Combustion-Derived Pollutants Linked with Kidney Disease in Low-Lying Flood-Affected Areas in the Balkans.

Tens of thousands of people in southern Europe suffer from Balkan endemic nephropathy (BEN), and four times as many are at risk. Incidental ingestion of aristolochic acids (AAs), stemming from the ubiquitousAristolochia clematitis(birthwort) weed in the region, leads to DNA adduct-induced toxicity in kidney cells, the primary cause of BEN. Numerous cofactors, including toxic organics and metals, have been investigated, but all have shown small contributions to the overall BEN relative to non-BEN village distribution gradients. Here, we reveal that combustion-derived pollutants from wood and coal burning in Serbia also contaminate arable soil and test as plausible causative factors of BEN. Using a GC-MS screening method, biomass-burning-derived furfural and coal-burning-derived medium-chain alkanes were detected in soil samples from BEN endemic areas levels at up to 63-times and 14-times higher, respectively, than in nonendemic areas. Significantly higher amounts were also detected in colocated wheat grains. Coexposure studies with cultured kidney cells showed that these pollutants enhance DNA adduct formation by AA, - the cause of AA nephrotoxicity and carcinogenicity. With the coincidence of birthwort-derived AAs and the widespread practice of biomass and coal burning for household cooking and heating purposes and agricultural burning in rural low-lying flood-affected areas in the Balkans, these results implicate combustion-derived pollutants in promoting the development of BEN.

Polyurethane Foam Face Masks as a Dosimeter for Quantifying Personal Exposure to Airborne Volatile and Semi-Volatile Organic Compounds.

Airborne volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) are commonly quantitated by collecting the analytes on solid sorbent tubes or passive air samplers, followed by solvent extraction and instrumental analysis, or by grab bag/canister measurements. We report herein a user-friendly sampling method by breathing through polyurethane foam (PUF) face masks to collect airborne VOCs and SVOCs for chemical analysis. Specifically, dibasic esters, phthalate esters, polycyclic aromatic hydrocarbons, linalool, and nicotine trapped on PUF masks were quantitated by gas chromatography-mass spectrometry analysis as model VOCs and SVOCs. Results showed that the amount of these model VOCs and SVOCs trapped on PUF masks is proportional to the exposure duration. After cross-validation by parallel sampling using XAD-2 packed sorbent tubes, the method was used to quantitate VOCs and SVOCs in a variety of indoor and outdoor environments with varying air concentrations of analytes, temperature, humidity, and wind speed. Because air pollution is considered a major cause of many human diseases and premature deaths and the developed PUF mask sampling method showed high trapping efficiencies for both VOCs and SVOCs, it is believed that the developed sampling method will find wide application in assessing air pollution-associated disease risks with possible extension to more classes of VOCs and SVOCs when coupled with suitable instrumental detection methods.

Multiscale Temporal Variations of Atmospheric Mercury Distinguished by the Hilbert-Huang Transform Analysis Reveals Multiple El Niño-Southern Oscillation Links.

Atmospheric mercury (Hg) cycling is sensitive to climate-driven changes, but links with various teleconnections remain unestablished. Here, we revealed the El Niño-Southern Oscillation (ENSO) influence on gaseous elemental mercury (GEM) concentrations recorded at a background station in East Asia using the Hilbert-Huang transform (HHT). The timing and magnitude of GEM intrinsic variations were clearly distinguished by ensemble empirical mode decomposition (EEMD), revealing the amplitude of the GEM concentration interannual variability (IAV) is greater than that for diurnal and seasonal variability. We show that changes in the annual cycle of GEM were modulated by significant IAVs at time scales of 2-7 years, highlighted by a robust GEM IAV-ENSO relationship of the associated intrinsic mode functions. With confirmation that ENSO modulates the GEM annual cycle, we then found that weaker GEM annual cycles may have resulted from El Niño-accelerated Hg evasion from the ocean. Furthermore, the relationship between ENSO and GEM is sensitive to extreme events (i.e., 2015-2016 El Niño), resulting in perturbation of the long-term trend and atmospheric Hg cycling. Future climate change will likely increase the number of extreme El Niño events and, hence, could alter atmospheric Hg cycling and influence the effectiveness evaluation of the Minamata Convention on Mercury.

Deployment of a mobile platform to characterize spatial and temporal variation of on-road fine particles in an urban area.

