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.
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.
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.
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.
Formaldehyde is an environmental and occupational chemical carcinogen implicated in the damage of proteins and nucleic acids. However, whether formaldehyde provokes modifications of RNAs such as ...8-oxo-7,8-dihydroguanine (8-oxoG) and the role that these modifications play on conferring long-term adverse health effects remains unexplored. Here, we profile 8-oxoG modifications using RNA-immunoprecipitation and RNA sequencing (8-oxoG RIP-seq) to identify 343 RNA transcripts heavily enriched in oxidations in human bronchial epithelial BEAS-2B cell cultures exposed to 1 ppm formaldehyde for 2 h. RNA oxidation altered expression of many transcripts involved in chromatin modification and p53-mediated DNA-damage responses, two pathways that play key roles in sustaining genome integrity and typically deregulated in tumorigenesis. Given that these observations were identified in normal cells exhibiting minimal cell stress and death phenotypes (for example, lack of nuclear shrinkage, F-actin alterations or increased LDH activity); we hypothesize that oxidative modification of specific RNA transcripts following formaldehyde exposure denotes an early process occurring in carcinogenesis analogous to the oxidative events surfacing at early stages of neurodegenerative diseases. As such, we provide initial investigations of RNA oxidation as a potentially novel mechanism underlying formaldehyde-induced tumorigenesis.
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 (NO x ) remain unexplored. Here, we investigate chlorine–isoprene reactions under low- and high-NO x 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-NO x 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, India, is the second most populated city in the world and routinely experiences some of the highest particulate matter concentrations of any megacity on the planet, posing acute challenges to ...public health (World Health Organization, 2018). However, the current understanding of the sources and dynamics of PM pollution in Delhi is limited. Measurements at the Delhi Aerosol Supersite (DAS) provide long-term chemical characterization of ambient submicron aerosol in Delhi, with near-continuous online measurements of aerosol composition. Here we report on source apportionment based on positive matrix factorization (PMF), conducted on 15 months of highly time-resolved speciated submicron non-refractory PM1 (NR-PM1) between January 2017 and March 2018. We report on seasonal variability across four seasons of 2017 and interannual variability using data from the two winters and springs of 2017 and 2018. We show that a modified tracer-based organic component analysis provides an opportunity for a real-time source apportionment approach for organics in Delhi. Phase equilibrium modeling of aerosols using the extended aerosol inorganics model (E-AIM) predicts equilibrium gas-phase concentrations and allows evaluation of the importance of the ventilation coefficient (VC) and temperature in controlling primary and secondary organic aerosol. We also find that primary aerosol dominates severe air pollution episodes, and secondary aerosol dominates seasonal averages.
Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O
...surface concentrations. Although iodic acid (HIO
) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO
via reactions (R1) IOIO + O
→ IOIO
and (R2) IOIO
+ H
O → HIO
+ HOI +
O
. The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO
in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.
Comprehensive identification of aerosol sources and their constituent organic compounds requires aerosol-phase molecular-level characterization with a high time resolution. While real-time chemical ...characterization of aerosols is becoming increasingly common, information about functionalization and structure is typically obtained from offline methods. This study presents a method for determining the presence of carboxylic acid functional groups in real time using extractive electrospray ionization mass spectrometry based on measurements of M – H + 2Na+ adducts. The method is validated and characterized using standard compounds. A proof-of-concept application to α-pinene secondary organic aerosol (SOA) shows the ability to identify carboxylic acids even in complex mixtures. The real-time capability of the method allows for the observation of the production of carboxylic acids, likely formed in the particle phase on short time scales (<120 min). Our research explains previous findings of carboxylic acids being a significant component of SOA and a quick decrease in peroxide functionalization following SOA formation. We show that the formation of these acids is commensurate with the increase of dimers in the particle phase. Our results imply that SOA is in constant evolution through condensed-phase processes, which lower the volatility of the aerosol components and increase the available condensed mass for SOA growth and, therefore, aerosol mass loading in the atmosphere. Further work could aim to quantify the effect of particle-phase acid formation on the aerosol volatility distributions.
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