Increased Contribution of Circumpolar Deep Water Upwelling to Methylmercury in the Upper Ocean around Antarctica: Evidence from Mercury Isotopes in the Ornithogenic Sediments.

Upwelling plays a pivotal role in supplying methylmercury (MeHg) to the upper oceans, contributing to the bioaccumulation of MeHg in the marine food web. However, the influence of the upwelling of Circumpolar Deep Water (CDW), the most voluminous water mass in the Southern Ocean, on the MeHg cycle in the surrounding oceans and marine biota of Antarctica remains unclear. Here, we study the mercury (Hg) isotopes in an ornithogenic sedimentary profile strongly influenced by penguin activity on Ross Island, Antarctica. Results indicate that penguin guano is the primary source of Hg in the sediments, and the mass-independent isotope fractionation of Hg (represented by Δ199Hg) can provide insights on the source of marine MeHg accumulated by penguin. The Δ199Hg in the sediments shows a significant decrease at ∼1550 CE, which is primarily attributed to the enhanced upwelling of CDW that brought more MeHg with lower Δ199Hg from the deeper seawater to the upper ocean. We estimate that the contribution of MeHg from the deeper seawater may reach more than 38% in order to explain the decline in Δ199Hg at ∼1550 CE. Moreover, we found that the intensified upwelling may have increased the MeHg exposure for marine organisms, highlighting the importance of CDW upwelling on the MeHg cycle in Antarctic coastal ecosystems.

The Marginal Ice Zone as a dominant source region of atmospheric mercury during central Arctic summertime.

Atmospheric gaseous elemental mercury (GEM) concentrations in the Arctic exhibit a clear summertime maximum, while the origin of this peak is still a matter of debate in the community. Based on summertime observations during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition and a modeling approach, we further investigate the sources of atmospheric Hg in the central Arctic. Simulations with a generalized additive model (GAM) show that long-range transport of anthropogenic and terrestrial Hg from lower latitudes is a minor contribution (~2%), and more than 50% of the explained GEM variability is caused by oceanic evasion. A potential source contribution function (PSCF) analysis further shows that oceanic evasion is not significant throughout the ice-covered central Arctic Ocean but mainly occurs in the Marginal Ice Zone (MIZ) due to the specific environmental conditions in that region. Our results suggest that this regional process could be the leading contributor to the observed summertime GEM maximum. In the context of rapid Arctic warming and the observed increase in width of the MIZ, oceanic Hg evasion may become more significant and strengthen the role of the central Arctic Ocean as a summertime source of atmospheric Hg.

Elevated methylmercury in Antarctic surface seawater: The role of phytoplankton mass and sea ice.

Methylmercury is a neurotoxin that is biomagnified in marine food webs. Its distribution and biogeochemical cycle in Antarctic seas are still poorly understood due to scarce studies. Here, we report the total methylmercury profiles (up to 4000 m) in unfiltered seawater (MeHgT) from the Ross Sea to the Amundsen Sea. We found high MeHgT levels in oxic unfiltered surface seawater (upper 50 m depth) in these regions. It was characterized by an obviously higher maximum concentration level of MeHgT (up to 0.44 pmol/L, at a depth of 3.35 m), which is higher than other open seas (including the Arctic Ocean, the North Pacific Ocean and the equatorial Pacific), and a high MeHgT average concentration in the summer surface water (SSW, 0.16 ± 0.12 pmol/ L). Further analyses suggest that the high phytoplankton mass and sea-ice fraction are important drivers of the high MeHgT level that we observed in the surface water. For the influence of phytoplankton, the model simulation showed that the uptake of MeHg by phytoplankton would not fully explain the high levels of MeHgT, and we speculated that high phytoplankton mass may emit more particulate organic matter as microenvironments that can sustain Hg in-situ methylation by microorganisms. The presence of sea-ice may not only harbor a microbial source of MeHg to surface water but also trigger increased phytoplankton mass, facilitating elevation of MeHg in surface seawater. This study provides insight into the mechanisms that impact the content and distribution of MeHgT in the Southern Ocean.

Indoor air particles in research vessel from Shanghai to Antarctic: Characteristics, influencing factors, and potential controlling pathway.

Despite millions of seafarers and passengers staying on ships each year, few studies have been conducted on the indoor air quality inside ship hulls. In this study, we investigated the levels and size distribution of indoor particulate matter during two cruises of the research vessel "Xuelong" from Shanghai to Antarctica. The results showed that the particle size less than 2.5 µm (PM2.5), and particle size less than 10 µm (PM10) concentrations in different rooms of the ship widely varied. We observed high particulate matter (PM) levels in some of the rooms. The mass concentration distribution was dominated by 1-4 µm particles, which may have been caused by the hygroscopic growth of fine particles. The dominant factors influencing PM concentrations were indoor temperature, relative humidity, and human activity. We quantified contributions of these factors to the levels of indoor particles using a generalized additive model. In clean rooms, the levels of indoor particles were controlled by temperature and relative humidity, whereas in polluted rooms, the levels of indoor particles were mainly influenced by temperature and human activity, which implied that controlling temperature and human activity would efficiently reduce the levels of indoor particles.