Traffic-related air pollutants (TRAPs) pose a serious health hazard for residents and commuters in urban areas. In this study, a real-time mobile monitoring system was deployed in Taipei, a typical East Asian city with an overlap of high population density, traffic, and special structures (e.g., viaducts), to capture the on-road TRAPs at different times of the day. In general, black carbon, ultrafine particles (UFPs), CO concentrations, and lung deposition surface area (LDSA) were positively correlated with traffic flow, and for PM2.5, a more independent fluctuating concentration was observed. During rush-hour periods, the mean concentrations of UFPs, PM2.5, and LDSA were 6.12 × 104 ± 3.83 × 104 cm-3, 23 ± 8 µg/m3, and 2.29 × 102 ± 1.20 × 102 µm2/cm3, respectively. Additionally, the UFP number concentration and LDSA were two times higher along the high-traffic commuting route than along the lower traffic route. Pollutants tended to accumulate at sites near viaducts and high buildings and were significantly influenced by vehicle composition. In this study, the ratio of LDSA to total particle surface area concentration was used as an indicator of the degree of particle irregularity, which was directly related to aging during transport.

On the Flip Side of Mask Wearing: Increased Exposure to Volatile Organic Compounds and a Risk-Reducing Solution.

Surgical masks have been worn by the public worldwide during the COVID-19 pandemic, yet hazardous chemicals in the petroleum-derived polymer layer of masks are currently ignored and unregulated. These organic compounds pose potential health risks to the mask wearer through dermal contact or inhalation. Here, we show that surgical masks from around the world are loaded with semivolatile and volatile organic compounds (VOCs), including alkanes, polycyclic aromatic hydrocarbons (PAHs), phthalate esters, and reactive carbonyls at ng to µg/mask levels. Naphthalene was the most abundant mask-borne PAH, accounting for over 80% of total PAH levels; acrolein, a mutagenic carbonyl, was detected in most of the mask samples, and di(2-ethylhexyl) phthalate, an androgen antagonist, was detected in one-third of the samples. Furthermore, there is large mask-to-mask variability of the residue VOCs, revealing the uneven quality of masks. We confirm that masks containing more residue VOCs lead to significantly higher exposure levels and associated disease risks to the wearer, which should warrant the attention of the general public and regulatory agencies. We find that heating the masks at 50 °C for as short as 60 min lowers the total VOC content by up to 80%, providing a simple method to limit our exposure to mask-borne VOCs.

Fabric Masks as a Personal Dosimeter for Quantifying Exposure to Airborne Polycyclic Aromatic Hydrocarbons.

In this study, we assessed the feasibility of using ordinary face masks as a sampling means to collect airborne polycyclic aromatic hydrocarbons (PAHs). Nonwoven fabric masks can trap three-ring or larger PAHs at a high efficiency (>70%) and naphthalene at ∼17%. The sampling method is quantitative as confirmed by comparison with the standard method of the National Institute for Occupational Safety and Health. In conjunction with sensitive fluorescence detection, the method was applied to quantify nine airborne PAHs in a range of indoor and outdoor environments. Wearing the mask for 2 h allowed quantification of individual PAHs as low as 0.07 ng/m3. The demonstration shows applicability of the method in monitoring PAHs down to ∼30-80 ng/m3 in university office and laboratory settings and up to ∼900 ng/m3 in an incense-burning temple. Compared with traditional filter-/sorbent tube-based approaches, which require a sampling pump, our new method is simple, convenient, and inexpensive. More importantly, it closely tracks human exposure down to the individual level, thus having great potential to facilitate routine occupational exposure monitoring and large-scale surveillance of PAH concentrations in indoor and outdoor environments.

Field Evidence of Fe-Mediated Photochemical Degradation of Oxalate and Subsequent Sulfate Formation Observed by Single Particle Mass Spectrometry.

