Important Roles and Formation of Atmospheric Organosulfates in Marine Organic Aerosols: Influence of Phytoplankton Emissions and Anthropogenic Pollutants.

Organosulfates (OSs) could be potentially important compounds in marine organic aerosols, while their formation in marine atmospheres is far from clear due to a lack of cruise observations. In this work, shipboard atmospheric observations were conducted over the Yellow Sea and Bohai Sea to investigate the abundance and formation of biogenic isoprene/monoterpene-OSs in marine aerosols. The quantified OSs and NOSs accounted for 0.04-6.9% of marine organic aerosols and were 0.07-2.2% of the non-sea-salt (nss) sulfate in terms of sulfur content. Isoprene-related (nitrooxy-)OSs occupied 27-87% of the total quantified OSs, following the abundance order of summer > autumn > spring or winter. This order was driven by the marine phytoplankton biomass and sea surface temperature (SST), which controlled the seawater and atmospheric isoprene concentration levels. Under the severe impacts of anthropogenic pollutants from the East Asia continent in winter, monoterpene nitrooxy-OSs, generated with NOx involved in, increased to 34.4 ± 35.5 ng/m3 and contributed 68% of the quantified (nitrooxy-)OSs. Our results highlight the notable roles of biogenic OSs in marine organic aerosols over regions with high biological activity and high SST. The formation of biogenic OSs and their roles in altering marine aerosol properties calls for elaboration through cruise observations in different marine environments.

Global impact of atmospheric arsenic on health risk: 2005 to 2015.

Arsenic is a toxic pollutant commonly found in the environment. Most of the previous studies on arsenic pollution have primarily focused on arsenic contamination in groundwater. In this study, we examine the impact on human health from atmospheric arsenic on the global scale. We first develop an improved global atmospheric arsenic emission inventory and connect it to a global model (Goddard Earth Observing System [GEOS]-Chem). Model evaluation using observational data from a variety of sources shows the model successfully reproduces the spatial distribution of atmospheric arsenic around the world. We found that for 2005, the highest airborne arsenic concentrations were found over Chile and eastern China, with mean values of 8.34 and 5.63 ng/m3, respectively. By 2015, the average atmospheric arsenic concentration in India (4.57 ng/m3) surpassed that in eastern China (4.38 ng/m3) due to the fast increase in coal burning in India. Our calculation shows that China has the largest population affected by cancer risk due to atmospheric arsenic inhalation in 2005, which is again surpassed by India in 2015. Based on potential exceedance of health-based limits, we find that the combined effect by including both atmospheric and groundwater arsenic may significantly enhance the risks, due to carcinogenic and noncarcinogenic effects. Therefore, this study clearly implies the necessity in accounting for both atmospheric and groundwater arsenic in future management.

Aerosol Iron Solubility Specification in the Global Marine Atmosphere with Machine Learning.

Aerosol iron (Fe) solubility is a key factor for the assessment of atmospheric nutrients input to the ocean but poorly specified in models because the mechanism of determining the solubility is unclear. We develop a deep learning model to project the solubility based on the data that we observed in a coastal city of China. The model has five variables: the size range of particles, relative humidity, and the ratios of sulfate, nitrate and oxalate to total Fe (TFe) contents in aerosol particles. Results show excellent statistical agreements with the solubility in the literature over most worldwide seas and margin areas with the Pearson correlation coefficients (r) as large as 0.73-0.97. The exception is the Atlantic Ocean, where good agreement is obtained with the model trained using local data (r: 0.34-0.66). The model further uncovers that the ratio of oxalate/TFe is the most important variable influencing the solubility. These results indicate the feasibility of treating the solubility as a function of the six factors in deep learning models with careful training and validation. Our model and projected solubility provide innovative options for better quantification of air-to-sea input of aerosol soluble Fe in observational and model studies in the global marine atmosphere.

Competitive Uptake of Dimethylamine and Trimethylamine against Ammonia on Acidic Particles in Marine Atmospheres.