Spatiotemporal distribution and influencing factors of secondary organic aerosols in the summer atmosphere from the Bering Sea to the western North Pacific.

To better understand the formation process of biogenic and anthropogenic secondary organic aerosols (BSOA and ASOA) in the marine atmosphere under the background of global warming, aerosol samples were collected over three summers (i.e., 2014, 2016 and 2018) from the Bering Sea (BS) to the western North Pacific (WNP). The results showed that temporally, atmospheric concentrations of isoprene-derived SOA (SOAI) tracers were the lowest in 2014 regardless of the marine region, while atmospheric concentrations of monoterpenes-derived SOA (SOAM) tracers in this year were the highest and the aerosols were more aged than those in the other two years. In comparison, the concentrations of ß-caryophyllene-derived and toluene-derived SOA (SOAC and SOAA) tracers were relatively low overall. Spatially, the concentrations of SOA tracers were significantly higher over the WNP than over the BS, with SOA tracers over the BS mainly coming from marine sources, while the WNP was strongly influenced by terrestrial inputs. In particular, for land-influenced samples from the WNP, NOx-channel products of SOAI were more dependent on O3 and SO2 relative to HO2-channel product, and the high atmospheric oxidation capacity and SO2 could promote the formation of later-generation SOAM products. The extent of terrestrial influence was further quantified using a principal component analysis (PCA)-generalized additive model (GAM), which showed that terrestrial emissions explained more than half of the BSOA tracers' concentrations and contributed almost all of the ASOA tracer. In addition, the assessment of secondary organic carbon (SOC) highlighted the key role of anthropogenic activities in organic carbon levels in offshore areas. Our study revealed significant contributions of terrestrial natural and anthropogenic sources to different SOA over the WNP, and these relevant findings help improve knowledge about SOA in the marine atmosphere.

Molecular characteristics, sources and influencing factors of isoprene and monoterpenes secondary organic aerosol tracers in the marine atmosphere over the Arctic Ocean.

Biogenic secondary organic aerosols (BSOA) are important components of the remote marine atmosphere. However, the response of BSOA changes to sea ice reduction over the Arctic Ocean remains unclear. Here we investigated isoprene and monoterpenes secondary organic aerosol (SOAI and SOAM) tracers in three years of summer aerosol samples collected from the Arctic Ocean atmosphere. The results indicated that methyltetrols were the most abundant SOAI tracers, while the main oxidation products of monoterpenes varied over the years owing to different aerosol aging. The results of the principal component analysis (PCA)-generalized additive model (GAM) combined with correlation analysis suggested that SOAI tracers were mainly generated by the oxidation of isoprene from marine emissions, while SOAM tracers were probably more influenced by terrestrial transport. Estimation of secondary organic carbon (SOC) indicated that monoterpenes oxidation contributed more than isoprene and that sea ice changes had a relatively small effect on biogenic SOC concentration levels. Our study quantified the contribution of influencing factors to the atmospheric concentration of BSOA tracers in the Arctic Ocean, and showed that there were differences in the sources of precursors for different BSOA. Hence, our findings have contributed to a better understanding of the characteristics, sources and formation of SOA in the atmosphere of the Arctic Ocean.

Mixing state and distribution of iodine-containing particles in Arctic Ocean during summertime.

Iodine chemistry plays a key role in ozone destruction and new aerosol formation in the marine boundary layer (MBL), especially in polar regions. We investigated iodine-containing particles (0.2-2 µm) in the Arctic Ocean using a ship-based single particle aerosol mass spectrometer from July to August 2017. Seven main particle types were identified: dust, biomass combustion particles, sea salt, organic S, aromatics, hydrocarbon-like compounds, and amines. The number fraction of iodine-containing particles was higher inside the Arctic Circle (>65°N) than outside (55-65°N). According to the air mass back trajectories, the latitudinal distribution of iodine-containing particles can be mainly attributed to iodine emissions from the sea ice edge region. Diurnal trends were found, especially during the second half of cruise, with peak iodine-containing particle number fractions during low-light conditions and relatively low number fractions at midday. These results imply that solar radiation plays a significant role in modulating particulate iodine in the Arctic atmosphere.

Quantify the role of anthropogenic emission and meteorology on air pollution using machine learning approach: A case study of PM2.5 during the COVID-19 outbreak in Hubei Province, China.

Air pollution is becoming serious in developing country, and how to quantify the role of local emission and/or meteorological factors is very important for government to implement policy to control pollution. Here, we use a random forest model, a machine learning (ML) approach, combined with a de-weather method to analyze the PM2.5 level during the COVID-19 outbreak in Hubei Province. The results show that changes in anthropogenic emissions have reduced PM2.5 concentrations in February and March 2020 by about 33.3% compared to the same period in 2019, while changes in meteorological conditions have increased PM2.5 concentrations by about 8.8%. Moreover, the impact of meteorological conditions is more significant in the central region, which is likely to be related to regional transport. After excluding the contribution of meteorological conditions, the PM2.5 concentration in Hubei Province in February and March 2020 is lower than the secondary standard of China (35 µ g/m3). Our estimates also indicate that under similar meteorological conditions as in February and March 2019, an emission reduction intensity equivalent to about 48% of the emission reduction intensity during the lockdown may bring the annual average PM2.5 concentration to the standard (35 µ g/m3). Our study shows that machine learning is a powerful tool to quantify the influencing factors of PM2.5, and the results further emphasize the need for scientific emission reduction as well as joint regional control measures in future.