In this work, we deployed a single particle aerosol mass spectrometer (SPAMS) at a suburban coastal site in Hong Kong from February 04 to April 17, 2013 to study individual oxalate particles and a monitor for aerosols and gases in ambient air (MARGA) to track the bulk oxalate concentrations in particle matter smaller than 2.5 µm in diameter (PM2.5). A shallow dip in the bulk oxalate concentration was consistently observed before 10:00 am in the morning throughout the observation campaign, corresponding to a 20% decrease in the oxalate concentration on average during the decay process. Such a decrease in PM oxalate was found to be coincident with a decrease in Fe-containing oxalate particles, providing persuasive evidence of Fe-mediated photochemical degradation of oxalate. Oxalate mixed with Fe and Fe_NaK particles, from industry sources, were identified as the dominant factors for oxalate decay in the early morning. We further found an increase of sulfate intensity by a factor of 1.6 on these individual Fe-containing particles during the oxalate decomposition process, suggesting a facilitation of sulfur oxidation. This is the first report on the oxalate-Fe decomposition process with individual particle level information and provides unique evidence to advance our current understanding of oxalate and Fe cycling. The present work also indicates the importance of anthropogenic sourced iron in oxalate-Fe photochemical processing. In addition, V-containing oxalate particles, from ship emissions, also showed evidence of morning photodegradation and need further attention since current models rarely consider photochemical processing of oxalate_V particles.

Aromatic formulas in ambient PM2.5 samples from Hong Kong determined using FT-ICR ultrahigh-resolution mass spectrometry.

Many aromatic compounds (e.g., polycyclic aromatic hydrocarbons (PAHs)) found in atmospheric aerosols are toxic and exist in both unsubstituted and substituted forms. Previous studies have mainly concentrated on investigating unsubstituted PAHs, leaving the substituted compounds largely uncharacterized. This study focuses on detection of both unsubstituted and substituted aromatics in ambient aerosol samples using ultrahigh-resolution mass spectrometry. Aerosol samples collected from roadside, urban, and suburban sites in Hong Kong were characterized by Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) coupled with atmospheric pressure photoionization (APPI) or electrospray ionization (ESI). In the APPI+ mode, 166 aromatic CH formulas (i.e., formulas containing C and H only and with a double bond equivalent (DBE) of 4 or higher) were determined through molecular formula calculations based on an accurate m/z determination. Among the determined aromatic CH formulas, 141 are possible alkylated monocyclic aromatic hydrocarbon (MAH) or PAH formulas, and account for ≥ 45% of the total intensity by aromatic CH+ formulas. Both APPI+ and ESI+ are effective in detecting nitroaromatics (i.e., CHO2N1 formulas and DBE ≥ 5). The two ionization modes provide complementary formula coverage, with formulas determined by APPI+ extending to higher DBE and those by ESI+ covering higher carbon numbers. Alkylated nitrobenzene compounds are the most abundant among nitroaromatics, and they, together with alkylated nitro-PAHs, account for > 80% of the total intensity of aromatic CHO2N+ formulas, indicating the importance of these compounds in real aerosol samples. Aromatic CHN+ and CHO+ formulas are also determined, confirming the atmospheric presence of some previously reported O- and N-containing aromatic compounds and revealing new possible formulas. The determination of aromatic organic formulas in this study provides useful guidance for future quantitative analysis of hazardous aromatic compounds. Future work is needed to determine the abundance and to study the toxicity of alkylated MAHs and PAHs outside the 16 US EPA priority PAH compounds. Graphical abstract.

Sulfate Formation Enhanced by a Cocktail of High NOx, SO2, Particulate Matter, and Droplet pH during Haze-Fog Events in Megacities in China: An Observation-Based Modeling Investigation.

In recent years in a few Chinese megacities, fog events lasting one to a few days have been frequently associated with high levels of aerosol loading characterized by high sulfate (as high as 30 µg m(-3)), therefore termed as haze-fog events. The concomitant pollution characteristics include high gas-phase mixing ratios of SO2 (up to 71 ppbv) and NO2 (up to 69 ppbv), high aqueous phase pH (5-6), and smaller fog droplets (as low as 2 µm), resulting from intense emissions from fossil fuel combustion and construction activities supplying abundant Ca(2+). In this work, we use an observation-based model for secondary inorganic aerosols (OBM-SIA) to simulate sulfate formation pathways under conditions of haze-fog events encountered in Chinese megacities. The OBM analysis has identified, at a typical haze-fogwater pH of 5.6, the most important pathway to be oxidation of S(IV) by dissolved NO2, followed by the heterogeneous reaction of SO2 on the aerosol surface. The aqueous phase oxidation of S(IV) by H2O2 is a very minor formation pathway as a result of the high NOx conditions suppressing H2O2 formation. The model results indicate that the unique cocktail of high fogwater pH, high concentrations of NO2, SO2, and PM, and small fog droplets are capable of greatly enhancing sulfate formation. Such haze-fog conditions could lead to rapid sulfate production at night and subsequently high PM2.5 in the morning when the fog evaporates. Sulfate formation is simulated to be highly sensitive to fogwater pH, PM, and precursor gases NO2 and SO2. Such insights on major contributing factors imply that reduction of road dust and NOx emissions could lessen PM2.5 loadings in Chinese megacities during fog events.

