Underestimation of Thermogenic Methane Emissions in New York City.

Recent studies have shown that methane emissions are underestimated by inventories in many US urban areas. This has important implications for climate change mitigation policy at the city, state, and national levels. Uncertainty in both the spatial distribution and sectoral allocation of urban emissions can limit the ability of policy makers to develop appropriately focused emission reduction strategies. Top-down emission estimates based on atmospheric greenhouse gas measurements can help to improve inventories and inform policy decisions. This study presents a new high-resolution (0.02 × 0.02°) methane emission inventory for New York City and its surrounding area, constructed using the latest activity data, emission factors, and spatial proxies. The new high-resolution inventory estimates of methane emissions for the New York-Newark urban area are 1.3 times larger than those for the gridded Environmental Protection Agency inventory. We used aircraft mole fraction measurements from nine research flights to optimize the high-resolution inventory emissions within a Bayesian inversion. These sectorally optimized emissions show that the high-resolution inventory still significantly underestimates methane emissions within the New York-Newark urban area, primarily because it underestimates emissions from thermogenic sources (by a factor of 2.3). This suggests that there remains a gap in our process-based understanding of urban methane emissions.

Carbon Monoxide Emissions from the Washington, DC, and Baltimore Metropolitan Area: Recent Trend and COVID-19 Anomaly.

We analyze airborne measurements of atmospheric CO concentration from 70 flights conducted over six years (2015-2020) using an inverse model to quantify the CO emissions from the Washington, DC, and Baltimore metropolitan areas. We found that CO emissions have been declining in the area at a rate of ≈-4.5 % a-1 since 2015 or ≈-3.1 % a-1 since 2016. In addition, we found that CO emissions show a "Sunday" effect, with emissions being lower, on average, than for the rest of the week and that the seasonal cycle is no larger than 16 %. Our results also show that the trend derived from the NEI agrees well with the observed trend, but that NEI daytime-adjusted emissions are ≈50 % larger than our estimated emissions. In 2020, measurements collected during the shutdown in activity related to the COVID-19 pandemic indicate a significant drop in CO emissions of 16 % relative to the expected emissions trend from the previous years, or 23 % relative to the mean of 2016 to February 2020. Our results also indicate a larger reduction in April than in May. Last, we show that this reduction in CO emissions was driven mainly by a reduction in traffic.

Direct detection of atmospheric atomic bromine leading to mercury and ozone depletion.

Bromine atoms play a central role in atmospheric reactive halogen chemistry, depleting ozone and elemental mercury, thereby enhancing deposition of toxic mercury, particularly in the Arctic near-surface troposphere. However, direct bromine atom measurements have been missing to date, due to the lack of analytical capability with sufficient sensitivity for ambient measurements. Here we present direct atmospheric bromine atom measurements, conducted in the springtime Arctic. Measured bromine atom levels reached 14 parts per trillion (ppt, pmol mol-1; 4.2 × 108 atoms per cm-3) and were up to 3-10 times higher than estimates using previous indirect measurements not considering the critical role of molecular bromine. Observed ozone and elemental mercury depletion rates are quantitatively explained by the measured bromine atoms, providing field validation of highly uncertain mercury chemistry. Following complete ozone depletion, elevated bromine concentrations are sustained by photochemical snowpack emissions of molecular bromine and nitrogen oxides, resulting in continued atmospheric mercury depletion. This study provides a breakthrough in quantitatively constraining bromine chemistry in the polar atmosphere, where this chemistry connects the rapidly changing surface to pollutant fate.

Wintertime CO2, CH4, and CO Emissions Estimation for the Washington, DC-Baltimore Metropolitan Area Using an Inverse Modeling Technique.

