Impact of Ship Emissions on Air Quality in the Greater Bay Area in China under the Latest Global Marine Fuel Regulation.

As the main anthropogenic source in open seas and coastal areas, ship emissions impact the climate, air quality, and human health. The latest marine fuel regulation with a sulfur content limit of 0.5% went into effect globally on January 1, 2020. Investigations of ship emissions after fuel switching are necessary. In this study, online field measurements at an urban coastal site and modeling simulations were conducted to detect the impact of ship emissions on air quality in the Greater Bay Area (GBA) in China under new fuel regulation. By utilizing a high mass-resolution single particle mass spectrometer, the vanadium(V) signal was critically identified and was taken as a robust indicator for ship-emitted particles (with relative peak area > 0.1). The considerable number fractions of high-V particles (up to 30-40% during ship plumes) indicated that heavy fuel oils via simple desulfurization or blending processes with low-sulfur fuels were extensively used in the GBA to meet the global 0.5% sulfur cap. Our results showed that ship-emitted particulate matter and NOx contributed up to 21.4% and 39.5% to the ambient, respectively, in the summertime, significantly affecting the air quality in the GBA. The sea-land breeze circulation also played an important role in the transport pattern of ship-emitted pollutants in the GBA.

Absorption Enhancement of Black Carbon Aerosols Constrained by Mixing-State Heterogeneity.

Atmospheric black carbon (BC) has a large yet highly uncertain contribution to global warming. When mixed with non-BC/coating material during atmospheric aging, the BC light absorption can be enhanced through the lensing effect. Laboratory and modeling studies have consistently found strong BC absorption enhancement, while the results in ambient measurements are conflicting, with some reporting weak absorption enhancement even for particles with large bulk coating amounts. Here, from our direct field observations, we report both large and minor absorption enhancement factors for different BC-containing particle populations with large bulk non-BC-to-BC mass ratios. By gaining insights into the measured coating material distribution across each particle population, we find that the level of absorption enhancement is strongly dependent on the particle-resolved mixing state. Our study shows that the greater mixing-state heterogeneity results in the larger difference between observed and predicted absorption enhancement. We demonstrate that by considering the variability in coating material thickness in the optical model, the previously observed model measurement discrepancy of absorption enhancement can be reconciled. The observations and improved optical models reported here highlight the importance of mixing-state heterogeneity on BC's radiative forcing, which should be better resolved in large-scale models to increase confidence when estimating the aerosol radiation effect.

Humidity Dependence of the Condensational Growth of α-Pinene Secondary Organic Aerosol Particles.

The influence of relative humidity (RH) on the condensational growth of organic aerosol particles remains incompletely understood. Herein, the RH dependence was investigated via a series of experiments for α-pinene ozonolysis in a continuously mixed flow chamber in which recurring cycles of particle growth occurred every 7 to 8 h at a given RH. In 5 h, the mean increase in the particle mode diameter was 15 nm at 0% RH and 110 nm at 75% RH. The corresponding particle growth coefficients, representing a combination of the thermodynamic driving force and the kinetic resistance to mass transfer, increased from 0.35 to 2.3 nm2 s-1. The chemical composition, characterized by O:C and H:C atomic ratios of 0.52 and 1.48, respectively, and determined by mass spectrometry, did not depend on RH. The Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) was applied to reproduce the observed size- and RH-dependent particle growth by optimizing the diffusivities Db within the particles of the condensing molecules. The Db values increased from 5 α-1 × 10-16 at 0% RH to 2 α-1 × 10-12 cm-2 s-1 at 75% RH for mass accommodation coefficients α of 0.1 to 1.0, highlighting the importance of particle-phase properties in modeling the growth of atmospheric aerosol particles.

Insights into the formation of secondary organic carbon in the summertime in urban Shanghai.

To investigate formation mechanisms of secondary organic carbon (SOC) in Eastern China, measurements were conducted in an urban site in Shanghai in the summer of 2015. A period of high O3 concentrations (daily peak > 120 ppb) was observed, during which daily maximum SOC concentrations exceeding 9.0 µg/(C·m3). Diurnal variations of SOC concentration and SOC/organic carbon (OC) ratio exhibited both daytime and nighttime peaks. The SOC concentrations correlated well with Ox (= O3 + NO2) and relative humidity in the daytime and nighttime, respectively, suggesting that secondary organic aerosol formation in Shanghai is driven by both photochemical production and aqueous phase reactions. Single particle mass spectrometry was used to examine the formation pathways of SOC. Along with the daytime increase of SOC, the number fraction of elemental carbon (EC) particles coated with OC quickly increased from 38.1% to 61.9% in the size range of 250-2000 nm, which was likely due to gas-to-particle partitioning of photochemically generated semi-volatile organic compounds onto EC particles. In the nighttime, particles rich in OC components were highly hygroscopic, and number fraction of these particles correlated well with relative humidity and SOC/OC nocturnal peaks. Meanwhile, as an aqueous-phase SOC tracer, particles that contained oxalate-Fe(III) complex also peaked at night. These observations suggested that aqueous-phase processes had an important contribution to the SOC nighttime formation. The influence of aerosol acidity on SOC formation was studied by both bulk and single particle level measurements, suggesting that the aqueous-phase formation of SOC was enhanced by particle acidity.

