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.

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.

Isotopic comparison of ammonium between two summertime field campaigns in 2013 and 2021 at a background site of North China.

Ammonia (NH3) is the primary atmospheric alkaline gas, playing a crucial role in the atmospheric chemistry. Recently, non-agricultural emissions have been identified as the dominant sources of NH3 in urban areas. However, few studies have quantified the contributions of different sources to regional NH3. This study conducted two summertime field observations in 2013 and 2021 at a background site of North China to comprehensively explore the regional variations in concentration, nitrogen isotope composition (δ15N), and sources of ammonium (NH4+). The results indicate that NHx (NHx = NH3 + NH4+) concentration has increased in 2021, but the fNH4+ (NH4+/ NHx) has decreased significantly. The δ15N-NH4+ values show a significant increase, ranging from -4.7 ± 8.1 ‰ to +12.0 ± 2.4 ‰. The increase can be attributed to two primary factors: changes in fNH4+ resulting from the reduction of atmospheric acid gases and alterations in the sources of NH3. Bayesian simulation analysis reveals substantial variations in NH3 sources between 2013 and 2021 observations. Non-agricultural sources have significantly increased their contribution to NHx concentration, with vehicle exhaust and NH3 slip experiencing growth rates of 187 % and 104 %, respectively. Our results confirm the dominate contribution of non-agricultural sources to regional NH3 at the present stage and propose relevant mitigation strategies, which would provide essential insights for reducing NH3 emissions in North China.

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.

Phosphorus and its solubility in aerosols from continental and marine sources in the sea areas near China: Results from a 40-day cruise mission in late spring.

Accurate assessments of soluble phosphorus (P) in aerosol particles are essential to understand the atmospheric nutrients supply to the marine ecosystem. We quantified total P (TP) and dissolved P (DP) in the aerosol particles collected in the sea areas near China in a cruise mission from May 1 to June 11, 2016. The overall concentrations of TP and DP were 3.5-99.9 ng m-3 and 2.5-27.0 ng m-3, respectively. When the air originating from the desert areas, TP and DP were 28.7-99.9 ng m-3 and 10.8-27.0 ng m-3, respectively, and P solubility was 24.1-54.6 %. When the air influenced mainly by anthropogenic emissions from eastern China, TP and DP were 11.7-12.3 ng m-3 and 5.7-6.3 ng m-3, respectively, and P solubility was 46.0-53.7 %. More than half of the TP and more than 70 % of the DP were from pyrogenic particles, with a considerable DP converted via aerosol acidification after the particles met humid marine air. On average, aerosol acidification promoted the fractional solubility of dissolved inorganic P (DIP) to TP from 22 % to 43 %. When the air originating from the marine areas, TP and DP were 3.5-22.0 ng m-3 and 2.5-8.4 ng m-3, respectively, and P solubility was 34.6-93.6 %. About one-third of the DP was from biological emissions in organic forms (DOP), leading to higher solubility than in the particles from continental sources. These results reveal the dominance of inorganic P in TP and DP from the desert and anthropogenic mineral dust and the significant contribution of organic P from marine sources. The results also indicate the necessity to treat aerosol P carefully according to different sources of the aerosol particles and atmospheric processes the particles experience in assessing aerosol P input to seawater.

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.

Environmental factors driving the formation of water-soluble organic aerosols: A comparative study under contrasting atmospheric conditions.

Water-soluble organic carbon (WSOC), as major fractions of atmospheric aerosols, have gained attention due to their light-absorption properties. To illustrate the sources and key environmental factors driving WSOC formation under different atmospheric conditions, a comparative study was conducted by summarizing the results obtained from five field campaigns at inland (urban, suburban or regional) sites and a coastal site during different seasons. Organic carbon concentrations varied from 8.5 µg/m3 at the summer regional site to 17.5 µg/m3 at the winter urban site, with 46 %- 89 % of the mass as WSOC. Based on correlation analysis, primary combustion emissions were more important in winter than in summer, and secondary formation was an important source of WSOC during winter, summer and autumn. Atmospheric oxidants (NO2, O3), aerosol liquid water (ALW) and ambient RH were important factors influencing the WSOC formation, while their roles varied in different atmospheres. We observed a seasonal transition of atmospheric oxidants dominating the WSOC formation from O3 and NO2-driven conditions in summer to NO2-driven conditions in winter. Elevated ALW or ambient RH generally favor the WSOC formation, while the WSOC dependence of ALW varied among different ALW ranges. As the increasing of ALW or ambient RH, a transition of WSOC formation from "RH/ALW-limited regime" under low-ALW conditions, to "RH/ALW and precursor-driven regime" under medium-ALW/RH, and to "precursor-limited (RH/ALW-excess) regime" were observed for the inland atmospheric conditions. Under the high-RH and ALW conditions in coastal areas, ALW or ambient RH was generally not a limiting factor for WSOC formation.