Since greenhouse gas mitigation efforts are mostly being implemented in cities, the ability to quantify emission trends for urban environments is of paramount importance. However, previous aircraft work has indicated large daily variability in the results. Here we use measurements of CO2, CH4, and CO from aircraft over 5 days within an inverse model to estimate emissions from the DC-Baltimore region. Results show good agreement with previous estimates in the area for all three gases. However, aliasing caused by irregular spatiotemporal sampling of emissions is shown to significantly impact both the emissions estimates and their variability. Extensive sensitivity tests allow us to quantify the contributions of different sources of variability and indicate that daily variability in posterior emissions estimates is larger than the uncertainty attributed to the method itself (i.e., 17% for CO2, 24% for CH4, and 13% for CO). Analysis of hourly reported emissions from power plants and traffic counts shows that 97% of the daily variability in posterior emissions estimates is explained by accounting for the sampling in time and space of sources that have large hourly variability and, thus, caution must be taken in properly interpreting variability that is caused by irregular spatiotemporal sampling conditions.

Active molecular iodine photochemistry in the Arctic.

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiagvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I- measurements showed enrichments of up to ∼1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2 is likely a dominant source of iodine atoms in the Arctic.

Observations of Methane Emissions from Natural Gas-Fired Power Plants.

Current research efforts on the atmospheric impacts of natural gas (NG) have focused heavily on the production, storage/transmission, and processing sectors, with less attention paid to the distribution and end use sectors. This work discusses 23 flights at 14 natural gas-fired power plants (NGPPs) using an aircraft-based mass balance technique and methane/carbon dioxide enhancement ratios (ΔCH4/ΔCO2) measured from stack plumes to quantify the unburned fuel. By comparing the ΔCH4/ΔCO2 ratio measured in stack plumes to that measured downwind, we determined that, within uncertainty of the measurement, all observed CH4 emissions were stack-based, that is, uncombusted NG from the stack rather than fugitive sources. Measured CH4 emission rates (ER) ranged from 8 (±5) to 135 (±27) kg CH4/h (±1σ), with the fractional CH4 throughput lost (loss rate) ranging from -0.039% (±0.076%) to 0.204% (±0.054%). We attribute negative values to partial combustion of ambient CH4 in the power plant. The average calculated emission factor (EF) of 5.4 (+10/-5.4) g CH4/million British thermal units (MMBTU) is within uncertainty of the Environmental Protection Agency (EPA) EFs. However, one facility measured during startup exhibited substantially larger stack emissions with an EF of 440 (+660/-440) g CH4/MMBTU and a loss rate of 2.5% (+3.8/-2.5%).

Synthesis of Urban CO2 Emission Estimates from Multiple Methods from the Indianapolis Flux Project (INFLUX).

Urban areas contribute approximately three-quarters of fossil fuel derived CO2 emissions, and many cities have enacted emissions mitigation plans. Evaluation of the effectiveness of mitigation efforts will require measurement of both the emission rate and its change over space and time. The relative performance of different emission estimation methods is a critical requirement to support mitigation efforts. Here we compare results of CO2 emissions estimation methods including an inventory-based method and two different top-down atmospheric measurement approaches implemented for the Indianapolis, Indiana, U.S.A. urban area in winter. By accounting for differences in spatial and temporal coverage, as well as trace gas species measured, we find agreement among the wintertime whole-city fossil fuel CO2 emission rate estimates to within 7%. This finding represents a major improvement over previous comparisons of urban-scale emissions, making urban CO2 flux estimates from this study consistent with local and global emission mitigation strategy needs. The complementary application of multiple scientifically driven emissions quantification methods enables and establishes this high level of confidence and demonstrates the strength of the joint implementation of rigorous inventory and atmospheric emissions monitoring approaches.

Springtime Nitrogen Oxide-Influenced Chlorine Chemistry in the Coastal Arctic.

