder

Fine particle pH and the partitioning of nitric acid during winter in the northeastern United States: PARTICLE PH AND NITRIC ACID PARTITIONING

Particle pH is a critical but poorly constrained quantity that affects many aerosol processes and properties, including aerosol composition, concentrations, and toxicity. We assess PM1 pH as a function of geographical location and altitude, focusing on the northeastern US, based on aircraft measurements from the Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) campaign (01 Feb to 15 Mar 2015). Particle pH and water were predicted with the ISORROPIA-II thermodynamic model and validated by comparing predicted to observed partitioning of inorganic nitrate between the gas and particle phases. Good agreement was found for relative humidity (RH) above 40%; at lower RH observed particle nitrate was higher than predicted, possibly due to organic-inorganic phase separations or nitrate measurement uncertainties associated with low concentrations (nitrateu2009<u20091 µgm-3). Including refractory ions in the pH calculations did not improve model predictions, suggesting they were externally mixed with PM1 sulfate, nitrate, and ammonium. Sample line volatilization artifacts were found to be minimal. Overall, particle pH for altitudes up to 5000u2009m ranged between -0.51 and 1.9 (10th and 90th percentiles) with a study mean of 0.77u2009±u20090.96, similar to those reported for the southeastern US and eastern Mediterranean. This expansive aircraft data set is used to investigate causes in variability in pH and pH-dependent aerosol components, such as PM1 nitrate, over a wide range of temperatures (-21 to 19u2009°C), RH (20 to 95%), inorganic gas and particle concentrations and also provides further evidence that particles with low pH are ubiquitous.

Flight Deployment of a High‐Resolution Time‐of‐Flight Chemical Ionization Mass Spectrometer: Observations of Reactive Halogen and Nitrogen Oxide Species

We describe the University of Washington airborne high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) and evaluate its performance aboard the NCAR-NSF C-130 aircraft during the recent Wintertime INvestigation of Transport, Emissions and Reactivity (WINTER) experiment in February–March of 2015. New features include (i) a computer-controlled dynamic pinhole that maintains constant mass flow-rate into the instrument independent of altitude changes to minimize variations in instrument response times; (ii) continuous addition of low flow-rate humidified ultrahigh purity nitrogen to minimize the difference in water vapor pressure, hence instrument sensitivity, between ambient and background determinations; (iii) deployment of a calibration source continuously generating isotopically labeled dinitrogen pentoxide (N2O5) for in-flight delivery; and (iv) frequent instrument background determinations to account for memory effects resulting from the interaction between sticky compounds and instrument surface following encounters with concentrated air parcels. The resulting improvements to precision and accuracy, along with the simultaneous acquisition of these species and the full set of their isotopologues, allow for more reliable identification, source attribution, and budget accounting, for example, by speciating the individual constituents of nocturnal reactive nitrogen oxides (NOz = ClNO2 + 2 × N2O5 + HNO3 + etc.). We report on an expanded set of species quantified using iodide-adduct ionization such as sulfur dioxide (SO2), hydrogen chloride (HCl), and other inorganic reactive halogen species including hypochlorous acid, nitryl chloride, chlorine, nitryl bromide, bromine, and bromine chloride (HOCl, ClNO2, Cl2, BrNO2, Br2, and BrCl, respectively).

Heterogeneous N2O5 Uptake During Winter: Aircraft Measurements During the 2015 WINTER Campaign and Critical Evaluation of Current Parameterizations

Nocturnal dinitrogen pentoxide (N2O5) heterogeneous chemistry impacts regional air quality and the distribution and lifetime of tropospheric oxidants. Formed from the oxidation of nitrogen oxides, N2O5 is heterogeneously lost to aerosol with a highly variable reaction probability, γ(N2O5), dependent on aerosol composition and ambient conditions. Reaction products include soluble nitrate (HNO3 or NO3 ) and nitryl chloride (ClNO2). We report the first-ever derivations of γ(N2O5) from ambient wintertime aircraft measurements in the critically important nocturnal residual boundary layer. Box modeling of the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign over the eastern United States derived 2,876 individual γ(N2O5) values with a median value of 0.0143 and range of 2 × 10 5 to 0.1751. WINTER γ(N2O5) values exhibited the strongest correlation with aerosol water content, but weak correlations with other variables, such as aerosol nitrate and organics, suggesting a complex, nonlinear dependence on multiple factors, or an additional dependence on a nonobserved factor. This factor may be related to aerosol phase, morphology (i.e., core shell), or mixing state, none of which are commonly measured during aircraft field studies. Despite general agreement with previous laboratory observations, comparison of WINTER data with 14 literature parameterizations (used to predict γ(N2O5) in chemical transport models) confirms that none of the current methods reproduce the full range of γ(N2O5) values. Nine reproduce the WINTER median within a factor of 2. Presented here is the first field-based, empirical parameterization of γ(N2O5), fit to WINTER data, based on the functional form of previous parameterizations.

