Characteristics of aerosol aminiums over a coastal city in North China: Insights from the divergent impacts of marine and terrestrial influences.

Aminium ions, as crucial alkaline components within fine atmospheric particles, have a notable influence on new particle formation and haze occurrence. Their concentrations within coastal atmosphere depict considerable variation due to the interplay of distinctive marine and terrestrial sources, further complicated by dynamic meteorological conditions. This study conducted a comprehensive examination of aminiums ions concentrations, with a particular focus on methylaminium (MMAH+), dimethylaminium (DMAH+), trimethylaminium (TMAH+), and triethylaminium (TEAH+) within PM2.5, over varying seasons (summer, autumn, and winter of 2019 and summer of 2021), at an urban site in the coastal megacity of Qingdao, Northern China. The investigations revealed that the total concentration of particulate aminium ions (∑Aminium) was 21.6 ± 23.6 ng/m3, exhibiting higher values in the autumn and winter compared to the two summer periods. Considering diurnal variations during autumn and winter, concentrations of particulate aminium ions (excluding TEAH+) exhibited a slight increase during the day compared to night, with a notable peak during the morning hours. However, it was not the case for TEAH+, which was argued to be readily oxidized by ambient oxidants in the afternoon. Additionally, the ∑Aminium within the summer demonstrated markedly elevated levels during the day compared to night, potentially attributed to daytime sea fog associated with sea-land breeze interactions. Positive matrix factorization results indicate terrestrial anthropogenic emissions, including vehicle emission mixed with road dust and primary pollution, as the primary sources of MMAH+ and DMAH+. Conversely, TMAH+ was predominantly emitted from agricultural and marine sources. With the dominance of sea breeze in summer, TMAH+ was identified as a primary marine emission correlated with sea salt, while MMAH+, DMAH+, and TEAH+ were postulated to undergo secondary formation. Furthermore, a notable inverse correlation was observed between TMAH+ and methanesulfonate in PM2.5, consistent with dynamic emissions of sulfur-content and nitrogen-content gases reported in the literature.

The important role of nitrate in iron and manganese dissolution and sulfate formation in fine particles at a coastal site in Northern China.

Bioavailable transition trace elements, such as soluble iron (Fes) and soluble manganese (Mns) in aerosols, play a crucial role in atmospheric sulfate formation and marine ecosystems. In this study conducted during the spring of 2017 in Qingdao, a coastal city in Northern China, we applied a combined approach of multiple linear regression (MLR) incorporating the results of positive matrix factorization (PMF) to estimate the solubility of Fe and Mn from various sources. PMF analysis showed that dust was the largest contributor to total Fe (FeT) (45.5 %), followed by non-ferrous smelting (20.3 %) and secondary formation processes (17.8 %). However, secondary formation processes (33.2 %), vehicle exhaust (19.3 %) and aqueous-phase processes (19.0 %) were found to be the primary contributors to Fes. For total Mn (MnT) and Mns, dust (21.2 % âˆ¼ 35.0 %), secondary formation processes (20.3 % âˆ¼ 25.6 %) and industry (12.6 % âˆ¼ 16.3 %) were identified as the dominant contributors. The solubilities of Fe and Mn varied significantly depending on their sources. Interestingly, nitrate played a more pronounced role than sulfate in facilitating the dissolution of Fe and Mn during the acid processing due to the high molar ratio of NO3-/2SO42- (1.72 ± 0.54) under the average RH of 56 % ± 15 %. This phenomenon suggested that the acid processing was primarily triggered by nitrate formation due to the low deliquescence relative humidity (DRH) of nitrate. Additionally, we discovered that the catalytic oxidation of SO2 in aerosol water was primarily driven by Fe rather than Mn, serving as a more significant pathway for sulfate formation within a pH range of 2.0 to 4.4. These findings provide valuable insights into the impact of acidification on the dissolution of Fe and Mn under conditions of moderate RH in the real ambient atmosphere with the increasing of NO3-/2SO42- molar ratio.

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.

Ambient particle characteristics by single particle aerosol mass spectrometry at a coastal site in Hong Kong: a case study affected by the sea-land breeze.

The sea-land breeze (SLB) circulation plays a vital role in the transport of atmospheric pollutants in coastal cities. In this study, a single particle aerosol mass spectrometer (SPAMS) and combined bulk aerosol instruments were deployed to investigate the ambient particle characteristic at a suburban coastal site in Hong Kong from February 22 to March 10, 2013. Significant SLB circulations were captured from March 6-10, 2013, during the campaign. During the SLB periods, air quality worsened, with PM2.5 concentrations reaching a peak of 55.6 µg m-3 and an average value of 42.8 ± 4.5 µg m-3. A total of 235,894 particles were measured during the SLB stage. Eight major sources were identified by investigating the mixing states of the total particles, including the coal-burning related particles (48.1%), biomass burning particles (6.7%), vehicle emission-related particles (16.4%), sea salt (9.2%), ship emission particles (2.7%), dust/steeling industries (3.7%), waste incineration (6.3%), and road dust (3.9%). It was noteworthy that the PM2.5 concentrations and particle numbers increased sharply during the transition of land wind to the sea breeze. Meanwhile, the continental sourced pollutants recirculated back to land resulting in a cumulative increase in pollutants. Both individual and bulk measurements support the above results, with high contributions from coal burning, biomass burning, bulk K+, and NO3 -, which were probably from the regional transportation from the nearby area. In contrast, the ship and vehicle emissions increased during the SLB period, with a high sulfate concentration partially originating from the ship emission. In this study, field evidence of continental-source pollutants backflow to land with the evolution of sea breeze was observed and helped our current understanding of the effect of SLB on air quality in the coastal city.

Investigation of a haze-to-dust and dust swing process at a coastal city in northern China part I: Chemical composition and contributions of anthropogenic and natural sources.

The long retention of dust air masses in polluted areas, especially in winter, may efficiently change the physicochemical properties of aerosols, causing additional health and ecological effects. A large-scale haze-to-dust weather event occurred in the North China Plain (NCP) region during the autumn-to-winter transition period in 2018, affecting the coastal city Qingdao several times between Nov. 27th and Dec. 1st. To study the evolution of the pollution process, we analyzed the chemical characteristics of PM2.5 and PM10-2.5 and source apportionments of PM2.5 and PM10, The dust stagnated around NCP and moved out and back to the site, noted as dust swing process, promoting SO42- formation in PM2.5 and NO3- formation in PM10-2.5. Source apportionments were analyzed using the Positive Matrix Factorization (PMF) receptor model and weighted potential source contribution function (WPSCF). Before the dust invasion, Qingdao was influenced by severe haze; waste incineration and coal burning were the major contributors (~80 %) to PM2.5, and the source region was in the southwest of Shandong Province. During the initial dust event, mineral dust and the mixed factor of dust and sea salt were the major contributors (46.0 % of PM2.5 and 86.5 % of PM10). During the polluted dust period, the contributions of regional transported biomass burning (22.3 %), vehicle emissions (20.8 %), and secondary aerosols (33.8 %) to PM2.5 from the Beijing-Tianjin-Hebei region significantly increased. The secondary aerosols source was more regional than that of vehicle emissions and biomass burning and contributed considerably to PM10 (30.8 %) during the dust swing process. Our findings demonstrate that environmental managers should consider the possible adverse effects of winter dust on regional and local pollution.

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.