Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), and organic mass-to-organic carbon (OM : OC) ratios, and of carbon oxidation state (OS _C) for a vastly expanded laboratory data set of multifunctional oxidized OA standards. For the expanded standard data set, the method introduced by Aiken et al. (2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios (referred to here as "Aiken-Explicit"), reproduces known O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12%, respectively. The more commonly used method, which uses empirically estimated H₂O⁺ and CO⁺ ion intensities to avoid gas phase air interferences at these ions (referred to here as "Aiken-Ambient"), reproduces O : C and H : C of multifunctional oxidized species within 28 and 14% of known values. The values from the latter method are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H₂O⁺, CO⁺, and CO₂⁺ fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO⁺ and especially H₂O⁺ produced from many oxidized species. Combined AMS–vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method uses specific ion fragments as markers to correct for molecular functionality-dependent systematic biases and reproduces known O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C (H : C) values is smaller for theoretical standard mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The OS _C values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 OS _C units). This indicates that OS _C is a more robust metric of oxidation than O : C, likely since OS _C is not affected by hydration or dehydration, either in the atmosphere or during analysis.

Delhi, India, routinely experiences some of the world's highest urban particulate matter concentrations. We established the Delhi Aerosol Supersite study to provide long-term characterization of the ambient submicron aerosol composition in Delhi. Here we report on 1.25 years of highly time-resolved speciated submicron particulate matter (PM₁) data, including black carbon (BC) and nonrefractory PM₁ (NR-PM₁), which we combine to develop a composition-based estimate of PM₁ (“C-PM₁” = BC + NR-PM₁) concentrations. We observed marked seasonal and diurnal variability in the concentration and composition of PM₁ owing to the interactions of sources and atmospheric processes. Winter was the most polluted period of the year, with average C-PM₁ mass concentrations of ∼210 µg m⁻³. The monsoon was hot and rainy, consequently making it the least polluted (C-PM₁ ∼50 µg m⁻³) period. Organics constituted more than half of the C-PM₁ for all seasons and times of day. While ammonium, chloride, and nitrate each were ∼10 % of the C-PM₁ for the cooler months, BC and sulfate contributed ∼5 % each. For the warmer periods, the fractional contribution of BC and sulfate to C-PM₁ increased, and the chloride contribution decreased to less than 2 %. The seasonal and diurnal variation in absolute mass loadings were generally consistent with changes in ventilation coefficients, with higher concentrations for periods with unfavorable meteorology – low planetary boundary layer height and low wind speeds. However, the variation in C-PM₁ composition was influenced by temporally varying sources, photochemistry, and gas–particle partitioning. During cool periods when wind was from the northwest, episodic hourly averaged chloride concentrations reached 50–100 µg m⁻³, ranking among the highest chloride concentrations reported anywhere in the world. We estimated the contribution of primary emissions and secondary processes to Delhi's submicron aerosol. Secondary species contributed almost 50 %–70 % of Delhi's C-PM₁ mass for the winter and spring months and up to 60 %–80 % for the warmer summer and monsoon months. For the cooler months that had the highest C-PM₁ concentrations, the nighttime sources were skewed towards primary sources, while the daytime C-PM₁ was dominated by secondary species. Overall, these findings point to the important effects of both primary emissions and more regional atmospheric chemistry on influencing the extreme particle concentrations that impact the Delhi megacity region. Future air quality strategies considering Delhi's situation in both a regional and local context will be more effective than policies targeting only local, primary air pollutants.

The House Observations of Microbial and Environmental Chemistry (HOMEChem) study is a collaborative field investigation designed to probe how everyday activities influence the emissions, chemical transformations and removal of trace gases and particles in indoor air. Sequential and layered experiments in a research house included cooking, cleaning, variable occupancy, and window-opening. This paper describes the overall design of HOMEChem and presents preliminary case studies investigating the concentrations of reactive trace gases, aerosol particles, and surface films. Cooking was a large source of VOCs, CO₂, NO_x, and particles. By number, cooking particles were predominantly in the ultrafine mode. Organic aerosol dominated the submicron mass, and, while variable between meals and throughout the cooking process, was dominated by components of hydrocarbon character and low oxygen content, similar to cooking oil. Air exchange in the house ensured that cooking particles were present for only short periods. During unoccupied background intervals, particle concentrations were lower indoors than outdoors. The cooling coils of the house ventilation system induced cyclic changes in water soluble gases. Even during unoccupied periods, concentrations of many organic trace gases were higher indoors than outdoors, consistent with housing materials being potential sources of these compounds to the outdoor environment. Organic material accumulated on indoor surfaces, and exhibited chemical signatures similar to indoor organic aerosol.