Gasified Grass and Wood Biochars Facilitate Plant Establishment in Acid Mine Soils.

Heavy metals in exposed mine tailings threaten ecosystems that surround thousands of abandoned mines in the United States. Biochars derived from the pyrolysis or gasification of biomass may serve as a valuable soil amendment to revegetate mine sites. We evaluated the ability of two biochars, produced by gasification of either Kentucky bluegrass seed screenings (KB) or mixed conifer wood (CW), to support the growth of plants in mine spoils from the abandoned Formosa and Almeda Mines in Oregon. To evaluate the potential for plant establishment in mine tailings, wheat was grown in tailings amended with biochar at rates ranging from 0 to 9% (w/w). Both KB and CW biochars promoted plant establishment by increasing soil pH, increasing concentrations of macro- and micronutrients, and decreasing the solubility and plant uptake of heavy metals. Formosa tailings required at least 4% biochar and Almeda soil required at least 2% biochar to promote healthy wheat growth. A complimentary experiment in which mine spoils were leached with simulated precipitation indicated that biochar amendment rates ≥4% were sufficient to neutralize the elution pH and reduce concentrations of potentially toxic elements (Zn, Cu, Ni, Al) to levels near or below concern. These findings support the use of gasified biochar amendments to revegetate acid mine soils.

An Atmospheric Constraint on the NO2 Dependence of Daytime Near-Surface Nitrous Acid (HONO).

Recent observations suggest a large and unknown daytime source of nitrous acid (HONO) to the atmosphere. Multiple mechanisms have been proposed, many of which involve chemistry that reduces nitrogen dioxide (NO2) on some time scale. To examine the NO2 dependence of the daytime HONO source, we compare weekday and weekend measurements of NO2 and HONO in two U.S. cities. We find that daytime HONO does not increase proportionally to increases in same-day NO2, i.e., the local NO2 concentration at that time and several hours earlier. We discuss various published HONO formation pathways in the context of this constraint.

Spatial and temporal patterns of dissolved nitrogen and phosphorus in surface waters of a multi-land use basin.

Research on relationships between dissolved nutrients and land-use at the watershed scale is a high priority for protecting surface water quality. We measured dissolved nitrogen (DN) and ortho-phosphorus (P) along 130 km of the Calapooia River (Oregon, USA) and 44 of its sub-basins for 3 years to test for associations with land-use. Nutrient concentrations were analyzed for spatial and seasonal patterns and for relationships with land-use and stream discharge. Ortho-P and DN were higher in lower-elevation sub-basins dominated by poorly drained soils and agricultural production compared with higher-elevation sub-basins dominated by well-drained soils and forests. Eight lower basins had at least one sample period with nitrate-N > 10 mg L(-1). The Calapooia River had lower concentrations of dissolved nutrients compared with lower sub-basins, often by an order of magnitude. Dissolved organic N represented a greater proportion of DN in the upper forested sub-basins. Seasonal nutrient concentrations had strong positive correlations to the percent of a sub-basin that was managed for agriculture in all seasons (p values ≤ 0.019) except summer. Results suggest that agricultural lands are contributing to stream nutrient concentrations. However, poorly drained soils in agricultural areas may also contribute to the strong relationships that we found between dissolved nutrients and agriculture.

A traffic-induced shift of ultrafine particle sources under COVID-19 soft lockdown in a subtropical urban area.