Alkaline gases such as NH3 and amines play important roles in neutralizing acidic particles in the atmosphere. Here, two common gaseous amines (dimethylamine (DMA) and trimethylamine (TMA)), NH3, and their corresponding ions in PM2.5 were measured semicontinuously using an ambient ion monitor-ion chromatography (AIM-IC) system in marine air during a round-trip cruise of approximately 4000 km along the coastline of eastern China. The concentrations of particulate DMA, detected as DMAH+, varied from <4 to 100 ng m-3 and generally decreased with increasing atmospheric NH3 concentrations. Combining observations with thermodynamic equilibrium calculations using the extended aerosol inorganics model (E-AIM) indicated that the competitive uptake of DMA against NH3 on acidic aerosols generally followed thermodynamic equilibria and appeared to be sensitive to DMA/NH3 molar ratios, resulting in molar ratios of DMAH+ to DMA + DMAH+ of 0.31 ± 0.16 (average ± standard deviation) at atmospheric NH3 concentrations over 1.8 µg m-3 (with a corresponding DMA/NH3 ratio of (1.8 ± 1.0) × 10-3), 0.80 ± 0.15 at atmospheric NH3 concentrations below 0.3 µg m-3 (with a corresponding DMA/NH3 ratio of (1.3 ± 0.6) × 10-2), and 0.56 ± 0.19 in the remaining cases. Particulate TMA concentrations, detected as TMAH+, ranged from <2 to 21 ng m-3 and decreased with increasing concentrations of atmospheric NH3. However, TMAH+ was depleted concurrently with the formation of NH4NO3 under low concentrations of atmospheric NH3, contradictory to the calculated increase in the equilibrated concentration of TMAH+ by the E-AIM.

Development and Assessment of a High-Resolution Biogenic Emission Inventory from Urban Green Spaces in China.

Biogenic volatile organic compound (BVOC) emissions have long been known to play vital roles in modulating the formation of ozone and secondary organic aerosols (SOAs). While early studies have evaluated their impact globally or regionally, the BVOC emissions emitted from urban green spaces (denoted as U-BVOC emissions) have been largely ignored primarily due to the failure of low-resolution land cover in resolving such processes, but also because their important contribution to urban BVOCs was previously unrecognized. In this study, by utilizing a recently released high-resolution land cover dataset, we develop the first set of emission inventories of U-BVOCs in China at spatial resolutions as high as 1 km. This new dataset resolved densely distributed U-BVOCs in urban core areas. The U-BVOC emissions in megacities could account for a large fraction of total BVOC emissions, and the good agreement of the interannual variations between the U-BVOC emissions and ozone concentrations over certain regions stresses their potentially crucial role in influencing ozone variations. The newly constructed U-BVOC emission inventory is expected to provide an improved dataset to enable the research community to re-examine the modulation of BVOCs on the formation of ozone, SOA, and atmospheric chemistry in urban environments.

Nonlinear effect of air pollution on adult pneumonia hospital visits in the coastal city of Qingdao, China: A time-series analysis.

Many studies have illustrated adverse effects of short-term exposure to air pollution on human health, which usually assumes a linear exposure-response (E-R) function in the delineation of health effects due to air pollution. However, nonlinearity may exist in the association between air pollutant concentrations and health outcomes such as adult pneumonia hospital visits, and there is a research gap in understanding the nonlinearity. Here, we utilized both the distributed lag model (DLM) and nonlinear model (DLNM) to compare the linear and nonlinear impacts of air pollution on adult pneumonia hospital visits in the coastal city of Qingdao, China. While both models show adverse effects of air pollutants on adult pneumonia hospital visits, the DLNM shows an attenuation of E-R curves at high concentrations. Moreover, the DLNM may reveal delayed health effects that may be missed in the DLM, e.g., ozone exposure and pneumonia hospital visits. With the stratified analysis of air pollutants on adult pneumonia hospital visits, both models consistently reveal that the influence of air pollutants is higher during the cold season than during the warm season. Nevertheless, they may behave differently in terms of other subgroups, such as age, gender and visit types. For instance, while no significant impact due to PM2.5 in any of the subgroups abovementioned emerges based on DLM, the results from DLNM indicate statistically significant impacts for the subgroups of elderly, female and emergency department (ED) visits. With respect to adjustment by two-pollutants, PM10 effect estimates for pneumonia hospital visits were the most robust in both DLM and DLNM, followed by NO2 and SO2 based on the DLNM. Considering the estimated health effects of air pollution relying on the assumed E-R functions, our results demonstrate that the traditional linear association assumptions may overlook some potential health risks.