Internal exposure potential of water-soluble organic molecules in urban PM2.5 evaluated by non-covalent adductome of human serum albumin.

Water-soluble organic molecules (WSOMs) in inhaled PM2.5 can readily translocate from the lungs into the blood circulation, facilitating their distribution to and health effects on distant organs and tissues in the human body. Human serum albumin (HSA), the most abundant protein carrier in the blood, readily binds exogenous substances to form non-covalent adducts and subsequently transports them throughout the circulatory system, thereby indicating their internal exposure. The direct internal exposure of WSOMs in PM2.5 needs to be understood. In this study, the non-covalent HSA-WSOM adductome was developed as a dosimeter to evaluate the internal exposure potential of WSOMs in urban PM2.5. The WSOM composition was acquired from non-target high-resolution mass spectrometry analysis coupled with multiple ionizations. The binding level of HSA-WSOM non-covalent adducts was obtained from surface plasma resonance. Machine learning combined WSOM composition and the binding level of HSA-WSOM non-covalent adducts to screen bindable (also internalizable) WSOMs. The concentration of WSOM ranged from 4 to 13 µg/m3 during our observation period. Of the 17,513 mass spectral features detected, 9,484 contributed to the non-covalent adductome and possessed the internal exposure potential. 102 major contributors accounted for 90.6 % of the HSA-WSOM binding level. The fraction of internalizable WSOMs in PM2.5 varied from 11.9 % to 61.3 %, averaging 26.2 %. WSOMs that have internal exposure potential were primarily lignin-like and lipid-like substances. The HSA-WSOMs non-covalent adductome represents direct internal exposure potential, which can provide crucial insights into the molecular diagnosis of PM2.5 exposure and precise assessments of PM2.5 health effects.

Impact of antioxidants on PM2.5 oxidative potential, radical level, and cytotoxicity.

Antioxidants are typically seen as agents that mitigate environmental health risks due to their ability to scavenge free radicals. However, our research presents a paradox where these molecules, particularly those within lung fluid, act as prooxidants in the presence of airborne particulate matter (PM2.5), thus enhancing PM2.5 oxidative potential (OP). In our study, we examined a range of antioxidants found in the respiratory system (e.g., vitamin C, glutathione (GSH), and N-acetylcysteine (NAC)), in plasma (vitamin A, vitamin E, and ß-carotene), and in food (tert-butylhydroquinone (TBHQ)). We aimed to explore antioxidants' prooxidant and antioxidant interactions with PM2.5 and the resulting OP and cytotoxicity. We employed OH generation assays and electron paramagnetic resonance assays to assess the pro-oxidative and anti-oxidative effects of antioxidants. Additionally, we assessed cytotoxicity interaction using a Chinese hamster ovary cell cytotoxicity assay. Our findings revealed that, in the presence of PM2.5, all antioxidants except vitamin E significantly increased the PM2.5 OP by generating more OH radicals (OH generation rate: 0.16-24.67 pmol·min-1·m-3). However, it's noteworthy that these generated OH radicals were at least partially neutralized by the antioxidants themselves. Among the pro-oxidative antioxidants, vitamin A, ß-carotene, and TBHQ showed the least ability to quench these radicals, consistent with their observed impact in enhancing PM2.5 cytotoxicity (PM2.5 LC50 reduced to 91.2 %, 88.8 %, and 75.1 % of PM2.5's original level, respectively). Notably, vitamin A and TBHQ-enhanced PM2.5 OP were strongly associated with the presence of metals and organic compounds, particularly with copper (Cu) contributing significantly (35 %) to TBHQ's pro-oxidative effect. Our study underscores the potential health risks associated with the interaction between antioxidants and ambient pollutants.

Seasonal variation of driving factors of ambient PM2.5 oxidative potential in Shenzhen, China.

Reactive oxygen species (ROS) play a central role in health effects of ambient fine particulate matter (PM2.5). In this work, we screened for efficient and complementary oxidative potential (OP) measurements by comparing the response values of multiple chemical probes (OPDTT, OPOH, OPGSH) to ambient PM2.5 in Shenzhen, China. Combined with meteorological condition and PM2.5 chemical composition analysis, we explored the effects of different chemical components and emission sources on the ambient PM2.5 OP and analyzed their seasonal variations. The results show that OPmDTT(mass-normalized) and OPmGSH-SLF were highly correlated (r = 0.77). OPDTT was mainly influenced by organic carbon, while OPOH was highly dominated by heavy metals. The combination of OPDTT and OPOH provides an efficient and comprehensive measurement of OP. Temporally, the OPs were substantially higher in winter than in summer (1.4 and 4 times higher for OPmDTT and OPmOH, respectively). The long-distance transported biomass burning sources from the north dominated the OPDTT in winter, while the ship emissions mainly influenced the summer OP. The OPmDTT increased sharply with the decrease of PM2.5 mass concentration, especially when the PM2.5 concentration was lower than 30 µg/m3. The huge differences in wind fields between the winter and summer cause considerable variations in PM2.5 concentrations, components, and OP. Our work emphasizes the necessity of long-term, multi-method, multi-component assessment of the OP of PM2.5.