During the unprecedented COVID-19 city lockdown, a unique opportunity arose to dissect the intricate dynamics of urban air quality, focusing on ultrafine particles (UFPs) and volatile organic compounds (VOCs). This study delves into the nuanced interplay between traffic patterns and UFP emissions in a subtropical urban setting during the spring-summer transition of 2021. Leveraging meticulous roadside measurements near a traffic nexus, our investigation unravels the intricate relationship between particle number size distribution (PNSD), VOCs mixing ratios, and detailed vehicle activity metrics. The soft lockdown era, marked by a 20-27% dip in overall traffic yet a surprising surge in early morning motorcycle activity, presented a natural experiment. We observed a consequential shift in the urban aerosol regime: the decrease in primary emissions from traffic substantially amplified the role of aged particles and secondary aerosols. This shift was particularly pronounced under stagnant atmospheric conditions, where reduced dilution exacerbated the influence of alternative emission sources, notably solvent evaporation, and was further accentuated with the resumption of normal traffic flows. A distinct seasonal trend emerged as warmer months approached, with aromatic VOCs such as toluene, ethylbenzene, and xylene not only increasing but also significantly contributing to more frequent particle growth events. These findings spotlight the criticality of targeted strategies at traffic hotspots, especially during periods susceptible to weak atmospheric dilution, to curb UFP and precursor emissions effectively. As we stand at the cusp of widespread vehicle electrification, this study underscores the imperative of a holistic approach to urban air quality management, embracing the complexities of primary emission reductions and the resultant shifts in atmospheric chemistry.

Embedded information of aerosol type, hygroscopicity and scattering enhancement factor revealed by the relationship between PM2.5 and aerosol optical depth.

Satellite aerosol optical depth (AOD) provides an alternative way to depict the spatial distribution of near-surface PM2.5. In this study, a mathematical formulation of how PM2.5 is related to AOD is presented. When simplified to a linear equation, a functional dependence of the slope on the aerosol type, scattering enhancement factor f(RH), and boundary layer height is revealed, while the influence of the vertical aerosol profile is embedded in the intercept. Specifically, we focus on the effects of aerosol properties and employ a new aerosol index (Normalized Gradient Aerosol Index, NGAI) for classifying aerosol subtypes. The combination of AOD difference at shorter wavelengths over longer-wavelength AOD from AERONET data could distinguish and subclassify aerosol types previously indistinguishable by AE (i.e., urban-industrial pollution, U/I, and biomass burning, BB). AOD-PM2.5 regressions are performed on these aerosol subtypes at various relative humidity (RH) levels. The results suggest that BB aerosols are nearly hydrophobic until the RH exceeds 80 %, while the AOD-PM2.5 regressions for U/I depend on RH levels. Moreover, the scattering enhancement factor f(RH) can be calculated by taking the ratio of intercepts between dry and humidity conditions, which is proposed and tested for the first time in this study. Our results show an f(RH ≥ 80 %) of ∼2.6 for U/I-dominated aerosols, whereas the value is not over 1.5 for BB aerosols. The f(RH) can be further used to derive the optical hygroscopicity parameter (κsca), demonstrating that the NGAI can be used to exploit differences in aerosol hygroscopicity and improve the AOD-PM2.5 relationship.

Concurrent measurements of nitrate at urban and suburban sites identify local nitrate formation as a driver for urban episodic PM2.5 pollution.

Nitrate (NO3-) is often among the leading components of urban particulate matter (PM) during PM pollution episodes. However, the factors controlling its prevalence remain inadequately understood. In this work, we analyzed concurrent hourly monitoring data of NO3- in PM2.5 at a pair of urban and suburban locations (28 km apart) in Hong Kong for a period of two months. The concentration gradient in PM2.5 NO3- was 3.0 ± 2.9 (urban) vs. 1.3 ± 0.9 µg m-3 (suburban) while that for its precursors nitrogen oxides (NOx) was 38.1 vs 4.1 ppb. NO3- accounted for 45 % of the difference in PM2.5 between the sites. Both sites were characterized to have more available NH3 than HNO3. Urban nitrate episodes, defined as periods of urban-suburban NO3- difference exceeding 2 µg m-3, constituted 21 % of the total measurement hours, with an hourly NO3- average gradient of 4.2 and a peak value of 23.6 µg m-3. Our comparative analysis, together with 3-D air quality model simulations, indicates that the high NOx levels largely explain the excessive NO3- concentrations in our urban site, with the gas phase HNO3 formation reaction contributing significantly during the daytime and the N2O5 hydrolysis pathway playing a prominent role during nighttime. This study presents a first quantitative analysis that unambiguously shows local formation of NO3- in urban environments as a driver for urban episodic PM2.5 pollution, suggesting effective benefits of lowering urban NOx.

Humic-like substances (HULIS) in springtime aerosols at a high-altitude background station in the western North Pacific: Source attribution, abundance, and light-absorption.