Latitudinal Distribution of Gaseous Elemental Mercury in Tropical Western Pacific: The Role of the Doldrums and the ITCZ.

The role of the tropical western Pacific in the latitudinal distribution of atmospheric mercury is still unclear. In this study, we conducted continuous measurements of gaseous elemental mercury (GEM) in the marine boundary layer (MBL) along a large latitudinal transect (∼60° S to ∼30° N) of the western Pacific, accompanied by measurements of dissolved gaseous mercury (DGM) in the surface seawater. We found that the GEM latitudinal gradient is the most significant in the tropical western Pacific, which to some extent might be attributed to the impact of the doldrums and the Intertropical Convergence Zone (ITCZ) in this area. For the doldrums, calm weather may delay the transport of GEM, facilitating its accumulation in the tropical western Pacific. Furthermore, the regional transport, and low O3 and sea-salt aerosol levels in this area which would not favor the oxidation of GEM in the MBL, would intensify the accumulation of GEM in the tropical western Pacific. For the ITCZ, the vast wet deposition of Hg would drive elevated DGM in the surface seawater, which can increase the evasion flux and may further influence the spatial distribution of GEM. This study provides insight into the role of the tropical western Pacific in the regional atmospheric mercury cycle.

The observation of isotopic compositions of atmospheric nitrate in Shanghai China and its implication for reactive nitrogen chemistry.

The occurrence of PM2.5 pollution in China is usually associated with the formation of atmospheric nitrate, the oxidation product of nitrogen oxides (NOX = NO + NO2). The oxygen-17 excess of nitrate (Δ17O(NO3-)) can be used to reveal the relative importance of nitrate formation pathways and get more insight into reactive nitrogen chemistry. Here we present the observation of isotopic composition of atmospheric nitrate (Δ17O and δ15N) collected from January to June 2016 in Shanghai China. Concentrations of atmospheric nitrate ranged from 1.4 to 24.1 µg m-3 with the mean values being (7.6 ± 4.4 (1SD)), (10.2 ± 5.8) and (4.1 ± 2.4) µg m-3 in winter, spring and summer respectively. Δ17O(NO3-) varied from 20.5‰ to 31.9‰ with the mean value being (26.9 ± 2.8) ‰ in winter, followed by (26.6 ± 1.7) ‰ in spring and the lowest (23.2 ± 1.6) ‰ in summer. Δ17O(NO3-)-constrained estimates suggest that the conversion of NOX to nitrate is dominated by NO2 + OH and/or NO2 + H2O, with the mean possible contribution of 55-77% in total and even higher (84-92%) in summer. A diurnal variation of Δ17O(NO3-) featured by high values at daytime (28.6 ± 1.2‰) and low values (25.4 ± 2.8‰) at nighttime was observed during our diurnal sampling period. This trend is related to the atmospheric life of nitrate (τ) and calculations indicate τ is around 15 h during the diurnal sampling period. In terms of δ15N(NO3-), it changed largely in our observation, from -2.9‰ to 18.1‰ with a mean of (6.4 ± 4.4) ‰. Correlation analysis implies that the combined effect of NOX emission sources and isotopic fractionation processes are responsible for δ15N(NO3-) variations. Our observations with the aid of model simulation in future study will further improve the understanding of reactive nitrogen chemistry in urban regions.

The role of sulfate and its corresponding S(IV)+NO2 formation pathway during the evolution of haze in Beijing.

To better understand the role of stationary sources during the evolution of haze, we investigated sulfate formation characteristics at different stages of four haze events in Beijing, China. The mass fraction of sulfate in PM2.5 increased while that of nitrate declined slightly during the worsening process of most haze events, consistent with higher ratios of SO42-/NO3- on haze days (0.50 on average) than those on clean days (0.32 on average). Further calculations indicated that sulfate had a higher mass growth rate than nitrate during the haze-worsening process, probably due to regional transport of sulfate from heavy industrial areas accompanied by increased sulfate secondary transformation during polluted periods. We quantitatively evaluated the contribution of the S(IV) + NO2 reaction (pH-dependent) in sulfate formation during the haze evolution. The production rate (PS(IV)+NO2) of the S(IV) + NO2 pathway ranged from 1.97 × 10-4 to 5.91 (mean: 0.39) µg·m-3·h-1. Its proportion to sulfate total heterogeneous production rate (PS(IV)+NO2/Phet) was generally correlated positively with PM2.5 concentrations, indicating the relative importance of this pathway on haze days. Due to the mutual restriction between aerosol pH and aerosol liquid water content (ALWC) during haze evolution, the relative contribution of the S(IV) + NO2 pathway to sulfate heterogeneous formation was generally limited to 40%.