Atomic chlorine (Cl) is a strong atmospheric oxidant that shortens the lifetimes of pollutants and methane in the springtime Arctic, where the molecular halogens Cl2 and BrCl are known Cl precursors. Here, we quantify the contributions of reactive chlorine trace gases and present the first observations, to our knowledge, of ClNO2 (another Cl precursor), N2O5, and HO2NO2 in the Arctic. During March - May 2016 near Utqiagvik, Alaska, up to 21 ppt of ClNO2, 154 ppt of Cl2, 27 ppt of ClO, 71 ppt of N2O5, 21 ppt of BrCl, and 153 ppt of HO2NO2 were measured using chemical ionization mass spectrometry. The main Cl precursor was calculated to be Cl2 (up to 73%) in March, while BrCl was a greater contributor (63%) in May, when total Cl production was lower. Elevated levels of ClNO2, N2O5, Cl2, and HO2NO2 coincided with pollution influence from the nearby town of Utqiagvik and the North Slope of Alaska (Prudhoe Bay) Oilfields. We propose a coupled mechanism linking NOx with Arctic chlorine chemistry. Enhanced Cl2 was likely the result of the multiphase reaction of Cl-(aq) with ClONO2, formed from the reaction of ClO and NO2. In addition to this NOx-enhanced chlorine chemistry, Cl2 and BrCl were observed under clean Arctic conditions from snowpack photochemical production. These connections between NOx and chlorine chemistry, and the role of snowpack recycling, are important given increasing shipping and fossil fuel extraction predicted to accompany Arctic sea ice loss.

Bouncier Particles at Night: Biogenic Secondary Organic Aerosol Chemistry and Sulfate Drive Diel Variations in the Aerosol Phase in a Mixed Forest.

Aerosol phase state is critical for quantifying aerosol effects on climate and air quality. However, significant challenges remain in our ability to predict and quantify phase state during its evolution in the atmosphere. Herein, we demonstrate that aerosol phase (liquid, semisolid, solid) exhibits a diel cycle in a mixed forest environment, oscillating between a viscous, semisolid phase state at night and liquid phase state with phase separation during the day. The viscous nighttime particles existed despite higher relative humidity and were independently confirmed by bounce factor measurements and atomic force microscopy. High-resolution mass spectrometry shows the more viscous phase state at night is impacted by the formation of terpene-derived and higher molecular weight secondary organic aerosol (SOA) and smaller inorganic sulfate mass fractions. Larger daytime particulate sulfate mass fractions, as well as a predominance of lower molecular weight isoprene-derived SOA, lead to the liquid state of the daytime particles and phase separation after greater uptake of liquid water, despite the lower daytime relative humidity. The observed diel cycle of aerosol phase should provoke rethinking of the SOA atmospheric lifecycle, as it suggests diurnal variability in gas-particle partitioning and mixing time scales, which influence aerosol multiphase chemistry, lifetime, and climate impacts.

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.

Reconciling divergent estimates of oil and gas methane emissions.

Published estimates of methane emissions from atmospheric data (top-down approaches) exceed those from source-based inventories (bottom-up approaches), leading to conflicting claims about the climate implications of fuel switching from coal or petroleum to natural gas. Based on data from a coordinated campaign in the Barnett Shale oil and gas-producing region of Texas, we find that top-down and bottom-up estimates of both total and fossil methane emissions agree within statistical confidence intervals (relative differences are 10% for fossil methane and 0.1% for total methane). We reduced uncertainty in top-down estimates by using repeated mass balance measurements, as well as ethane as a fingerprint for source attribution. Similarly, our bottom-up estimate incorporates a more complete count of facilities than past inventories, which omitted a significant number of major sources, and more effectively accounts for the influence of large emission sources using a statistical estimator that integrates observations from multiple ground-based measurement datasets. Two percent of oil and gas facilities in the Barnett accounts for half of methane emissions at any given time, and high-emitting facilities appear to be spatiotemporally variable. Measured oil and gas methane emissions are 90% larger than estimates based on the US Environmental Protection Agency's Greenhouse Gas Inventory and correspond to 1.5% of natural gas production. This rate of methane loss increases the 20-y climate impacts of natural gas consumed in the region by roughly 50%.

Inland Sea Spray Aerosol Transport and Incomplete Chloride Depletion: Varying Degrees of Reactive Processing Observed during SOAS.