Weakened fertilization impact of anthropogenic aerosols on marine phytoplankton-A comparative analysis of dust and haze particles.

Although increases in air pollutants are changing chemical compositions of atmosphere, the resultant impacts on marine biogeochemistry remains elusive. We performed a collective analysis of 12 microcosm experimental data concerning treatments of dust particles (DPs, typically mineral aerosols), haze particles (HPs, typically anthropogenic aerosols), and various nutrients in varying trophic seawaters of the Northwest Pacific Ocean. The addition of DPs and HPs generally stimulated phytoplankton growth, as indicated by total chlorophyll a (Chl a), and shifted the phytoplankton size structure towards larger cells (> 2 µm in cell size), as indicated by size-fractionated Chl a. We further found that DP/HP-derived Chl a increase relative to the control (RCChl a) was proportional to the proportion of nitrogen (N) supplied by DPs/HPs relative to the baseline N concentration in seawater (PSN) and was higher than that in the N alone treatment when the PSN exceeded ~480%. The enhanced utilization of dissolved organic P potentially contributed to the stimulation of DPs/HPs. The slope of fitted line based on RCChl a and PSN in the DP treatments (0.14) was higher than that in the HP treatments (0.11). When the particle loading was extremely high (2 mg L-1), the addition of HPs exhibited an obvious inhibition impact on phytoplankton and was adverse to the shift of the size structure towards larger cells. These results suggest that the impact of HPs on phytoplankton is a composite result of stimulation by nutrients and inhibition by toxic matter, which may affect carbon sequestration efficiency in the ocean by regulating phytoplankton biomass and size structure.

Alterations in microbial community during the remediation of a black-odorous stream by acclimated composite microorganisms.

Microbial application is an efficient, economical, and ecofriendly method for remediating black-odorous rivers. In this study, the field treatment effect and microbial community changes were monitored during remediation by the acclimated complex microorganisms of a typical black-odorous stream. After the treatment, the total phosphorus and ammonia contents decreased by 74.0% and 76.3% and the concentrations of dissolved oxygen increased from 1.65 to 4.90 mg/L, indicating the effectiveness of the acclimated composite microorganisms. The proportion of Bacteroidetes decreased significantly by 48.1% and that of Firmicutes increased by 2.23% on average, and the microbial diversity index first increased and then tended to be uniform. Redundancy analysis demonstrated that the pH, dissolved oxygen, and oxidation-reduction potential together determined the composition of the microbial communities (p < 0.05). These findings showed that the acclimated composite microorganisms can effectively remediate the black odor.

Process analysis of PM2.5 pollution events in a coastal city of China using CMAQ.

US EPA's Community Multiscale Air Quality modeling system (CMAQ) with Process Analysis tool was used to simulate and quantify the contribution of individual atmospheric processes to PM2.5 concentration in Qingdao during three representative PM2.5 pollution events in the winter of 2015 and 2016. Compared with the observed surface PM2.5 concentrations, CMAQ could reasonably reproduce the temporal and spatial variations of PM2.5 during these three events. Process analysis results show that primary emissions accounted for 72.7%-93.2% of the accumulation of surface PM2.5 before and after the events. When the events occurred, primary emissions were still the major contributor to the increase of PM2.5 in Qingdao, however the contribution percentage reduced significantly, which only account for 51.4%-71.8%. Net contribution from horizontal and vertical transport to the accumulation of PM2.5 was also positive and its percentage increased when events occurred. Only 1.1%-4.6% of aerosol accumulation was due to PM processes and aqueous chemical processes before and after events. When the events occurred, contribution from PM processes and aqueous chemistry increased to 6.0%-11.8%. Loss of PM2.5 was mainly through horizontal transport, vertical transport and dry deposition, no matter during or outside the events. Wet deposition would become the main removal pathway of PM2.5, when precipitation occurred.

Real-World Emission Factors of Gaseous and Particulate Pollutants from Marine Fishing Boats and Their Total Emissions in China.

