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Sea salt aerosols play an important role in the radiation budget and atmospheric composition over the Arctic, where the climate is rapidly changing. Previous observational studies have shown that Arctic sea ice leads are an important source of sea salt aerosols, and modeling efforts have also proposed blowing snow sublimation as a source. In this study, size-resolved atmospheric particle number concentrations and chemical composition were measured at the Arctic coastal tundra site of Utqiaġvik, Alaska, during spring (3 April–7 May 2016). Blowing snow conditions were observed during 25 % of the 5-week study period and were overpredicted by a commonly used blowing snow parameterization based solely on wind speed and temperature. Throughout the study, open leads were present locally. During periods when blowing snow was observed, significant increases in the number concentrations of 0.01–0.06 µm particles (factor of 6, on average) and 0.06–0.3 µm particles (67 %, on average) and a significant decrease (82 %, on average) in 1–4 µm particles were observed compared to low wind speed periods. These size distribution changes were likely caused by the generation of ultrafine particles from leads and/or blowing snow, with scavenging of supermicron particles by blowing snow. At elevated wind speeds, both submicron and supermicron sodium and chloride mass concentrations were enhanced, consistent with wind-dependent local sea salt aerosol production. At moderate wind speeds below the threshold for blowing snow as well as during observed blowing snow, individual sea spray aerosol particles were measured. These individual salt particles were enriched in calcium relative to sodium in seawater due to the binding of this divalent cation with organic matter in the sea surface microlayer and subsequent enrichment during seawater bubble bursting. The chemical composition of the surface snowpack also showed contributions from sea spray aerosol deposition. Overall, these results show the contribution of sea spray aerosol production from leads on both aerosols and the surface snowpack. Therefore, if blowing snow sublimation contributed to the observed sea salt aerosol, the snow being sublimated would have been impacted by sea spray aerosol deposition rather than upward brine migration through the snowpack. Sea spray aerosol production from leads is expected to increase, with thinning and fracturing of sea ice in the rapidly warming Arctic.

The hydroxyl radical (OH) is the main atmospheric oxidant responsible for the removal of many reduced trace gases and the formation of secondary air pollutants. However, due to technical difficulties in measuring OH, the existing measurements of atmospheric OH concentrations are limited, and its sources and sinks are not well understood under low-nitrogen-oxide (NOx) conditions. In this study, we observed the OH concentrations using chemical ionization mass spectrometry at a coastal site in Hong Kong from October to November 2020. The average noontime OH concentration over the study period was measured at 4.9±2.1×106 cm−3. We found that a box model with comprehensive observational constraints reproduced the observed daytime OH concentrations when air parcels originated from the continental regions. However, this model overpredicted the observed daytime OH concentrations for coastal air parcels by 142 % on average. Unaccounted-for OH sinks in the model are proposed to be the cause of this overprediction. A missing OH reactivity, which is defined as the pseudo-first-order rate coefficient for OH loss by unmeasured trace gases, was estimated as 5.0±2.6 s−1 (lower limit) in the coastal air, and the missing reactivity increased with decreasing concentrations of NOx and volatile organic compounds (VOCs). Further studies are needed to find out the exact cause of the model overestimation and to identify the suspected unmeasured chemical species that contribute to the OH budget, in order to better quantify the formation of secondary air pollutants.

Sulfate plays a key role in the formation and growth of aerosol particles and cloud droplets in the troposphere and is thus important for air quality and climate. The formation mechanisms of sulfate vary with oxidant levels and environmental conditions and can be partially revealed by its isotopic signatures. Here we measure oxygen (16O, 17O, 18O) and sulfur isotopes (32S, 34S) of the sulfate aerosol samples collected at coastal Hong Kong, downwind of the highly urbanized Pearl River Delta region. Based on ion measurements, most (95%) of the sulfate collected is non-sea-salt sulfate. The δ34S of sulfate is on average 4.0±2.0 ‰ (range 0.7 – 8.0 ‰), at an average sulfur oxidation ratio of 79±9%. The average oxygen-17 excess (Δ17O) is -0.1±0.3 ‰, suggesting an important role of OH / transition metals / reactive halogens. The δ18O of sulfate is on average 4.9±2.1 ‰. The Markov-Chain Monte Carlo model will be used to further constrain sulfate formation mechanisms.