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

Significance Exposure to fine particulate matter is a leading cause of premature deaths and illnesses globally. In the eastern United States, substantial cuts in sulfur dioxide and nitrogen oxides emissions have considerably lowered particulate sulfate and nitrate concentrations for all seasons except winter. Simulations that reproduce detailed airborne observations of wintertime atmospheric chemistry over the eastern United States indicate that particulate sulfate and nitrate formation is limited by the availability of oxidants and by the acidity of fine particles, respectively. These limitations relax at lower ambient concentrations, forming particulate matter more efficiently, and weaken the effect of emission reductions. These results imply that larger emission reductions, especially during winter, are necessary for substantial improvements in wintertime air quality in the eastern United States. Sulfate (SO42-) and nitrate (NO3-) 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 SO42- and NO3-. GEOS-Chem reproduces observed SO42-–NO3-–NH4+ particulate concentrations (2.45 μg sm-3) and composition (SO42-: 47%; NO3-: 32%; NH4+: 21%) during WINTER. Only 18% of SO2 emissions were regionally oxidized to SO42- 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 SO2 emissions from 2007 to 2015 and find that the H2O2 limitation on SO2 oxidation weakened, which increased the fraction of SO2 emissions oxidizing to SO42-. Simultaneously, NOx emissions decreased by 35%, but the modeled NO3- particle fraction increased as fine particle acidity decreased. These feedbacks resulted in a 40% decrease of modeled [SO42-] and no change in [NO3-], as observed. Wintertime [SO42-] and [NO3-] are expected to change slowly between 2015 and 2023, unless SO2 and NOx emissions decrease faster in the future than in the recent past.

Sources and Secondary Production of Organic Aerosols in the Northeastern United States during WINTER

Most intensive field studies investigating aerosols have been conducted in summer, and thus, wintertime aerosol sources and chemistry are comparatively poorly understood. An aerosol mass spectrometer was flown on the National Science Foundation/National Center for Atmospheric Research C-130 during the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) 2015 campaign in the northeast United States. The fraction of boundary layer submicron aerosol that was organic aerosol (OA) was about a factor of 2 smaller than during a 2011 summertime study in a similar region. However, the OA measured inWINTERwas almost as oxidized as OAmeasured in several other studies in warmermonths of the year. Fifty-eight percent of the OA was oxygenated (secondary), and 42% was primary (POA). Biomass burning OA (likely from residential heating) was ubiquitous and accounted for 33% of the OA mass. Using nonvolatile POA, one of two default secondary OA (SOA) formulations in GEOS-Chem (v10-01) shows very large underpredictions of SOA and O/C (5×) and overprediction of POA (2×). We strongly recommend against using that formulation in future studies. Semivolatile POA, an alternative default in GEOS-Chem, or a simplified parameterization (SIMPLE) were closer to the observations, although still with substantial differences. A case study of urban outflow from metropolitan New York City showed a consistent amount and normalized rate of added OA mass (due to SOA formation) compared to summer studies, although proceeding more slowly due to lower OH concentrations. A boxmodel and SIMPLE perform similarly forWINTER as for Los Angeles, with an underprediction at ages <6 hr, suggesting that fast chemistry might be missing from the models.

Laser Ablation-Aerosol Mass Spectrometry-Chemical Ionization Mass Spectrometry for Ambient Surface Imaging

Mass spectrometry imaging is becoming an increasingly common analytical technique due to its ability to provide spatially resolved chemical information. Here, we report a novel imaging approach combining laser ablation with two mass spectrometric techniques, aerosol mass spectrometry and chemical ionization mass spectrometry, separately and in parallel. Both mass spectrometric methods provide the fast response, rapid data acquisition, low detection limits, and high-resolution peak separation desirable for imaging complex samples. Additionally, the two techniques provide complementary information with aerosol mass spectrometry providing near universal detection of all aerosol molecules and chemical ionization mass spectrometry with a heated inlet providing molecular-level detail of both gases and aerosols. The two techniques operate with atmospheric pressure interfaces and require no matrix addition for ionization, allowing for samples to be investigated in their native state under ambient pressure conditions. We demonstrate the ability of laser ablation-aerosol mass spectrometry-chemical ionization mass spectrometry (LA-AMS-CIMS) to create 2D images of both standard compounds and complex mixtures. The results suggest that LA-AMS-CIMS, particularly when combined with advanced data analysis methods, could have broad applications in mass spectrometry imaging applications.