We report elevated levels of gaseous inorganic chlorinated and nitrogenated compounds in indoor air while cleaning with a commercial bleach solution during the House Observations of Microbial and Environmental Chemistry (HOMEChem) field campaign in summer 2018. Hypochlorous acid (HOCl), chlorine (Cl₂), and nitryl chloride (ClNO₂) reached part-per-billion by volume levels indoors during bleach cleaning—several orders of magnitude higher than typically measured in the outdoor atmosphere. Kinetic modeling revealed multiphase chemistry plays a central role in controlling indoor chlorine and reactive nitrogen chemistry during these periods. Cl₂ production occurred via heterogeneous reactions of HOCl on indoor surfaces. ClNO₂ and chloramine (NH₂Cl, NHCl₂, NCl₃) production occurred in the applied bleach via aqueous reactions involving nitrite (NO₂^-) and ammonia (NH₃), respectively. Aqueous-phase and surface chemistry resulted in elevated levels of gas-phase nitrogen dioxide (NO₂). We predict hydroxyl (OH) and chlorine (Cl) radical production during these periods (10⁶ and 10⁷ molecules cm^-3 s^-1, respectively) driven by HOCl and Cl₂ photolysis. Ventilation and photolysis accounted for <50% and <0.1% total loss of bleach-related compounds from indoor air, respectively; we conclude uptake to indoor surfaces is an important additional loss process. Indoor HOCl and nitrogen trichloride (NCl₃) mixing ratios during bleach cleaning reported herein are likely detrimental to human health.

There is considerable interest in using low-cost optical particle counters (OPCs) to supplement existing routine air quality networks that monitor particle mass concentrations. In order to do this, low-cost OPC data need to be comparable with particle mass reference instrumentation; however, there is currently no widely agreed upon methodology to accomplish this. Aerosol hygroscopicity is known to be a key parameter to consider when correcting particle mass concentrations derived from low-cost OPCs, particularly at high ambient relative humidity (RH). Correction factors have been developed that apply κ-Köhler theory to correct for the influence of water uptake by hygroscopic aerosols. We have used datasets of co-located reference particle measurements and low-cost OPC (OPC-N2, Alphasense) measurements, collected in four cities on three continents, to explore the performance of this correction factor. We provide evidence that the elevated particle mass concentrations, reported by the low-cost OPC relative to reference instrumentation, are due to bulk aerosol hygroscopicity under different RH conditions, which is determined by aerosol composition and, in particular, the levels of hygroscopic aerosols (sulfate and nitrate). We exploit measurements made in volcanic plumes in Nicaragua, which are predominantly composed of sulfate aerosol, as a natural experiment to demonstrate this behaviour in the ambient atmosphere; the observed humidogram from these measurements closely resembles the calculated pure sulfuric acid humidogram. The results indicate that the particle mass concentrations derived from low-cost OPCs during periods of high RH (>60 %) need to be corrected for aerosol hygroscopic growth. We employed a correction factor based on κ-Köhler theory and observed that the corrected OPC-N2 PM_2.5 mass concentrations were within 33 % of reference measurements at all sites. The results indicated that a κ value derived in situ (using suitable reference instrumentation) would lead to the most accurate correction relative to co-located reference instruments. Applying a κ values from the literature in the correction factor also resulted in improved OPC-N2 performance, with the measurements being within 50 % of the reference values. Therefore, for areas where suitable reference instrumentation for developing a local correction factor is lacking, using a literature κ value can result in a reasonable correction. For locations with low levels of hygroscopic aerosols and low RH values, a simple calibration against gravimetric measurements (using suitable reference instrumentation) would likely be sufficient. Whilst this study generated correction factors specific for the Alphasense OPC-N2 sensor, the calibration methodology developed is likely amenable to other low-cost PM sensors.

The Indian national capital, Delhi, routinely experiences some of the world's highest urban particulate matter concentrations. While fine particulate matter (PM_2.5) mass concentrations in Delhi are at least an order of magnitude higher than in many western cities, the particle number (PN) concentrations are not similarly elevated. Here we report on 1.25 years of highly time-resolved particle size distribution (PSD) data in the size range of 12–560 nm. We observed that the large number of accumulation mode particles – that constitute most of the PM_2.5 mass – also contributed substantially to the PN concentrations. The ultrafine particle (UFP; D_p<100 nm) fraction of PNs was higher during the traffic rush hours and for daytimes of warmer seasons, which is consistent with traffic and nucleation events being major sources of urban UFPs. UFP concentrations were found to be relatively lower during periods with some of the highest mass concentrations. Calculations based on measured PSDs and coagulation theory suggest UFP concentrations are suppressed by a rapid coagulation sink during polluted periods when large concentrations of particles in the accumulation mode result in high surface area concentrations. A smaller accumulation mode for warmer months results in an increased UFP fraction, likely owing to a comparatively smaller coagulation sink. We also see evidence suggestive of nucleation which may also contribute to the increased UFP proportions during the warmer seasons. Even though coagulation does not affect mass concentrations, it can significantly govern PN levels with important health and policy implications. Implications of a strong accumulation mode coagulation sink for future air quality control efforts in Delhi are that a reduction in mass concentration, especially in winter, may not produce a proportional reduction in PN concentrations. Strategies that only target accumulation mode particles (which constitute much of the fine PM_2.5 mass) may even lead to an increase in the UFP concentrations as the coagulation sink decreases.