The atmospheric multiphase reaction of dinitrogen pentoxide (N2O5) with chloride-containing aerosol particles produces nitryl chloride (ClNO2), which has been observed across the globe. The photolysis of ClNO2 produces chlorine radicals and nitrogen dioxide (NO2), which alter pollutant fates and air quality. However, the effects of local meteorology on near-surface ClNO2 production are not yet well understood, as most observational and modeling studies focus on periods of clear conditions. During a field campaign in Kalamazoo, Michigan, from January–February 2018, N2O5 and ClNO2 were measured using chemical ionization mass spectrometry, with simultaneous measurements of atmospheric particulate matter and meteorological parameters. We examine the impacts of atmospheric turbulence, precipitation (snow, rain) and fog, and ground cover (snow-covered and bare ground) on the abundances of ClNO2 and N2O5. N2O5 mole ratios were lowest during periods of lower turbulence and were not statistically significantly different between snow-covered and bare ground. In contrast, ClNO2 mole ratios were highest, on average, over snow-covered ground, due to saline snowpack ClNO2 production. Both N2O5 and ClNO2 mole ratios were lowest, on average, during rainfall and fog because of scavenging, with N2O5 scavenging by fog droplets likely contributing to observed increased particulate nitrate concentrations. These observations, specifically those during active precipitation and with snow-covered ground, highlight important processes, including N2O5 and ClNO2 wet scavenging, fog nitrate production, and snowpack ClNO2 production, that govern the variability in observed atmospheric chlorine and nitrogen chemistry and are missed when considering only clear conditions.

Reactive halogens play a prominent role in the atmospheric chemistry of the Arctic during springtime. Field measurements and modeling studies suggest that halogens are emitted into the atmosphere from snowpack and reactions on wind-blown snow-sourced aerosols. The relative importance of snowpack and blowing snow sources is still debated, both at local scales and regionally throughout the Arctic. To understand the implications of these halogen sources on a pan-Arctic scale, we simulate Arctic reactive bromine chemistry in the atmospheric chemical transport model GEOS-Chem. Two mechanisms are included: (1) a blowing snow sea salt aerosol formation mechanism and (2) a snowpack mechanism assuming uniform molecular bromine production from all snow surfaces. We compare simulations including neither mechanism, each mechanism individually, and both mechanisms to examine conditions where one process may dominate or the mechanisms may interact. We compare the models using these mechanisms to observations of bromine monoxide (BrO) derived from multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instruments on O-Buoy platforms on the sea ice and at a coastal site in Utqiaġvik, Alaska, during spring 2015. Model estimations of hourly and monthly average BrO are improved by assuming a constant yield of 0.1 % molecular bromine from all snowpack surfaces on ozone deposition. The blowing snow aerosol mechanism increases modeled BrO by providing more bromide-rich aerosol surface area for reactive bromine recycling. The snowpack mechanism led to increased model BrO across the Arctic Ocean with maximum production in coastal regions, whereas the blowing snow aerosol mechanism increases BrO in specific areas due to high surface wind speeds. Our uniform snowpack source has a greater impact on BrO mixing ratios than the blowing snow source. Model results best replicate several features of BrO observations during spring 2015 when using both mechanisms in conjunction, adding evidence that these mechanisms are both active during the Arctic spring. Extending our transport model throughout the entire year leads to predictions of enhanced fall BrO that are not supported by observations.

International audience; 17O-excess (Δ17O = δ17O − 0.52 × δ18O) of sulfate trapped in Antarctic ice cores has been proposed as a potential tool for assessing past oxidant chemistry, while insufficient understanding of atmospheric sulfate formation around Antarctica hampers its interpretation. To probe influences of regional specific chemistry, we compared year-round observations of Δ17O of non-sea-salt sulfate in aerosols (Δ17O(SO42−)nss) at Dome C and Dumont d'Urville, inland and coastal sites in East Antarctica, throughout the year 2011. Although Δ17O(SO42−)nss at both sites showed consistent seasonality with summer minima (∼1.0‰) and winter maxima (∼2.5‰) owing to sunlight-driven changes in the relative importance of O3 oxidation to OH and H2O2 oxidation, significant intersite differences were observed in austral spring–summer and autumn. The cooccurrence of higher Δ17O(SO42−)nss at inland (2.0‰ ± 0.1‰) than the coastal site (1.2‰ ± 0.1‰) and chemical destruction of methanesulfonate (MS–) in aerosols at inland during spring–summer (October–December), combined with the first estimated Δ17O(MS–) of ∼16‰, implies that MS– destruction produces sulfate with high Δ17O(SO42−)nss of ∼12‰. If contributing to the known postdepositional decrease of MS– in snow, this process should also cause a significant postdepositional increase in Δ17O(SO42−)nss over 1‰, that can reconcile the discrepancy between Δ17O(SO42−)nss in the atmosphere and ice. The higher Δ17O(SO42−)nss at the coastal site than inland during autumn (March–May) may be associated with oxidation process involving reactive bromine and/or sea-salt particles around the coastal region.

