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.

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.

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%.

Composition and spatial distribution of elements and isotopes of a giant human bladder stone and environmental implications.

The composition and spatial distribution of minerals, trace elements, as well as carbon and nitrogen isotopes from the outer crust to inner nucleus of a 20-year old giant human bladder stone comprising thirteen layers were intensively investigated. Calcium oxalate monohydrate (COM) was found to concentrate in the inner and middle layers, struvite was concentrated in middle and outer layers, and fluorapatite occurred in almost all layers. The spatial distribution of minerals has the potential to provide preliminary knowledge regarding the long-term urine composition, or even the physiological condition of the patient. The stable carbon isotope ratio (δ13C) and stable nitrogen isotope ratio (δ15N) were measured in each layer and significant correlation was found between δ13C with calcium oxalate monohydrate content and between δ15N and struvite content. Nearly constant values of -23.2‰ and 7.1‰ for δ13C and δ15N, respectively, were found in the organic components of the stone. Both isotope ratios indicate a long-term fixed diet consisting mainly of C3 plants, such as rice and wheat, for the 20-year time period of the stone formation. In addition, eighteen elements (Ca, P, Mg, K, Na, Al, Fe, Zn, Pb, Cu, Sr, Ba, Ti, V, Cr, Ni, Mn and Co) were measured in all the layers. The trace elements Al, Fe, Cu, Zn, Pb, Sr, Ba and Ti showed a similar spatial distribution pattern from the outer crust to the inner core. Although there were complex correlations between elements and minerals, Factor Analysis suggests that the occurrence of these elements in stones may be mainly the result of environmental exposure to metals during the formation of the stone, indicating that urinary stones may serve as potential long-term biomonitors. In particular, Ni and Cr showed a distinct distribution pattern in the stone, which may relate to human metabolic activities.