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.

The occurrence of lower-than-expected bulk NCCN values over the marginal seas of China - Implications for competitive activation of marine aerosols.

In this study, we combined the measured bulk particle number concentration (NCN), particle number size distribution (PNSD) and bulk cloud condensation nuclei concentration (NCCN) at various supersaturation (SS) levels to investigate competitive activation of aerosols in the marine atmospheres over the marginal seas of China during two winter campaigns Campaign A (December 9-19, 2019) and Campaign B (December 28, 2019-January 16, 2020). During the two campaigns, we observed various categories of aerosols, i.e., long-range transport continental aerosols, clean marine aerosols, grown new particles ranging from nucleation mode to larger sizes, and grown pre-existing particles ranging from Aitken mode to accumulation mode size, etc. We found that the measured NCCN increased by only approximately 30 % with increases in SS levels from 0.2 % to 1.0 %, e.g., (1.8 ± 1.4) × 103 cm-3 at SS = 0.2 % and (2.4 ± 1.4) × 103 cm-3 at SS = 1.0 % during Campaign A. We further calculated the hygroscopicity parameter kappa (κ) by combining simultaneously measured PNSD and bulk NCCN to explore the causes. The calculated κ values were below 0.1 at SS = 0.4 % during the 72 % (or 88 %) period of Campaign A (or Campaign B). When κ values below 0.1 (or 0.2) were excluded, the remaining κ values were apparently reasonable, with an average of 0.22 (or 0.36) and a standard deviation of 0.10 (or 0.21) at SS = 0.4 % during Campaign A (or Campaign B). The unexpectedly lower κ values were discussed in terms of competitive activation of aerosols in marine atmospheres together with its net contribution to lowering the measured bulk NCCN below the expected value.

Striking impacts of biomass burning on PM2.5 concentrations in Northeast China through the emission inventory improvement.

Biomass burning exerts substantial influences on air quality and climate, which in turn to further aggravate air quality. The biomass burning emissions in particular of the agricultural burning may suffer large uncertainties which limits the understanding of their impact on air quality. Based on an improved emission inventory of the Visible Infrared Imaging Radiometer Suite (VIIRS) relative to commonly used Global Fire Emissions Database (GFED), we thoroughly evaluate the impact of biomass burning on air quality and climate during the episodes of November 2017 in Northeast China which is rich in agriculture burning. The results first indicate substantial underestimates in simulated PM2.5 concentrations without the inclusion of biomass burning emission inventory, based on a regional air quality model Weather Research and Forecasting model and Community Multiscale Air Quality model (WRF-CMAQ). The addition of biomass burning emissions from GFED then reduces the bias to a certain extent, which is further reduced by replacing the agricultural fires data in GFED with VIIRS. Numerical sensitivity experiments show that based on the improved emission inventory, the contribution of biomass burning emissions to PM2.5 concentrations in Northeast China reaches 32%, contrasting to 15% based on GFED, during the episode from November 1 to 7, 2017. Aerosol direct radiative effects from biomass burning are finally elucidated, which not only reduce downward surface shortwave radiation and planetary boundary layer height, but also affect the vertical distribution of air temperature, wind speed and relative humidity, favorable to the accumulation of PM2.5. During November 1-7, 2017, the mean daily PM2.5 enhancement due to aerosol radiative effects from VIIRS_G is 16 µg m-3, a few times higher than that of 2.8 µg m-3 from GFED. The study stresses the critical role of biomass burning, particularly of small fires easily missed in the traditional low-resolution satellite products, on air quality.

Atmospheric input of silicon to the China adjacent seas: Non-negligible contributions from anthropogenic sources.

Atmospheric deposition is an important source of exogenous Si in the oceans. As a typical crustal element, Si in the atmosphere emitted from anthropogenic sources is ignored. In this study, the atmospheric dry deposition of anthropogenic Si to China adjacent seas was calculated using WRF-CMAQ in January and July 2019 to investigate the contribution of anthropogenic Si to the oceans. Si emitted from 13 anthropogenic sources in China, the Korean Peninsula, Japan, and marine ships was considered. Emissions of anthropogenic Si in January and July 2019 were 30.2 and 22.0 Gg, respectively. The highest Si emissions were concentrated over eastern China, e.g. Beijing-Tianjin-Hebei region, Shandong province, Yangtze river delta area (0.2-21.3 ng m-2 s-1), while the lowest emissions were in northwestern China (< 5.2 ng m-2 s-1). Among the Bohai (BS), Yellow (YS), and East China seas (ECS), dry deposition fluxes over the southern YS were highest (4.6-16.8 µg m-2 d-1), and those over the ECS were lowest (0.2-7.7 µg m-2 d-1). During pollution episodes, the outflow of polluted air masses from the continent caused a 10-fold increase in Si deposition compared with clear days. The relative contribution of continental anthropogenic emissions and ship combustion varied significantly in two seasons. In winter, deposition from continental anthropogenic emissions to total anthropogenic Si deposition was higher than 96 %. While in summer, the contributions from ship combustion increased obviously, accounting for 10-38 %. Deposition flux of dissolved Si from anthropogenic sources over China adjacent seas was about 4-38 % of that of dissolved mineral dust Si. The annual Si depositions from atmospheric anthropogenic sources to the Si fluxes from rivers to the China adjacent seas were 0.03 %-2.8 %. The marine primary productivity in the BS, YS, and ECS caused by atmospheric anthropogenic dissolved Si deposition were 1.3, 1.2, and 0.7 mg C m-2 a-1, respectively.