Reactive halogens play a prominent role in the atmospheric chemistry of the Arctic during springtime. Field measurements and models studies suggest that halogens are emitted to the atmosphere from snowpack and reactions on wind-blown snow. The relative importance of snowpack and blowing snow sources is still debated, both at local scales and regionally throughout the Arctic. To understand implications of these halogen sources on a pan-Arctic scale, we simulate Arctic reactive bromine chemistry in the atmospheric chemical transport model GEOS-Chem. Two mechanisms are included: 1) a blowing snow sea salt aerosol formation mechanism and 2) a snowpack mechanism assuming uniform molecular bromine production from all snow surfaces. We compare simulations including neither mechanism, each mechanism individually, and both mechanisms to examine conditions where one process may dominate or the mechanisms may interact. We compare the models using these mechanisms to observations of bromine monoxide (BrO) derived from multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instruments on O-Buoy platforms on the sea ice and at a coastal site in Utqiaġvik, Alaska during spring 2015. Model estimations of hourly and monthly average BrO are improved by assuming a constant yield of 0.1 % molecular bromine from all snowpack surfaces on ozone deposition. The blowing snow mechanism increases BrO by providing more surface area for reactive bromine recycling. The snowpack mechanism led to increased BrO across the Arctic Ocean with maximum production in coastal regions, whereas the blowing snow mechanism increases BrO in specific areas due to high surface windspeeds. Our uniform snowpack source has a greater impact on BrO mixing ratios than the blowing snow source. Model results best replicate several features of BrO observations during spring 2015 when using both mechanisms in conjunction, adding evidence that these mechanisms are both active during the Arctic Spring. Extending our transport model throughout the entire year leads to predictions of enhanced fall BrO that are not supported by observations.

We use the GEOS-Chem chemical transport model to examine the influence of bromine release from blowing-snow sea salt aerosol (SSA) on springtime bromine activation and O3 depletion events (ODEs) in the Arctic lower troposphere. We evaluate our simulation against observations of tropospheric BrO vertical column densities (VCD tropo ) from the GOME-2 (second Global Ozone Monitoring Experiment) and Ozone Monitoring Instrument (OMI) spaceborne instruments for 3 years (2007–2009), as well as against surface observations of O3 . We conduct a simulation with blowing-snow SSA emissions from first-year sea ice (FYI; with a surface snow salinity of 0.1 psu) and multi-year sea ice (MYI; with a surface snow salinity of 0.05 psu), assuming a factor of 5 bromide enrichment of surface snow relative to seawater. This simulation captures the magnitude of observed March–April GOME-2 and OMI VCD tropo to within 17 %, as well as their spatiotemporal variability ( r=0.76 –0.85). Many of the large-scale bromine explosions are successfully reproduced, with the exception of events in May, which are absent or systematically underpredicted in the model. If we assume a lower salinity on MYI (0.01 psu), some of the bromine explosions events observed over MYI are not captured, suggesting that blowing snow over MYI is an important source of bromine activation. We find that the modeled atmospheric deposition onto snow-covered sea ice becomes highly enriched in bromide, increasing from enrichment factors of ∼5 in September–February to 10–60 in May, consistent with composition observations of freshly fallen snow. We propose that this progressive enrichment in deposition could enable blowing-snow-induced halogen activation to propagate into May and might explain our late-spring underestimate in VCD tropo . We estimate that the atmospheric deposition of SSA could increase snow salinity by up to 0.04 psu between February and April, which could be an important source of salinity for surface snow on MYI as well as FYI covered by deep snowpack. Inclusion of halogen release from blowing-snow SSA in our simulations decreases monthly mean Arctic surface O3 by 4–8 ppbv (15 %–30 %) in March and 8–14 ppbv (30 %–40 %) in April. We reproduce a transport event of depleted O3 Arctic air down to 40 ∘ N observed at many sub-Arctic surface sites in early April 2007. While our simulation captures 25 %–40 % of the ODEs observed at coastal Arctic surface sites, it underestimates the magnitude of many of these events and entirely misses 60 %–75 % of ODEs. This difficulty in reproducing observed surface ODEs could be related to the coarse horizontal resolution of the model, the known biases in simulating Arctic boundary layer exchange processes, the lack of detailed chlorine chemistry, and/or the fact that we did not include direct halogen activation by snowpack chemistry.