Atmospheric humic-like substances (HULIS) are important components of biomass-burning (BB) emissions and highly associated with light-absorbing organic aerosols (often referred to as brown carbon). This study highlights the importance of BB-emitted HULIS aerosols in peninsular Southeast Asian outflow to the subtropical western North Pacific. We determined various key light-absorbing characteristics of HULIS i.e. mass absorption cross-section (MACHULIS), absorbing component of the refractive index (kHULIS), and absorption Ångström exponent (AAEHULIS) based on ground-based aerosol light absorption measurements along with HULIS concentrations in springtime aerosols at Lulin Atmospheric Background Station (LABS; 2862 m above mean sea level), which is a representative high-altitude remote site in the western North Pacific. Daily variations of HULIS (0.58-12.92 µg m-3) at LABS were mostly linked with the influence from incoming air-masses, while correlations with BB tracers and secondary aerosols indicated the attribution of primary and secondary sources. Stronger light absorption capability of HULIS was clearly evident from MACHULIS and kHULIS values at 370 nm, which were about ~1.5 times higher during BB-dominated days (1.16 ± 0.75 m2 g-1 and 0.05 ± 0.03, respectively) than that during non-BB days (0.77 ± 0.89 m2 g-1 and 0.03 ± 0.04, respectively). Estimates from a simple radiative transfer model showed that HULIS absorption can add as much as 15.13 W g-1 to atmospheric warming, and ~46% more during BB-dominated than non-BB period, highlighting that HULIS light absorption may significantly affect the Earth-atmosphere system and tropospheric photochemistry over the western North Pacific.

Particulate matter in a motorcycle-dominated urban area: Source apportionment and cancer risk of lung deposited surface area (LDSA) concentrations.

Source-apportioned particle concentrations are necessary to properly evaluate the health impacts of air pollution. In this study, a measurement station was established at an urban roadside in northern Taiwan to the investigate lung deposited surface area (LDSA) concentration, a relevant metric for the adverse health effects of aerosol exposure, along with PM1 and equivalent black carbon (eBC) concentrations, particle number concentration (PNC), and particle size distribution (PSD). Through positive matrix factorization and multi-linear regression analysis, we attributed 57% of LDSA to traffic emissions over the entire study. During rush hour, the motorcycle fraction increased to 0.83 and LDSA (77.6 ± 9.9 µm2/cm3) and PNC (14,000 ± 2400 particles/cm3) values peaked, while 74% of LDSA was attributed to traffic. The LDSA ratio, defined as the ratio of measured LDSA to that estimated from the particle size distribution with a spherical assumption, also increased, highlighting the greater degree of fractal morphology during rush hour. The relationship between LDSA emitted by traffic and PNC yielded a higher r2 (0.92) than the r2 between traffic LDSA and eBC (0.82). Finally, the excess lifetime cancer risk linked with traffic emission was 1.56 × 10-4 (i.e. 15.6 excess cancer cases for a population of 100,000 people) based on the LDSA apportionment results.

Insights into aerosol chemical composition and optical properties at Lulin Atmospheric Background Station (2862 m asl) during two contrasting seasons.

Continental outflows from peninsular Southeast Asia and East Asia dominate the widespread dispersal of air pollutants over subtropical western North Pacific during spring and autumn, respectively. This study analyses the chemical composition and optical properties of PM10 aerosols during autumn and spring at a representative high-altitude site, viz., Lulin Atmospheric Background Station (23.47°N, 120.87°E; 2862 m a.s.l.), Taiwan. PM10 mass was reconstructed and the contributions of major chemical components were also delineated. Aerosol scattering (σsp) and absorption (σap) coefficients were regressed on mass densities of major chemical components by assuming external mixing between them, and the site-specific mass scattering efficiency (MSE) and mass absorption efficiency (MAE) of individual components for dry conditions were determined. NH4NO3 exhibited the highest MSE among all components during both seasons (8.40 and 12.58 m2 g-1 at 550 nm in autumn and spring, respectively). (NH4)2SO4 and organic matter (OM) accounted for the highest σsp during autumn (51%) and spring (50%), respectively. Mean MAE (mean contribution to σap) of elemental carbon (EC) at 550 nm was 2.51 m2 g-1 (36%) and 7.30 m2 g-1 (61%) in autumn and spring, respectively. Likewise, the mean MAE (mean contribution to σap) of organic carbon (OC) at 550 nm was 0.84 m2 g-1 (64%) and 0.83 m2 g-1 (39%) in autumn and spring, respectively. However, a classification matrix, based on scattering Ångström exponent, absorption Ångström exponent, and single scattering albedo (ω), demonstrated that the composite absorbing aerosols were EC-dominated (with weak absorption; ω = 0.91-0.95) in autumn and a combination of EC-dominated and EC/OC mixture (with moderate absorption; ω = 0.85-0.92) in spring. This study demonstrates a strong link between chemical composition and optical properties of aerosol and provides essential information for model simulations to assess the imbalance in regional radiation budget with better accuracy over the western North Pacific.