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.

Effect of Anthropogenic Aerosol Addition on Phytoplankton Growth in Coastal Waters: Role of Enhanced Phosphorus Bioavailability.

Atmospheric deposition can supply nutrients to induce varying responses of phytoplankton of different sizes in the upper ocean. Here, we collected surface and subsurface chlorophyll a maximum (SCM) seawaters from the Yellow Sea and East China Sea to conduct a series of onboard incubation experiments, aiming to explore the impact of anthropogenic aerosol (AR, sampled in Qingdao, a coastal city in Northern China) addition on phytoplankton growth using schemes with (unfiltered seawater, UFS) and without (filtered seawater, FS) microsized (20-200 µm) cells. We found that AR addition stimulated phytoplankton growth obviously, as indicated by chlorophyll a (Chl a) in surface incubations, and had stimulatory or no effects in SCM incubations, which was related to nutrient statuses in seawater. The high ratio of nitrogen (N) to phosphorus (P) in the AR treatments demonstrated that P became the primary limiting nutrient. The alkaline phosphatase activity (APA), which can reflect the rate at which dissolved organic P (DOP) is converted into dissolved inorganic P, was 1.3-75.5 times higher in the AR treatments than in the control, suggesting that AR addition increased P bioavailability in the incubated seawater. Dinoflagellates with the capacity to utilize DOP showed the dominant growth in the AR treatments, corresponding to the shift in phytoplankton size structure toward larger cells. Surprisingly, we found that nanosized (2-20 µm) and picosized (0.2-2 µm) Chl a concentrations in UFS were generally higher than those in FS. The APA in UFS was at least 1.6 times higher than in FS and was proportional to the contribution of microsized cells to the total Chl a, suggesting that microsized cells play an important role in the increase in APA, which contributes to the growth of nanosized and picosized phytoplankton. Current work provides new insight into the increase of P bioavailability induced by atmospheric deposition and resultant ecological effect in coastal waters.

Threat by marine heatwaves to adaptive large marine ecosystems in an eddy-resolving model.

Marine heatwaves (MHWs), episodic periods of abnormally high sea surface temperature (SST), severely affect marine ecosystems. Large Marine Ecosystems (LMEs) cover ~22% of the global ocean but account for 95% of global fisheries catches. Yet how climate change affects MHWs over LMEs remains unknown, because such LMEs are confined to the coast where low-resolution climate models are known to have biases. Here, using a high-resolution Earth system model and applying a "future threshold" that considers MHWs as anomalous warming above the long-term mean warming of SSTs, we find that future intensity and annual days of MHWs over majority of the LMEs remain higher than in the present-day climate. Better resolution of ocean mesoscale eddies enables simulation of more realistic MHWs than low-resolution models. These increases in MHWs under global warming poses a serious threat to LMEs, even if resident organisms could adapt fully to the long-term mean warming.

Sunken oil detection and classification using MBES backscatter data.

Sunken oil incidents have occurred multiple times in the Bohai Sea over the past ten years. Currently, quick and effective sunken oil detection and classification remains a difficult problem. In this study, sonar detection experiments are conducted to obtain acoustic image samples using a multibeam echosounder (MBES) in a large seawater tank at the bottom of the area where the sunken oil is located. A series of MBES data corrections are constructed to generate backscatter strength images that can reflect the target characteristics directly. Meanwhile, eight-dimensional features are extracted, and a support vector machine (SVM) classification framework is built to classify the sunken oil and other interference targets. The results indicate that the MBES backscatter images provide an alternative approach for detecting and classifying sunken oil. The overall target classification accuracy reaches 88.5% by the SVM algorithm. Thus, this study provides a basis for further investigation of detecting sunken oil.

Wet deposition of atmospheric selenium and sensitivity to emission and precipitation patterns.