Pollutants from fishing boats have generally been neglected worldwide, and there is an acute shortage of measured emission data, especially in China. Therefore, on-board measurements of pollutants emitted from 12 different fishing boats in China (including gill net, angling, and trawler boats) were carried out in this study to investigate emission factors (EFs), characteristics and total emissions. The average EFs for CO2, CO, NO x, PM, and SO2 were 3074 ± 55.9, 50.6 ± 31.7, 54.2 ± 30.7, 9.54 ± 2.24, and 5.94 ± 6.38 g (kg fuel)-1, respectively, which were higher than those from previous studies of fishing boats. When compared to medium-speed and slow-speed engine vessels, high-speed engines on fishing boats had higher CO EFs but lower NO x EFs. Notably, when fishing boats were in low-load conditions, they always had higher EFs of CO, PM, and NO2 compared to other operating modes. The estimated results showed that emissions from motor-powered fishing boats in China in 2012 (232, 379, and 61.8 kt CO, NO x and PM) accounted for 10.7%, 10.9%, and 19.3% of the total CO, NO x and PM emitted from nonroad mobile sources, which means significant contribution of fishing boats to air pollution, especially in southern China areas.

Identification of Major Sources of Atmospheric NH3 in an Urban Environment in Northern China During Wintertime.

To assess the relative contributions of traffic emission and other potential sources to high levels of atmospheric ammonia (NH3) in urban areas in the wintertime, atmospheric NH3 and related pollutants were measured at an urban site, ∼300 m from a major traffic road, in northern China in November and December 2015. Hourly average NH3 varied from 0.3 to 10.8 ppb with an average of 2.4 ppb during the campaign. Contrary to the common perspective in literature, traffic emission was demonstrated to be a negligible contributor to atmospheric NH3. Atmospheric NH3 correlated well with ambient water vapor during many time periods lasting from tens of hours to several days, implying NH3 released from water evaporation is an important source. Emissions from local green space inside the urban areas were identified to significantly contribute to the observed atmospheric NH3 during ∼60% of the sampling times. Evaporation of predeposited NHx through wet precipitation combined with emissions from local green space likely caused the spikes of atmospheric NH3 mostly occurring 1-4 h after morning rush hours or after and during slight shower events. There are still ∼30% of the data samples with appreciable NH3 level for which major contributors are yet to be identified.

Size and elemental composition of dry-deposited particles during a severe dust storm at a coastal site of Eastern China.

Dry-deposited particles were collected during the passage of an extremely strong dust storm in March, 2010 at a coastal site in Qingdao (36.15 °N, 120.49 °E), a city located in Eastern China. The size, morphology, and elemental composition of the particles were quantified with a scanning electron microscope equipped with an energy dispersive X-ray instrument (SEM-EDX). The particles appeared in various shapes, and their size mainly varied from 0.4 to 10 µm, with the mean diameters of 0.5, 1.5, and 1.0 µm before, during, and after the dust storm, respectively. The critical size of the mineral particles settling on the surface in the current case was about 0.3-0.4 µm before the dust storm and about 0.5-0.7 µm during the dust storm. Particles that appeared in high concentration but were smaller than the critical size deposited onto the surface at a small number flux. The elements Al, Si and Mg were frequently detected in all samples, indicating the dominance of mineral particles. The frequency of Al in particles collected before the dust storm was significantly lower than for those collected during and after the dust storm. The frequencies of Cl and Fe did not show obvious changes, while those of S, K and Ca decreased after the dust arrival. These results indicate that the dust particles deposited onto the surface were less influenced by anthropogenic pollutants in terms of particle number.

Sources and characteristics of fine particles over the Yellow Sea and Bohai Sea using online single particle aerosol mass spectrometer.

Marine aerosols over the East China Seas are heavily polluted by continental sources. During the Chinese Comprehensive Ocean Experiment in November 2012, size and mass spectra of individual atmospheric particles in the size range from 0.2 to 2.0 µm were measured on board by a single particle aerosol mass spectrometer (SPAMS). The average hourly particle number (PN) was around 4560±3240 in the South Yellow Sea (SYS), 2900±3970 in the North Yellow Sea (NYS), and 1700±2220 in the Bohai Sea (BS). PN in NYS and BS varied greatly over 3 orders of magnitude, while that in SYS varied slightly. The size distributions were fitted with two log-normal modes. Accumulation mode dominated in NYS and BS, especially during episodic periods. Coarse mode particles played an important role in SYS. Particles were classified using an adaptive resonance theory based neural network algorithm (ART-2a). Six particle types were identified with secondary-containing, aged sea-salt, soot-like, biomass burning, fresh sea-salt, and lead-containing particles accounting for 32%, 21%, 18%, 16%, 4%, and 3% of total PN, respectively. Aerosols in BS were relatively enriched in particles from anthropogenic sources compared to SYS, probably due to emissions from more developed upwind regions and indicating stronger influence of continental outflow on marine environment. Variation of source types depended mainly on origins of transported air masses. This study examined rapid changes in PN, size distribution and source types of fine particles in marine atmospheres. It also demonstrated the effectiveness of high-time-resolution source apportionment by ART-2a.