YAP1 is a key mediator of the Hippo pathway capable of exerting a profound effect on organ size as well as tumorigenesis. Alternative mRNA splicing of human YAP1 results in at least 8 protein isoforms that differ within the 2nd WW motif and the transcriptional activation domain. Methods: To investigate the isoform-specific differences in their mRNA expression, transcriptional activity and tumor-promoting function, we cloned cDNA encoding all of the eight YAP1 protein isoforms. Then, we examined their mRNA expression, subcellular localization, transcriptional regulation properties, interactions with key regulatory partners, and protein stability in response to changes in cell density, as well as their effects on pancreatic cancer cell malignancy both in vitro and in vivo. Results: Multiple YAP1 mRNA isoforms are expressed in commonly used pancreatic cancer lines as well as human pancreatic cancer PDX lines. Based on the analysis of heterologous reporter and endogenous target genes, all YAP1 isoforms are capable of activating transcription, albeit to a different extent. Importantly, we unveiled a marked discrepancy between the mRNA and protein expression levels of the YAP1-1 and YAP1-2 isoforms. We further discovered that the YAP1-2 isoform, which contains two tandem WW motifs, is less stable at the protein level, particularly at high cell densities. Mechanistically, we found that the presence of the 2nd WW motif in YAP1-2 facilitates the de novo formation of the YAP1-2/AMOT/LATS1 complex and contributes to a stronger binding of YAP1-2 to LATS1 and subsequently increased YAP1-2 ubiquitination and degradation by β-TRCP. Conclusion: Our data reveals a potent effect of YAP1-1 on pancreatic cancer malignancy in vitro and in vivo and provides novel mechanistic insight into isoform-specific and cell density-dependent regulation of YAP1 stability, as well as its impact on cancer malignancy.

[This corrects the article DOI: 10.7150/thno.42795.].

The atmospheric multiphase reaction of dinitrogen pentoxide (N2O5) with chloride-containing aerosol particles produces nitryl chloride (ClNO2), which has been observed across the globe. The photolysis of ClNO2 produces chlorine radicals and nitrogen dioxide (NO2), which alter pollutant fates and air quality. However, the effects of local meteorology on near-surface ClNO2 production are not yet well understood, as most observational and modeling studies focus on periods of clear conditions. During a field campaign in Kalamazoo, Michigan from January–February 2018, N2O5 and ClNO2 were measured using chemical ionization mass spectrometry, with simultaneous measurements of atmospheric particulate matter and meteorological parameters. We examine the impacts of atmospheric turbulence, precipitation (snow, rain) and fog, and ground cover (snow-covered and bare ground) on the abundances of ClNO2 and N2O5. N2O5 mole ratios were lowest during periods of lower turbulence and were not statistically significantly different between snow-covered and bare ground. In contrast, ClNO2 mole ratios were highest, on average, over snow-covered ground, due to saline snowpack ClNO2 production. Both N2O5 and ClNO2 mole ratios were lowest, on average, during rainfall and fog because of scavenging, with N2O5 scavenging by fog droplets likely contributing to observed increased particulate nitrate concentrations. These observations, specifically those during active precipitation and with snow-covered ground, highlight important processes, including N2O5 and ClNO2 wet scavenging, fog nitrate production, and snowpack ClNO2 production, that govern the variability in observed atmospheric chlorine and nitrogen chemistry and are missed when considering only clear conditions.

Nitrous acid (HONO) plays an important role in the oxidative capacity of the atmosphere during wintertime via photolysis to produce hydroxyl radicals (OH). While it is known that HONO is emitted from the Arctic snowpack, sparse observations of HONO in the midlatitude urban wintertime environment have hindered our understanding of cold-season atmospheric chemistry. In this study, measurements of ambient HONO, particulate nitrite (pN(III); N(III) = NO2(aq)– + HONO(aq) + H2ONO(aq)+), and snow nitrite (sN(III)) were conducted in Kalamazoo, Michigan during January–February 2018. Elevated levels of HONO and particulate nitrite were observed over snow-covered ground, likely due to emissions of HONO from the snowpack, as well as weak turbulent mixing in the atmospheric boundary layer. The noontime peak in HONO of 87 ± 60 (1σ) parts per trillion (ppt) over snow-covered ground suggests photochemical snowpack HONO production, likely in part through snowpack nitrate photolysis, with only a minor contribution from par...

17O-excess (Δ17O = δ17O − 0.52 × δ18O) of sulfate trapped in Antarctic ice cores has been proposed as a potential tool for assessing past oxidant chemistry, while insufficient understanding of atmospheric sulfate formation around Antarctica hampers its interpretation. To probe influences of regional specific chemistry, we compared year-round observations of Δ17O of non-sea-salt sulfate in aerosols (Δ17O(SO42−)nss) at Dome C and Dumont d’Urville, inland and coastal sites in East Antarctica, throughout the year 2011. Although Δ17O(SO42–)nss at both sites showed consistent seasonality with summer minima (~1.0 ‰) and winter maxima (~2.5 ‰) owing to sunlight-driven changes in the relative importance of O3-oxidation to OH- and H2O2-oxidation, significant inter-site differences were observed in austral spring–summer and autumn. The co-occurrence of higher Δ17O(SO42–)nss at inland (2.0 ± 0.1 ‰) than the coastal site (1.2 ± 0.1 ‰) and chemical destruction of methanesulfonate (MS–) in aerosols at inland during spring–summer (October to December), combined with the first estimated Δ17O(MS–) of ~16 ‰, implies that MS– destruction produces sulfate with high Δ17O(SO42–)nss of ~12 ‰. If contributing to the known post-depositional decrease of MS– in snow, this process should also cause a significant post-depositional increase in Δ17O(SO42–)nss over 1 ‰, that can reconcile the discrepancy between Δ17O(SO42–)nss in the atmosphere and ice.