Multiphase reactions involving sea spray aerosol (SSA) impact trace gas budgets in coastal regions by acting as a reservoir for oxidized nitrogen and sulfur species, as well as being a source of halogen gases (HCl, ClNO2, etc.). Whereas most studies of multiphase reactions on SSA have focused on marine environments, far less is known about SSA transported inland. Herein, single-particle measurements of SSA are reported at a site >320 km from the Gulf of Mexico, with transport times of 7-68 h. Samples were collected during the Southern Oxidant and Aerosol Study (SOAS) in June-July 2013 near Centreville, Alabama. SSA was observed in 93% of 42 time periods analyzed. During two marine air mass periods, SSA represented significant number fractions of particles in the accumulation (0.2-1.0 µm, 11%) and coarse (1.0-10.0 µm, 35%) modes. Chloride content of SSA particles ranged from full to partial depletion, with 24% of SSA particles containing chloride (mole fraction of Cl/Na ≥ 0.1, 90% chloride depletion). Both the frequent observation of SSA at an inland site and the range of chloride depletion observed suggest that SSA may represent an underappreciated inland sink for NOx/SO2 oxidation products and a source of halogen gases.

Spatiotemporal Variability of Methane Emissions at Oil and Natural Gas Operations in the Eagle Ford Basin.

Methane emissions from oil and gas facilities can exhibit operation-dependent temporal variability; however, this variability has yet to be fully characterized. A field campaign was conducted in June 2014 in the Eagle Ford basin, Texas, to examine spatiotemporal variability of methane emissions using four methods. Clusters of methane-emitting sources were estimated from 14 aerial surveys of two ("East" or "West") 35 × 35 km grids, two aircraft-based mass balance methods measured emissions repeatedly at five gathering facilities and three flares, and emitting equipment source-types were identified via helicopter-based infrared camera at 13 production and gathering facilities. Significant daily variability was observed in the location, number (East: 44 ± 20% relative standard deviation (RSD), N = 7; West: 37 ± 30% RSD, N = 7), and emission rates (36% of repeat measurements deviate from mean emissions by at least ±50%) of clusters of emitting sources. Emission rates of high emitters varied from 150-250 to 880-1470 kg/h and regional aggregate emissions of large sources (>15 kg/h) varied up to a factor of ∼3 between surveys. The aircraft-based mass balance results revealed comparable variability. Equipment source-type changed between surveys and alterations in operational-mode significantly influenced emissions. Results indicate that understanding temporal emission variability will promote improved mitigation strategies and additional analysis is needed to fully characterize its causes.

Assessing the Methane Emissions from Natural Gas-Fired Power Plants and Oil Refineries.

Presently, there is high uncertainty in estimates of methane (CH4) emissions from natural gas-fired power plants (NGPP) and oil refineries, two major end users of natural gas. Therefore, we measured CH4 and CO2 emissions at three NGPPs and three refineries using an aircraft-based mass balance technique. Average CH4 emission rates (NGPPs: 140 ± 70 kg/h; refineries: 580 ± 220 kg/h, 95% CL) were larger than facility-reported estimates by factors of 21-120 (NGPPs) and 11-90 (refineries). At NGPPs, the percentage of unburned CH4 emitted from stacks (0.01-0.08%) was much lower than respective facility-scale losses (0.09-0.34%), and CH4 emissions from both NGPPs and refineries were more strongly correlated with enhanced H2O concentrations (R2avg = 0.65) than with CO2 (R2avg = 0.21), suggesting noncombustion-related equipment as potential CH4 sources. Additionally, calculated throughput-based emission factors (EF) derived from the NGPP measurements made in this study were, on average, a factor of 4.4 (stacks) and 37 (facility-scale) larger than industry-used EFs. Subsequently, throughput-based EFs for both the NGPPs and refineries were used to estimate total U.S. emissions from these facility-types. Results indicate that NGPPs and oil refineries may be large sources of CH4 emissions and could contribute significantly (0.61 ± 0.18 Tg CH4/yr, 95% CL) to U.S. emissions.

Toward a better understanding and quantification of methane emissions from shale gas development.