Characterization of odorous industrial plumes by coupling fast and slow mass spectrometry techniques for volatile organic compounds.

This study aimed to develop a technique to chemically characterize odor issues in neighborhoods of designated industrial zones with pronounced emissions of volatile organic compounds (VOCs). Due to the elusive nature of odor plumes, speedy detection with sufficient sensitivity is required to capture the plumes. In this demonstration, proton-transfer-reaction mass spectrometry (PTR-MS) was used as the front-line detection tool in an industrial zone to guide sampling canisters for in-laboratory analysis of 106 VOCs by gas chromatography-mass spectrometry/flame ionization detector (GC-MS/FID). The fast but less accurate PTR-MS coupled with the slow but accurate GC-MS/FID method effectively eliminates the drawbacks of each instrument and fortifies the strength of both when combined. A 10-day PTR-MS field screening period was conducted to determine suitable trigger VOC species with exceedingly high mixing ratios that were likely the culprits of foul odors. Twenty canister samples were then collected, triggered by m/z 43, 61 (ethyl acetate, fragments, EA), m/z 73 (methyl ethyl ketone, MEK), or m/z 88 (morpholine) in all cases. Internal consistency was confirmed by the high correlation of critical species in the PTR-MS and trigger samples. Several long-lived halocarbons were exploited as the intrinsic internal reference for quality assurance. Oxygenated VOCs (OVOCs) accounted for 15%-75% of the total VOC mixing ratios in the triggered samples. However, EA and MEK, the most prominent OVOC species, did not appear to have common sources with morpholine, which presented with PTR-MS peaks incoherent with the other OVOCs. Nevertheless, these distinctive OVOC plumes were consistent with the multiple types of odor reported by the local residents. In contrast with the triggered sampling, random samples in the same industrial zone and roadside samples in a major metropolitan area were collected. The pronounced OVOC content in the triggered samples highlighted the advantage over random grab sampling to address odor issues.

Secondary inorganic aerosol chemistry and its impact on atmospheric visibility over an ammonia-rich urban area in Central Taiwan.

This study investigated the hourly inorganic aerosol chemistry and its impact on atmospheric visibility over an urban area in Central Taiwan, by relying on measurements of aerosol light extinction, inorganic gases, and PM2.5 water-soluble ions (WSIs), and simulations from a thermodynamic equilibrium model. On average, the sulfate (SO42-), nitrate (NO3-), and ammonium (NH4+) components (SNA) contributed ∼90% of WSI concentrations, which in turn made up about 50% of the PM2.5 mass. During the entire observation period, PM2.5 and SNA concentrations, aerosol pH, aerosol liquid water content (ALWC), and sulfur and nitrogen conversion ratios all increased with decreasing visibility. In particular, the NO3- contribution to PM2.5 increased, whereas the SO42- contribution decreased, with decreasing visibility. The diurnal variations of the above parameters indicate that the interaction and likely mutual promotion between NO3- and ALWC enhanced the hygroscopicity and aqueous-phase reactions conducive for NO3- formation, thus led to severely impaired visibility. The high relative humidity (RH) at the study area (average 70.7%) was a necessary but not sole factor leading to enhanced NO3- formation, which was more directly associated with elevated ALWC and aerosol pH. Simulations from the thermodynamic model depict that the inorganic aerosol system in the study area was characterized by fully neutralized SO42- (i.e. a saturated factor in visibility reduction) and excess NH4+ amidst a NH3-rich environment. As a result, PM2.5 composition was most sensitive to gas-phase HNO3, and hence NOx, and relatively insensitive to NH3. Consequently, a reduction of NOx would result in instantaneous cuts of NO3-, PM2.5, and ALWC, and hence improved visibility. On the other hand, a substantial amount of NH3 reduction (>70%) would be required to lower the aerosol pH, driving more than 50% of the particulate phase NO3- to the gas phase, thereby making NH3 a limiting factor in shifting PM2.5 composition.