Pancreatic ductal adenocarcinoma (PDAC) is the most aggressive human malignancy and intrinsically resistant to conventional therapies. YAP1, as a key downstream effector of the Hippo pathway, plays an important role in tumorigenesis including PDAC. Alternative mRNA splicing of YAP1 results in at least 8 protein isoforms, which are divided into two subgroups (YAP1-1 and YAP1-2) based on the presence of either a single or double WW domains. We investigated the functions and regulatory mechanisms of YAP1-1 and YAP1-2 in PDAC cells induced by TGF-β to undergo epithelial-to-mesenchymal transition (EMT). CRISPR-Cas9 and shRNA were used to silence YAP1 expression in pancreatic cancer cells. Re-constituted lentivirus mediated overexpression of each single YAP1 isoform was generated in the parental knockout L3.6 cells. EMT was induced by treatment with TGF-β, EGF and bFGF in parental and the constructed stable cell lines. Western blot and qPCR were used to detect the expression of EMT markers. Scratch wound healing and transwell assays were used to detect cell migration. The stability and subcellular localization of YAP1 proteins were determined by Western blot analysis, immunofluorescence, as well as ubiquitination assays. We showed that TGF-β, EGF and bFGF all significantly promoted EMT in PDAC cells, which was inhibited by knockdown of YAP1 expression. Interestingly, YAP1-1 stable cells exhibited a stronger migratory ability than YAP1-2 cells under normal culture condition. However, upon TGF-β treatment, L3.6-YAP1-2 cells exhibited a stronger migratory ability than L3.6-YAP1-1 cells. Mechanistically, TGF-β treatment preferentially stabilizes YAP1-2 and enhances its nuclear localization. Furthermore, TGF-β-induced EMT and YAP1-2 activity were both blocked by inhibition of AKT signaling. Our results showed that both YAP1-1 and YAP1-2 isoforms are important mediators in the EMT process of pancreatic cancer. However, YAP1-2 is more important in mediating TGF-β-induced EMT, which requires AKT signaling.

The formation of inorganic nitrate is the main sink for nitrogen oxides (NOx = NO + NO2). Due to the importance of NOx for the formation of tropospheric oxidants such as the hydroxyl radical (OH) and ozone, understanding the mechanisms and rates of nitrate formation is paramount for our ability to predict the atmospheric lifetimes of most reduced trace gases in the atmosphere. The oxygen isotopic composition of nitrate (Δ17O(nitrate)) is determined by the relative importance of NOx sinks, and thus can provide an observational constraint for NOx chemistry. Until recently, the ability to utilize Δ17O(nitrate) observations for this purpose was hindered by our lack of knowledge about the oxygen isotopic composition of ozone (Δ17O(O3)). Recent and spatially widespread observations of Δ17O(O3) have greatly reduced this uncertainty, and allow for an updated comparison of modeled and observed Δ17O(nitrate) and a reassessment of modeled nitrate formation pathways. Model updates based on recent laboratory studies of heterogeneous reactions renders dinitrogen pentoxide (N2O5) hydrolysis as important as NO2 + OH (both 41 %) for global inorganic nitrate production near the surface. All other nitrate production mechanisms represent less than 6 % of global nitrate production near the surface, but can be dominant locally. Updated reaction rates for aerosol uptake of NO2 result in significant reduction of nitrate and nitrous acid (HONO) formed through this pathway in the model, and render NO2 hydrolysis a negligible pathway for nitrate formation globally. Although photolysis of aerosol nitrate may have implications for NOx, HONO and oxidant abundances, it does not significantly impact the relative importance of nitrate formation pathways. Modeled Δ17O(nitrate) (28.6 ± 4.5 ‰) compares well with the average of a global compilation of observations (27.6 ± 5.0 ‰), giving confidence in the model's representation of the relative importance of ozone versus HOx (= OH + HO2 + RO2) in NOx cycling and nitrate formation.