Dry deposition of PM10 over the Yellow Sea during Asian dust events from 2001 to 2007.

Dry deposition velocities and fluxes of PM10 during Asian dust events over the Yellow Sea from 2001 to 2007 were investigated using observation data in Qingdao, China and Jeju, Korea. The dry deposition velocities of PM10 during dust events over the Yellow Sea ranged from 0.19 to 8.17 cm/sec, with an average of 3.38 cm/sec. Dry deposition fluxes of PM10 during dust events over the Yellow Sea were in the range of 68.5-2647.1 mg/(m2 x day), with an average of 545.4 mg/(m2 x day), which is 2-10 times higher than those reported by other studies for both dust and non-dust periods. It was estimated that 2.6 x 10(11) -48.7 x 10(11) g dust particles deposit to the Yellow Sea during dust events through dry deposition every year. Compared with the results in previous studies, it was found that the dry deposition of PM10 over the Yellow Sea during dust events in the years with high frequency of dust could account for a large or overwhelming fraction of the annual total dry deposition. Backward air mass trajectory analysis showed that dust events influenced Jeju mainly originated from the desert regions located in Mongolia and Inner Mongolia, China. There were 119 backward trajectories influenced both Qingdao and Jeju during 15 dust events from 2001 to 2007, accounting for 61.3% of the total trajectories of 194, indicating that Qingdao and Jeju were usually on the same pathway of dust transport downwind from source areas.

Settling velocity of atmospheric particles in seawater: Based on hydrostatic sedimentation method using video imaging techniques.

When atmospheric particles deposit to the ocean, their settling velocities and residence times associated are critical for their effects on oceanic ecosystems. We developed a hydrostatic sedimentation method using video imaging techniques to track particles of 5-20 µm in diameter falling into seawater and determine the particle settling velocities in relation to their diameter, shape, organic matter contained, and seawater salinity. The measured settling velocities varied from 0.025 to 0.41 mm/s. Irregular particle shape and organic matter contained in particles also, however, reduced the values. The settling velocities were decelerated by the dissolution process of particle in seawater. Combined with the experimental results, a formula for calculating the settling velocity formulae for atmospheric particles was estimated. Using this equation, the residence time of particles is estimated to be less than one month in continental shelf sea and more than 100 days in the oceans.

Statistical analysis and environmental impact of pre-existing particle growth events in a Northern Chinese coastal megacity: A 725-day study in 2010-2018.

Pre-existing particles usually constitute the major fraction of atmospheric particles, except during some episodes in the presence of strong emissions and/or secondary generation of fresh particles. Previous case studies have investigated the growth of pre-existing particles and their potential environmental and climate impacts. However, there is limited knowledge about the statistical characteristics of these growth events and related effects. In this study, we examine pre-existing particle growth events using a large dataset (725 days from 2010 to 2018) collected at a coastal megacity in northern China. The occurrence frequency of pre-existing particle growth events was 12.4 % (90 out of 725 days). When these events were related to measured criteria air pollutants, no significant differences were found in PM2.5, SO2, NO2 and NO2 + O3 concentrations between periods with and without pre-existing particle growth events. These 90-day events can be further classified into two categories, i.e., Category 1, with 68 % of events representing the growth of pre-existing particles alone, and Category 2, with 32 % of events representing the simultaneous growth of pre-existing and newly formed particles. In Category 2, the growth rates of pre-existing particles and newly formed particles were close in 21 % of the cases, while pre-existing particles exhibited significantly larger growth rates in 69 % of the cases. Conversely, in 10 % of the cases, the growth rates of newly formed particles were larger. The different growth rate mechanisms were discussed in terms of the volatility of atmospheric condensation vapors. In addition, we present case studies on the impact of pre-existing particle growth on cloud condensation nuclei simultaneously measured, specifically considering the chemistry of condensation vapors and pre-existing particles.

