Recent studies have found concentrations of reactive chlorine species to be higher than expected, suggesting that atmospheric chlorine chemistry is more extensive than previously thought. Chlorine ...radicals can interact with hydroperoxy (HOx) radicals and nitrogen oxides (NOx) to alter the oxidative capacity of the atmosphere. They are known to rapidly oxidize a wide range of volatile organic compounds (VOCs) found in the atmosphere, yet little is known about secondary organic aerosol (SOA) formation from chlorine-initiated photooxidation and its atmospheric implications. Environmental chamber experiments were carried out under low-NOx conditions with isoprene and chlorine as primary VOC and oxidant sources. Upon complete isoprene consumption, observed SOA yields ranged from 7 to 36 %, decreasing with extended photooxidation and SOA aging. Formation of particulate organochloride was observed. A high-resolution time-of-flight chemical ionization mass spectrometer was used to determine the molecular composition of gas-phase species using iodide–water and hydronium–water cluster ionization. Multi-generational chemistry was observed, including ions consistent with hydroperoxides, chloroalkyl hydroperoxides, isoprene-derived epoxydiol (IEPOX), and hypochlorous acid (HOCl), evident of secondary OH production and resulting chemistry from Cl-initiated reactions. This is the first reported study of SOA formation from chlorine-initiated oxidation of isoprene. Results suggest that tropospheric chlorine chemistry could contribute significantly to organic aerosol loading.
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 (PM.sub.1) data, including black carbon (BC) and nonrefractory PM.sub.1 (NR-PM.sub.1 ), which we combine to develop a composition-based estimate of PM.sub.1 ("C-PM.sub.1 " = BC + NR-PM.sub.1) concentrations.
The interaction between water vapor and atmospheric aerosol leads to enhancement in aerosol water content, which facilitates haze development, but its concentrations, sources, and impacts remain ...largely unknown in polluted urban environments. Here, we show that the Indian capital, Delhi, which tops the list of polluted capital cities, also experiences the highest aerosol water yet reported worldwide. This high aerosol water promotes secondary formation of aerosols and worsens air pollution. We report that severe pollution events are commonly associated with high aerosol water which enhances light scattering and reduces visibility by 70%. Strong light scattering also suppresses the boundary layer height on winter mornings in Delhi, inhibiting dispersal of pollutants and further exacerbating morning pollution peaks. We provide evidence that ammonium chloride is the largest contributor to aerosol water in Delhi, making up 40% on average, and we highlight that regulation of chlorine-containing precursors should be considered in mitigation strategies.
Present methodologies for source apportionment assume fixed source profiles. Since meteorology and human activity patterns change seasonally and diurnally, application of source apportionment ...techniques to shorter rather than longer time periods generates more representative mass spectra. Here, we present a new method to conduct source apportionment resolved by time of day using the underlying approach of positive matrix factorization (PMF). We call this approach “time-of-day PMF” and statistically demonstrate the improvements in this approach over traditional PMF. We report on source apportionment conducted on four example time periods in two seasons (winter and monsoon seasons of 2017), using organic aerosol measurements from an aerosol chemical speciation monitor (ACSM). We deploy the EPA PMF tool with the underlying Multilinear Engine (ME-2) as the PMF solver. Compared to the traditional seasonal PMF approach, we extract a larger number of factors as well as PMF factors that represent the expected sources of primary organic aerosol using time-of-day PMF. By capturing diurnal time series patterns of sources at a low computational cost, time-of-day PMF can utilize large datasets collected using long-term monitoring and improve the characterization of sources of organic aerosol compared to traditional PMF approaches that do not resolve by time of day.
Chlorine-initiated oxidation of n-alkanes (C8−12) under high-nitrogen oxide conditions was investigated. Observed secondary organic aerosol yields (0.16 to 1.65) are higher than those for ...OH-initiated oxidation of C8−12 alkanes (0.04 to 0.35). A high-resolution time-of-flight chemical ionization mass spectrometer coupled to a Filter Inlet for Gases and AEROsols (FIGAERO–CIMS) was used to characterize the gas- and particle-phase molecular composition. Chlorinated organics were observed, which likely originated from chlorine addition to the double bond present on the heterogeneously produced dihydrofurans. A two-dimensional thermogram representation was developed to visualize the composition and relative volatility of organic aerosol components using unit-mass resolution data. Evidence of oligomer formation and thermal decomposition was observed. Aerosol yield and oligomer formation were suppressed under humid conditions (35 % to 67 % RH) relative to dry conditions (under 5 % RH). The temperature at peak desorption signal, Tmax, a proxy for aerosol volatility, was shown to change with aerosol filter loading, which should be constrained when evaluating aerosol volatilities using the FIGAERO–CIMS. Results suggest that long-chain anthropogenic alkanes could contribute significantly to ambient aerosol loading over their atmospheric lifetime.
Organic aerosol emitted from cooking is a major concern for indoor air quality. During the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign, we simulated cooking, ...cleaning and occupancy activities in a realistic residential setting and measured resulting gas- and particle-phase emissions using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer with a Filter Inlet for Gases and Aerosols (FIGAERO-HR-ToF-CIMS). We identified ∼480 molecular formulas for compounds emitted on cooking-centered days and attributed them to potential sources including cooking, commercial, personal care products, and occupancy. Compounds with molecular formulas containing carbon, hydrogen, and oxygen atoms only (CHO group) composed most of the CIMS-measured molar fraction at 74-85%, with nitrogen-containing molecular formulas (CHNO group) being the second largest contributor (12-19%). We investigated the volatility of identified species based on FIGAERO-CIMS data in three ways:
(1)
using the maximum desorption temperature from one-dimensional thermograms, T
max
,
(2)
calculating gas-particle partitioning, F
p
,
(3)
using a molecular corridor parameterization to estimate saturation concentrations based on molecular formulas. We used the kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP) to calculate equilibration timescales and found that under sampling conditions (T = 323 K), it can take up to 14 seconds for equilibrium conditions to be met, whereas sampling residence times are approximately 3 seconds. The chemical diversity and wide range of volatilities of species sampled during cooking-centered events highlight the importance of understanding aerosol emissions and partitioning in indoor spaces where people spend most of their time.