We use the GEOS-Chem chemical transport model to examine the influence of bromine release from blowing snow sea salt aerosol (SSA) on springtime bromine activation and O3 depletion events (ODEs) in the Arctic lower troposphere. We evaluate our simulation against observations of tropospheric BrO vertical column densities (VCDtropo) from the GOME-2 and OMI spaceborne instruments for three years (2007–2009), as well as against surface observations of O3. We conduct a simulation with blowing snow SSA emissions from first-year sea ice (FYI, with a surface snow salinity of 0.1 psu) and multi-year sea ice (MYI, with a surface snow salinity of 0.05 psu), assuming a factor of 5 bromide enrichment of surface snow relative to seawater. This simulation captures the magnitude of observed March–April GOME-2 and OMI VCDtropo to within 17 %, as well as their spatiotemporal variability (r = 0.76-0.85). Many of the large-scale bromine explosions are successfully reproduced, with the exception of events in May, which are absent or systematically underpredicted in the model. If we assume a lower salinity on MYI (0.01 psu) some of the bromine explosions events observed over MYI are not captured, suggesting that blowing snow over MYI is an important source of bromine activation. We find that the modeled atmospheric deposition onto snow-covered sea ice becomes highly enriched in bromide, increasing from enrichment factors of ~ 5 in September–February to 10–60 in May, consistent with freshly fallen snow composition observations. We propose that this progressive enrichment in deposition could enable blowing snow-induced halogen activation to propagate into May and might explain our late-spring underestimate in VCDtropo. We estimate that atmospheric deposition of SSA could increase snow salinity by up to 0.04 psu between February and April, which could be an important source of salinity for surface snow on MYI as well as FYI covered by deep snowpack. Inclusion of halogen release from blowing snow SSA in our simulations decreases monthly mean Arctic surface O3 by 4–8 ppbv (15–30 %) in March and 8–14 ppbv (30–40 %) in April. We reproduce a transport event of depleted O3 Arctic air down to 40º N observed at many sub-Arctic surface sites in early April 2007. While our simulation captures a few ODEs observed at coastal Arctic surface sites, it underestimates the magnitude of other events and entirely misses some events. We suggest that inclusion of direct snowpack activation, which is a strong local source of Br radicals in the shallow Arctic boundary layer, could help reconcile the success of our simulation at capturing satellite retrievals of VCDtropo with its difficulty in reproducing local ODEs.

Marine cloud brightening (MCB) is proposed to offset global warming by emitting sea salt aerosols to the tropical marine boundary layer, which increases aerosol and cloud albedo. Sea salt aerosol is the main source of tropospheric reactive chlorine (Cly) and bromine (Bry). The effects of additional sea salt on atmospheric chemistry have not been explored. We simulate sea salt aerosol injections for MCB under two scenarios (212–569 Tg/a) in the GEOS‐Chem global chemical transport model, only considering their impacts as a halogen source. Globally, tropospheric Cly and Bry increase (20–40%), leading to decreased ozone (−3 to −6%). Consequently, OH decreases (−3 to −5%), which increases the methane lifetime (3–6%). Our results suggest that the chemistry of the additional sea salt leads to minor total radiative forcing compared to that of the sea salt aerosol itself (~2%) but may have potential implications for surface ozone pollution in tropical coastal regions., Key Points Sea salt aerosol emissions for Marine Cloud Brightening geoengineering are implemented in a global chemical transport modelThis leads to changes in global tropospheric Bry and Cly (+20 to 40%), ozone (−3 to −6%), OH (−2 to −4%), and methane lifetime (+3 to 6%)Chemistry of the added sea salt leads to minor total radiative forcing (−20 to −50 mW/m2) but may have implications for ozone pollution

Air quality models have not been able to reproduce the magnitude of the observed concentrations of fine particulate matter (PM2.5) during wintertime Chinese haze events. The discrepancy has been at least partly attributed to low biases in modeled sulfate production rates, due to the lack of heterogeneous sulfate production on aerosols in the models. In this study, we explicitly implement four heterogeneous sulfate formation mechanisms into a regional chemical transport model, in addition to gas-phase and in-cloud sulfate production. We compare the model results with observations of sulfate concentrations and oxygen isotopes, Δ17O(SO42-), in the winter of 2014–2015, the latter of which is highly sensitive to the relative importance of different sulfate production mechanisms. Model results suggest that heterogeneous sulfate production on aerosols accounts for about 20 % of sulfate production in clean and polluted conditions, partially reducing the modeled low bias in sulfate concentrations. Model sensitivity studies in comparison with the Δ17O(SO42-) observations suggest that heterogeneous sulfate formation is dominated by transition metal ion-catalyzed oxidation of SO2.