Wet deposition has been well recognized to be affected by species concentration and precipitation; nevertheless, the regimes in the controlling factor of concentration or precipitation have not yet been clarified. Using a trace element, selenium (Se), with dual effects on human health as a testbed, we first reproduce the spatial distribution of atmospheric Se concentrations and wet deposition fluxes through GEOS-Chem on a global scale, and examine the spatial patterns and relative importance of anthropogenic emissions vs. natural emissions over various regions around the world. We find that over most Northern Hemisphere continental regions, anthropogenic emissions are the dominant source for atmospheric Se concentration and deposition, while it is dominated by natural sources in the other areas. Nested grid simulations covering China and the continental United States are further conducted. The factors (i.e., Se concentration and precipitation) controlling the wet deposition flux of atmospheric Se are analyzed in detail, through the construction of wet deposition-concentration-precipitation (WETD-C-P) diagram for two regions (mainland China and the continental United States) based on the monthly results. The two regions show distinctive features, reflecting the different spatial patterns of Se emissions and precipitation. Both Se emissions and precipitation are higher in the eastern United States than that in the western United States. In contrast, the emissions and precipitation in northern and southern China show dipole features with stronger emissions over the northern side and higher precipitation on the southern side. We further investigate the impacts of future emission changes in China on atmospheric Se deposition and its sensitivity to emissions and precipitation, revealing a modulation of regime shifts, i.e., from the precipitation dominant regime to the concurrent governance of both precipitation and emissions. The proposed WETD-C-P relationship is useful in elucidating the regime and factors governing the spatial and temporal variations in wet deposition.

Nitrogen isotopic composition of NOx from residential biomass burning and coal combustion in North China.

Stable nitrogen isotope (δ15N) technology has often been used as a powerful tool to separate nitrogen oxides (NOx) produced by residential combustion (i.e., biomass burning and coal combustion) from other sources. However, the insufficient measurement of δ15N-NOx fingerprints of these emissions limits its application, especially in North China where residential emissions are significant. This study conducted combustion experiments to determine the δ15N-NOx of typical residential fuels in North China, including ten biomass fuels and five types of coal. The results showed that the δ15N of biomass varied between -6.9‰ and 2.3‰, which was lower than the δ15N of residential coal (-0.2‰-4.6‰). After combustion, the δ15N of biomass residues increased greatly, while that of coal residues showed no significant upward trend (p > 0.05). The δ15N-NOx produced by biomass burning ranged from -5.6‰ to 3.2‰ (-0.4‰ ± 2.4‰), showing a significant linear relation with δ15N-biomass. Comparatively, the δ15N-NOx derived from residential coal combustion was much higher (16.1‰ ± 3.3‰), ranging from 11.7‰ to 19.7‰. It was not well correlated with δ15N-coal, and only slightly lower than the estimated δ15N-NOx of industrial coal combustion (17.9‰, p > 0.05). These observations indicate that the δ15N-NOx of residential coal combustion is a result of the mixture of thermal- and fuel-released NOx. Based on the isotopic characteristics observed in this study, we analyzed the reported δ15N-NOx, and provided more statistically robust δ15N-NOx distributions for biomass burning (1.3‰ ± 4.3‰; n = 101) and coal combustion (17.9‰ ± 3.1‰; n = 26), which could provide guidance for scientific studies aiming to quantify the origin of NOx in North China and in other regions.

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.

The enhanced role of atmospheric reduced nitrogen deposition in future over East Asia-Northwest Pacific.

The atmospheric nitrogen deposition plays a crucial role in natural ecosystem, and the changes in emissions substantially affect the amount of nitrogen deposition. Along with the decrease in NOx emissions and increase in NH3 emissions, the reduced nitrogen deposition may play a more important role in future. However, to what extent these changes may modify the reduced nitrogen deposition across East Asia, which is fulfilled with a large amount of nitrogen deposition, to the northwestern Pacific has not yet to be clear. Based on the results of multi-model ensemble of Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), the future changes of reduced nitrogen (NHx) deposition is firstly examined. Here we show the changes of NHx deposition flux is substantially modulated by both climate change and emissions, exhibiting an increasing trend over East Asia-Northwest Pacific in future under representative concentration pathways (RCP) 8.5 scenario, largely controlled by increase of NH3 emissions, contrasting to the oxidized nitrogen deposition which is projected to decrease. Specifically, the ratio of NHx to total nitrogen deposition in eastern China increases from 38% at present to 56% by the end of the century under RCP 8.5, indicative of a transition in the form of dominant nitrogen deposition from oxidized to reduced one. The increase is clearly discernable over the marginal seas and northwestern Pacific. Moreover, we identify a meridional shift of high wet NHx deposition from northern China in summer to southern China in the other seasons. Based on simulations from regional models Weather Research and Forecasting (WRF) and Community Multi-scale Air Quality (CMAQ), we find that the synergistically nonlinear modulation of NHx concentration and precipitation triggers the north-south shift of wet NHx deposition. The findings in this study indicate a potentially more important role of reduced nitrogen deposition on the natural ecosystem in future.