The development of chemopreventive strategies with the ability to prevent the progression of lung lesions to malignant cancers would reduce the mortality and morbidity resulting from this deadly ...disease. Delivery of microRNA (miRNA) by inhalation is a novel method for lung cancer prevention. In this study, we investigated the combined efficacy of aerosolized miR-138-5p and miR-200c miRNA mimics in lung cancer prevention. Combination of the two miRNAs inhibited Benzo(a)pyrene (B((a))P)-induced lung adenomas and N-nitroso-tris-chloroethylurea (NTCU)-induced lung squamous cell carcinomas with no detectable side effects. Using single-cell RNA sequencing (scRNA-seq) and imaging mass cytometry (IMC), we found that both miRNAs inhibited programmed cell death ligand 1 (PD-L1) expression. Our flow cytometry results showed that aerosolized delivery of combined miRNAs increased CD4+ and CD8+ T cells and reduced the expression of programmed cell death protein 1 (PD-1) and T-regulatory cells. Our results demonstrated that the delivery of aerosolized microRNAs targeting PD-L1 can be highly effective in preventing lung cancer development and progression in mice.
Fine particulate matter (PM2.5) is a key indicator of urban air quality. Secondary organic aerosol (SOA) contributes substantially to the PM2.5 concentration. Discrepancies between modeling and field ...measurements of SOA indicate missing sources and formation mechanisms. Recent studies report elevated concentrations of reactive chlorine species in inland and urban regions, which increase the oxidative capacity of the atmosphere and serve as sources for SOA and particulate chlorides. Chlorine-initiated oxidation of isoprene, the most abundant nonmethane hydrocarbon, is known to produce SOA under pristine conditions, but the effects of anthropogenic influences in the form of nitrogen oxides (NOx) remain unexplored. Here, we investigate chlorine–isoprene reactions under low- and high-NOx conditions inside an environmental chamber. Organic chlorides including C5H11ClO3, C5H9ClO3, and C5H9ClO4 are observed as major gas- and particle-phase products. Modeling and experimental results show that the secondary OH–isoprene chemistry is significantly enhanced under high-NOx conditions, accounting for up to 40% of all isoprene oxidized and leading to the suppression of organic chloride formation. Chlorine-initiated oxidation of isoprene could serve as a source for multifunctional (chlorinated) organic oxidation products and SOA in both pristine and anthropogenically influenced environments.
Delhi is a megacity subject to high local anthropogenic emissions and long-range transport of pollutants. This work presents for the first time time-resolved estimates of hygroscopicity parameter (κ) ...and cloud condensation nuclei (CCN), spanning for more than a year, derived from chemical composition and size distribution data. As a part of the Delhi Aerosol Supersite (DAS) campaign, the characterization of aerosol composition and size distribution was conducted from January 2017 to March 2018. Air masses originating from the Arabian Sea (AS), Bay of Bengal (BB), and southern Asia (SA) exhibited distinct characteristics of time-resolved sub-micron non-refractory PM1 (NRPM1) species, size distributions, and CCN number concentrations. The SA air mass had the highest NRPM1 loading with high chloride and organics, followed by the BB air mass, which was more contaminated than AS, with a higher organic fraction and nitrate. The primary sources were identified as biomass-burning, thermal power plant emissions, industrial emissions, and vehicular emissions. The average hygroscopicity parameter (κ), calculated by the mixing rule, was approximately 0.3 (varying between 0.13 and 0.77) for all the air masses (0.32±0.06 for AS, 0.31±0.06 for BB, and 0.32±0.10 for SA). The diurnal variations in κ were impacted by the chemical properties and thus source activities. The total, Aitken, and accumulation mode number concentrations were higher for SA, followed by BB and AS. The mean values of estimated CCN number concentration (NCCN; 3669–28926 cm−3) and the activated fraction (af; 0.19–0.87), for supersaturations varying from 0.1 % to 0.8 %, also showed the same trend, implying that these were highest in SA, followed by those in BB and then those in AS. The size turned out to be more important than chemical composition directly, and the NCCN was governed by either the Aitken or accumulation modes, depending upon the supersaturation (SS) and critical diameter (Dc). af was governed mainly by the geometric mean diameter (GMD), and such a high af (0.71±0.14 for the most dominant sub-branch of the SA air mass – R1 – at 0.4 % SS) has not been seen anywhere in the world for a continental site. The high af was a consequence of very low Dc (25–130 nm, for SS ranging from 0.1 % to 0.8 %) observed for Delhi. Indirectly, the chemical properties also impacted CCN and af by impacting the diurnal patterns of Aitken and accumulation modes, κ and Dc. The high-hygroscopic nature of aerosols, high NCCN, and high af can severely impact the precipitation patterns of the Indian monsoon in Delhi, impact the radiation budget, and have indirect effects and need to be investigated to quantify this impact.
PDF