We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant-aerosol-halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea-salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are small in comparison. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl + OH reaction and by heterogeneous conversion of sea-salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model simulates successfully the observed mixing ratios of HCl in marine air (highest at northern mid-latitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night with chlorine of sea salt origin transported inland as HCl and fine aerosol. It simulates successfully the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be explained by transport inland of the marine source. It does not reproduce the boundary layer Cl2 mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night compared to WINTER observations, which could be due to uncertainty in the rate of the ClNO2 + Cl− reaction, but we have no explanation for the daytime observations. The global mean tropospheric concentration of Cl atoms in the model is 620 cm−3 and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the HOBr + Cl− reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO2 chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter.

Molecular hydrogen (H2) is the second most abundant reduced trace gas (after methane) in the atmosphere, but its biogeochemical cycle is not well understood. Our study focuses on the soil production and uptake of H2 and the associated isotope effects. Air samples from a grass field and a forest site in the Netherlands were collected using soil chambers. The results show that uptake and emission of H2 occurred simultaneously at all sampling sites, with strongest emission at the grassland sites where clover (N2 fixing legume) was present. The H2 mole fraction and deuterium content were measured in the laboratory to determine the isotopic fractionation factor during H2 soil uptake (αsoil) and the isotopic signature of H2 that is simultaneously emitted from the soil (δDsoil). By considering all net-uptake experiments, an overall fractionation factor for deposition of αsoil = kHD / kHH = 0.945 ± 0.004 (95 % CI) was obtained. The difference in mean αsoil between the forest soil 0.937 ± 0.008 and the grassland 0.951 ± 0.026 is not statistically significant. For two experiments, the removal of soil cover increased the deposition velocity (vd) and αsoil simultaneously, but a general positive correlation between vd and αsoil was not found in this study. When the data are evaluated with a model of simultaneous production and uptake, the isotopic composition of H2 that is emitted at the grassland site is calculated as δDsoil = (−530 ± 40) ‰. This is less deuterium depleted than what is expected from isotope equilibrium between H2O and H2.

The oxidation of dimethyl sulfide (DMS) in the troposphere and subsequent chemical conversion into sulfur dioxide (SO2) and methane sulfonic acid (MSA) are key processes for the formation and growth of sulfur-containing aerosol and cloud condensation nuclei (CCN), but are highly simplified in large-scale models of the atmosphere. In this study, we implement a series of gas-phase and multiphase sulfur oxidation mechanisms into the Goddard Earth Observing System-Chemistry (GEOS-Chem) global chemical transport model-including two important intermediates, dimethyl sulfoxide (DMSO) and methane sulphinic acid (MSIA)-to investigate the sulfur cycle in the global marine troposphere. We found that DMS is mainly oxidized in the gas phase by OH (66%), NO3 (16%) and BrO (12%) globally. DMS+BrO is important for the model's ability to reproduce the observed seasonality of surface DMS mixing ratio in the Southern Hemisphere. MSA is mainly produced from multiphase oxidation of MSIA by OH(aq) (66%) and O3(aq) (30%) in cloud droplets and aerosols. Aqueous-phase reaction with OH accounts for only 12% of MSA removal globally, and a higher MSA removal rate is needed to reproduce observations of the MSA •nssSO42 ratio. The modeled conversion yield of DMS into SO2 and MSA is 75% and 15%, respectively, compared to 91% and 9% in the standard model run that includes only gas-phase oxidation of DMS by OH and NO3. The remaining 10% of DMS is lost via deposition of intermediates DMSO and MSIA. The largest uncertainties for modeling sulfur chemistry in the marine boundary layer (MBL) are unknown concentrations of reactive halogens (BrO and Cl) and OH(aq) concentrations in cloud droplets and aerosols. To reduce uncertainties in MBL sulfur chemistry, we should prioritize observations of reactive halogens and OH(aq).

Recent field studies have suggested that sea-salt particulate nitrate (NITs) photolysis may act as a significant local source of nitrogen oxides (NOx) over oceans. We present a study of the global impact of this process on oxidant concentrations in the marine boundary layer using the GEOS-Chem model, after first updating the model to better simulate observed gas/particle phase partitioning of nitrate in the marine boundary layer. Model comparisons with long-term measurements of NOx from the Cape Verde Atmospheric Observatory (CVAO) in the eastern tropical North Atlantic provide support for an in situ source of NOx from NITs photolysis, with NITs photolysis coefficients about 25–50 times larger than corresponding HNO3 photolysis coefficients. Short-term measurement of nitrous acid (HONO) at this location show a clear daytime peak, with average peak mixing ratios ranging from 3 to 6 pptv. The model reproduces the general shape of the diurnal HONO profile only when NITs photolysis is included, but the magnitude of the daytime peak mixing ratio is under-predicted. This under-prediction is somewhat reduced if HONO yields from NITs photolysis are assumed to be close to unity. The combined NOx and HONO analysis suggests that the upper limit of the ratio of NITs : HNO3 photolysis coefficients is about 100. The largest simulated relative impact of NITs photolysis is in the tropical and subtropical marine boundary layer, with peak local enhancements ranging from factors of 5–20 for NOx, 1.2–1.6 for OH, and 1.1–1.3 for ozone. Since the spatial extent of the sea-salt aerosol impact is limited, global impacts on NOx, ozone and OH mass burdens are small (~ 1–3 %). We also present preliminary analysis showing that particulate nitrate photolysis in accumulation-mode aerosols (predominantly over continental regions) could lead to ppbv-level increases in ozone in the continental boundary layer. Our results highlight the need for more comprehensive long-term measurements of NOx, and related species like HONO and sea-salt particulate nitrate, to better constrain the impact of particulate nitrate photolysis on marine boundary layer oxidant chemistry. Further field and laboratory studies on particulate nitrate photolysis in other aerosol types are also needed to better understand the impact of this process on continental boundary layer oxidant chemistry.