The identification and quantification of methane emissions from natural gas production has become increasingly important owing to the increase in the natural gas component of the energy sector. An instrumented aircraft platform was used to identify large sources of methane and quantify emission rates in southwestern PA in June 2012. A large regional flux, 2.0-14 g CH4 s(-1) km(-2), was quantified for a ∼ 2,800-km(2) area, which did not differ statistically from a bottom-up inventory, 2.3-4.6 g CH4 s(-1) km(-2). Large emissions averaging 34 g CH4/s per well were observed from seven well pads determined to be in the drilling phase, 2 to 3 orders of magnitude greater than US Environmental Protection Agency estimates for this operational phase. The emissions from these well pads, representing ∼ 1% of the total number of wells, account for 4-30% of the observed regional flux. More work is needed to determine all of the sources of methane emissions from natural gas production, to ascertain why these emissions occur and to evaluate their climate and atmospheric chemistry impacts.

Chemical characterization of α-pinene secondary organic aerosol constituents using gas chromatography, liquid chromatography, and paper spray-based mass spectrometry techniques.

RATIONALE: Despite ample research into the atmospheric oxidation of α-pinene, an important precursor to biogenic secondary organic aerosol formation, the identification of its reaction products, specifically organic nitrates, which impact atmospheric NOx concentrations, is still incomplete. This negatively impacts our understanding of α-pinene oxidation chemistry and its relation to air quality. METHODS: Photochemical chamber experiments were conducted in conjunction with mass spectrometric techniques, including gas chromatography/mass spectrometry (GC/MS), high-performance liquid chromatography/time-of-flight (HPLC/TOF), and paper spray ionization MS, to investigate products from the OH radical initiated oxidation of α-pinene under high NOx conditions. RESULTS: Over 30 compounds were tentatively identified, including those newly detected from photochemical chamber studies of α-pinene oxidation, pinocamphenol, fencholenic aldehyde, and α-pinene-derived nitrate isomers. α-Pinene-derived hydroxynitrate isomers were successfully detected using chromatographic methods, demonstrating, for the first time, the identification of individual first-generation organic nitrate products derived from α-pinene. The application of paper spray ionization to particle-phase compounds collected on filters represents a novel method for the direct analysis of filter samples at ambient pressure and temperature. CONCLUSIONS: The use of HPLC/TOF and paper spray ionization methods to identify previously unobserved α-pinene-derived products helps lower the uncertainty in α-pinene oxidation chemistry and provides new platforms that can be used to identify and quantify important atmospheric compounds that relate to air quality in a complex sample matrix, such as ambient aerosol particles. Additionally, the use of paper spray ionization for direct filter analysis is a fast, relatively inexpensive sample preparation technique that can be used to reduce sample manipulation from solvent-induced reactions. Copyright © 2016 John Wiley & Sons, Ltd.

Constraints on Arctic Atmospheric Chlorine Production through Measurements and Simulations of Cl2 and ClO.

During springtime, unique halogen chemistry involving chlorine and bromine atoms controls the prevalence of volatile organic compounds, ozone, and mercury in the Arctic lower troposphere. In situ measurements of the chlorine monoxide radical, ClO, and its precursor, Cl2, along with BrO and Br2, were conducted using chemical ionization mass spectrometry (CIMS) during the Bromine, Ozone, and Mercury Experiment (BROMEX) near Barrow, Alaska, in March 2012. To our knowledge, these data represent the first ClO measurements made using CIMS. A maximum daytime ClO concentration of 28 ppt was observed following an early morning peak of 75 ppt of Cl2. A zero-dimensional photochemistry model was constrained to Cl2 observations and used to simulate ClO during a 7-day period of the field campaign. The model simulates ClO within the measurement uncertainty, and the model results highlight the importance of chlorine chemistry participation in bromine radical cycling, as well as the dependence of halogen chemistry on NOx levels. The ClO measurements and simulations are consistent with Cl2 being the dominant Cl atom source in the Arctic boundary layer. Simulated Cl atom concentrations, up to ∼1 × 106 molecules cm-3, highlight the importance of chlorine chemistry in the degradation of volatile organic compounds, including the greenhouse gas methane.