Atmospheric deposition and river runoff stimulate the utilization of dissolved organic phosphorus in coastal seas.

In coastal seas, the role of atmospheric deposition and river runoff in dissolved organic phosphorus (DOP) utilization is not well understood. Here, we address this knowledge gap by combining microcosm experiments with a global approach considering the relationship between the activity of alkaline phosphatases and changes in phytoplankton biomass in relation to the concentration of dissolved inorganic phosphorus (DIP). Our results suggest that the addition of aerosols and riverine water stimulate the biological utilization of DOP in coastal seas primarily by depleting DIP due to increasing nitrogen concentrations, which enhances phytoplankton growth. This "Anthropogenic Nitrogen Pump" was therefore identified to make DOP an important source of phosphorus for phytoplankton in coastal seas but only when the ratio of chlorophyll a to DIP [Log10 (Chl a / DIP)] is larger than 1.20. Our study therefore suggests that anthropogenic nitrogen input might contribute to the phosphorus cycle in coastal seas.

Atmospheric dry deposition fluxes of trace metals over the Eastern China Marginal Seas: Impact of emission controls.

Atmospheric deposition is an important exogenous input of trace metals to Eastern China Marginal Seas (ECMS), which is strongly affected by human activities. With emission control practices implemented in China, it still remains unknown what changes have taken place in the atmospheric dry depositions of the trace metals over ECMS. This study aimed to estimate the atmospheric dry depositions of Zn, Pb, Cu, and Cd over ECMS via Weather Research and Forecasting Model-Community Multiscale Air Quality Modeling System (WRF-CMAQ) in the two winter periods of January 2012 and January 2019 as well as to explore the impacts of emission control on the depositions. The anthropogenic metal emissions from China, the Korean Peninsula, Japan, and marine ships were investigated in this study. In 2012, the dry deposition fluxes of Zn, Pb, Cu, and Cd over ECMS were in the ranges of 0.50-3.4 µg m-2 d-1, 0.22-1.9 µg m-2 d-1, 0.14-0.90 µg m-2 d-1, and 12-88 ng m-2 d-1, respectively. The deposition fluxes of the four metals over Bohai Sea (BS) and Yellow Sea (YS) were 2-3 times those over East China Sea (ECS). Outflow of polluted air masses from East Asia increased the metal depositions by 3- 5-fold relative to clear days. Compared with 2012, a 5-85 % reduction in the metal depositions over ECMS were estimated in 2019, largest reductions were found over YS and BS. Meteorological variation was able to decrease or increase the metal depositions. However, the emission control only caused a reduction in the entire study region. The metal inputs to the sea were significantly lower from the ship emissions than from the continental anthropogenic emissions, although the proportion of the ship emissions in the total metal depositions rose slightly from 2012 to 2019.

Interannual variations in the nutrient cycle in the central Bohai Sea in response to anthropogenic inputs.

In recent decades, there has been growing concern regarding the effects of human activities on the coastal nutrient cycle. However, interannual variations in the coastal nutrient cycle in response to anthropogenic nutrient input have rarely been quantified. In this study, a hydrodynamic-ecological model capable of describing the nitrogen and phosphorus cycles was used to analyze interannual variations in the nutrient cycle in the central Bohai Sea, a typical semi-enclosed sea in the Northwest Pacific. The results showed an increasing trend of dissolved inorganic nitrogen and particulate nitrogen from 1998 to 2017, whereas different forms of phosphorus showed no obvious interannual variations. The annual nutrient budgets were also quantitatively estimated from 1998 to 2017. This indicates that atmospheric nitrogen deposition plays an important role in interannual variations in the nitrogen cycle. A large amount of nitrogen from anthropogenic inputs was mainly removed by sedimentation processes instead of increasing the standing stock of nitrogen in the sea. With the reduction of anthropogenic inputs, the model showed that a variety of forms of nitrogen concentration decreased linearly, whereas phosphorus concentration increased slightly. Therefore, although environmental governance can effectively alleviate water eutrophication, it is necessary to avoid the situation where the dissolved inorganic nitrogen concentration in the sea becomes too low for phytoplankton to grow, which may determine the primary productivity and eventually affect fishery resources.