Sulfur and reactive bromine (Bry) play important roles in tropospheric chemistry and the global radiation budget. The oxidation of dissolved SO2 (S(IV)) by HOBr increases sulfate aerosol abundance and may also impact the Bry budget, but is generally not included in global climate and chemistry models. In this study, we implement HOBr + S(IV) reactions into the GEOS-Chem global chemical transport model and evaluate the global impacts on both sulfur and Bry budgets. Modeled HOBr mixing ratios on the order of 0.1-1.0 parts per trillion (ppt) lead to HOBr + S(IV) contributing to 8% of global sulfate production and up to 45% over some tropical ocean regions with high HOBr mixing ratios (0.6-0.9 ppt). Inclusion of HOBr + S(IV) in the model leads to a global Bry decrease of 50%, initiated by the decrease in bromide recycling in cloud droplets. Observations of HOBr are necessary to better understand the role of HOBr + S(IV) in tropospheric sulfur and Bry cycles.

Molecular hydrogen (H2) is the second most abundant reduced trace gas (after methane) in the atmosphere, but its biogeochemical cycle is not well understood. Our study focuses on the soil production and uptake of H2 and the associated isotope effects. Air samples from a grass field and a forest site in the Netherlands were collected using soil chambers. The results show that uptake and emission of H2 occurred simultaneously at all sampling sites, with strongest emission at the grassland sites where clover (N2 fixing legume) was present. The H2 mole fraction and deuterium content were measured in the laboratory to determine the isotopic fractionation factor during H2 soil uptake (αsoil) and the isotopic signature of H2 that is simultaneously emitted from the soil (δDsoil). By considering all net-uptake experiments, an overall fractionation factor for deposition of αsoil = kHD/kHH = 0.945 ± 0.004 (95 % CI) was obtained. The difference in mean αsoil between the forest soil 0.937 ± 0.008 and the grassland 0.951 ± 0.025 is not statistically significant. For two experiments, the removal of soil cover increased the deposition velocity (vd) and αsoil simultaneously, but a general positive correlation between vd and αsoil was not found in this study. When the data are evaluated with a model of simultaneous production and uptake, the isotopic composition of H2 that is emitted at the grassland site is calculated as δDsoil = (−530 ± 40) ‰. This is less deuterium-depleted than what is expected from isotope equilibrium between H2O and H2.

Endostatin is a potent angiogenesis inhibitor. The structure of endostatin is unique in that its secondary structure is mainly irregular loops and beta-sheets and contains only a small fraction of alpha-helices with two pairs of disulfide bonds in a nested pattern. We choose human endostatin as a model system to study the folding mechanism of this kind. Nuclear magnetic resonance (NMR), tryptophan emission fluorescence, and circular dichroism (CD) were used to monitor the unfolding process of endostatin upon acid titration. Urea-induced unfolding was used to measure the stability of endostatin under different conditions. Our results show that endostatin is very acid-resistant; some native structure still remains even at pH 2 as evidenced by (1)H NMR. Trifluoroethanol (TFE) destabilizes native endostatin, while it makes endostatin even more acid-resistant in the low pH region. Stability measurement of endostatin suggests that endostatin is still in native structure at pH 3.5 despite the decreased stability. Acid-induced unfolding of endostatin is reversible, although it requires a long time to reach equilibrium below pH 3. Surprisingly, the alpha-helical content of endostatin is increased when it is unfolded at pH 1.6, and the alpha-helical content of the polypeptide chain of unfolded endostatin increases linearly with TFE concentration in the range of 0-30%. This observation indicates that the polypeptide chain of unfolded endostatin has an intrinsic alpha-helical propensity. Our discoveries may provide clues for refolding endostatin more efficiently. The acid-resistance property of endostatin may have biological significance in that it cannot be easily digested by proteases in an acidic environment such as in a lysosome in the cell.