Black Carbon Emissions from Associated Natural Gas Flaring.

Approximately 150 billion cubic meters (BCM) of natural gas is flared and vented in the world annually, emitting greenhouse gases and other pollutants with no energy benefit. About 7 BCM per year is flared in the United States, and half is from North Dakota alone. There are few emission measurements from associated gas flares and limited black carbon (BC) emission factors have been previously reported from the field. Emission plumes from 26 individual flares in the Bakken formation in North Dakota were sampled. Methane, carbon dioxide, and BC were measured simultaneously, allowing the calculation of BC mass emission factors using the carbon balance method. Particle optical absorption was measured using a three-wavelength particle soot absorption photometer (PSAP) and BC particle number and mass concentrations were measured with a single particle soot photometer. The BC emission factors varied over 2 orders of magnitude, with an average and uncertainty range of 0.14 ± 0.12 g/kg hydrocarbons in associated gas and a median of 0.07 g/kg which represents a lower bound on these measurements. An estimation of the BC emission factor derived from PSAP absorption provides an upper bound at 3.1 g/kg. These results are lower than previous estimations and laboratory measurements. The BC mass absorption cross section was 16 ± 12 m(2)/g BC at 530 nm. The average absorption Ångström exponent was 1.2 ± 0.8, suggesting that most of the light absorbing aerosol measured was black carbon and the contribution of light absorbing organic carbon was small.

Direct and Indirect Measurements and Modeling of Methane Emissions in Indianapolis, Indiana.

This paper describes process-based estimation of CH4 emissions from sources in Indianapolis, IN and compares these with atmospheric inferences of whole city emissions. Emissions from the natural gas distribution system were estimated from measurements at metering and regulating stations and from pipeline leaks. Tracer methods and inverse plume modeling were used to estimate emissions from the major landfill and wastewater treatment plant. These direct source measurements informed the compilation of a methane emission inventory for the city equal to 29 Gg/yr (5% to 95% confidence limits, 15 to 54 Gg/yr). Emission estimates for the whole city based on an aircraft mass balance method and from inverse modeling of CH4 tower observations were 41 ± 12 Gg/yr and 81 ± 11 Gg/yr, respectively. Footprint modeling using 11 days of ethane/methane tower data indicated that landfills, wastewater treatment, wetlands, and other biological sources contribute 48% while natural gas usage and other fossil fuel sources contribute 52% of the city total. With the biogenic CH4 emissions omitted, the top-down estimates are 3.5-6.9 times the nonbiogenic city inventory. Mobile mapping of CH4 concentrations showed low level enhancement of CH4 throughout the city reflecting diffuse natural gas leakage and downstream usage as possible sources for the missing residual in the inventory.

Direct Measurement of pH in Individual Particles via Raman Microspectroscopy and Variation in Acidity with Relative Humidity.

Atmospheric aerosol acidity is an important characteristic of aqueous particles, which has been linked to the formation of secondary organic aerosol by catalyzing reactions of oxidized organic compounds that have partitioned to the particle phase. However, aerosol acidity is difficult to measure and traditionally estimated using indirect methods or assumptions based on composition. Ongoing disagreements between experiments and thermodynamic models of particle acidity necessitate improved fundamental understanding of pH and ion behavior in high ionic strength atmospheric particles. Herein, Raman microspectroscopy was used to determine the pH of individual particles (H2SO4+MgSO4) based on sulfate and bisulfate concentrations determined from νs(SO4(2-)) and νs(HSO4(-)), the acid dissociation constant, and activity coefficients from extended Debye-Hückel calculations. Shifts in pH and peak positions of νs(SO4(2-)) and νs(HSO4(-)) were observed as a function of relative humidity. These results indicate the potential for direct spectroscopic determination of pH in individual particles and the need to improve fundamental understanding of ion behavior in atmospheric particles.