Role of the stratosphere in the global mercury cycle.

Mercury (Hg) is a global pollutant with substantial risks to human and ecosystem health. By upward transport in tropical regions, mercury enters into the stratosphere, but the contribution of the stratosphere to global mercury dispersion and deposition remains unknown. We find that between 5 and 50% (passing through the 400-kelvin isentropic surface and tropopause, respectively) of the mercury mass deposited on Earth's surface is chemically processed in the lower stratosphere.

Marine emissions of methanethiol increase aerosol cooling in the Southern Ocean.

Ocean-emitted dimethyl sulfide (DMS) is a major source of climate-cooling aerosols. However, most of the marine biogenic sulfur cycling is not routed to DMS but to methanethiol (MeSH), another volatile whose reactivity has hitherto hampered measurements. Therefore, the global emissions and climate impact of MeSH remain unexplored.

Heterogenous Chemistry of IO as a Critical Step in Iodine Cycling.

Global iodine emissions have been increasing rapidly in recent decades, further influencing the Earth's climate and human health. However, our incomplete understanding of the iodine chemical cycle, especially the fate of higher iodine oxides, introduces substantial uncertainties into atmospheric modeling. IO was previously deemed a "dead end" in iodine chemistry; however, we provide atomic-level evidence that IO can undergo rapid air-water or air-ice interfacial reactions within several picoseconds; these reactions are facilitated by prevalent chemicals on seawater such as amines and halide ions, to produce photolabile reactive iodine species such as HOI and IX (X = I, Br, and Cl).

Calibration of Arctic ice core bromine enrichment records for past sea ice reconstructions.

Bromine in ice cores has been proposed as a qualitative sea ice proxy to produce sea ice reconstructions for the polar regions. Here we report the first statistical validation of this proxy with satellite sea ice observations by combining bromine enrichment (with respect to seawater, Br) records from three Greenlandic ice cores (SIGMA-A, NU and RECAP) with satellite sea ice imagery, over three decades. We find that during the 1984-2016 satellite-era, ice core Br values are significantly correlated with first-year sea ice formed in the Baffin Bay and Labrador Sea supporting that the gas-phase bromine enrichment processes, preferentially occurring over the sea ice surface, are the main driver for the Br signal in ice cores.

MAX-DOAS observations of ship emissions in the North Sea.

Shipping emissions were measured in Dunkirk, France. Elevated aerosol extinction coefficients (AEC), nitrogen dioxide (NO) and sulphur dioxide (SO) were observed up to 500 m from surface. Formaldehyde (HCHO) did not show an increase every time, which suggests that oxidation of emitted volatile organic compounds (VOCs) took longer than the transport to the observation path and dilution of direct emissions had occurred.

Spontaneous Molecular Bromine Production in Sea-Salt Aerosols.

Bromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea-salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br) by O and HO in the absence of additional oxidants.

Typhoon- and pollution-driven enhancement of reactive bromine in the mid-latitude marine boundary layer.

Tropospheric reactive bromine is important for atmospheric chemistry, regional air pollution, and global climate. Previous studies have reported measurements of atmospheric reactive bromine species in different environments, and proposed their main sources, e.g.

East Asian summer monsoon delivers large abundances of very-short-lived organic chlorine substances to the lower stratosphere.

Deep convection in the Asian summer monsoon is a significant transport process for lifting pollutants from the planetary boundary layer to the tropopause level. This process enables efficient injection into the stratosphere of reactive species such as chlorinated very-short-lived substances (Cl-VSLSs) that deplete ozone. Past studies of convective transport associated with the Asian summer monsoon have focused mostly on the south Asian summer monsoon.

Anthropogenic short-lived halogens increase human exposure to mercury contamination due to enhanced mercury oxidation over continents.

Mercury (Hg) is a contaminant of global concern, and an accurate understanding of its atmospheric fate is needed to assess its risks to humans and ecosystem health. Atmospheric oxidation of Hg is key to the deposition of this toxic metal to the Earth's surface. Short-lived halogens (SLHs) can provide halogen radicals to directly oxidize Hg and perturb the budget of other Hg oxidants (e.

Photodissociation of the CH2Br radical: A theoretical study.

Bromine atom (Br) reactions lead to ozone depletion in the troposphere and stratosphere. Photodegradation of bromocarbons is one of the main sources of bromine atoms in the atmosphere. Here, we use high-level ab initio methods, including spin-orbit effects, to study the photodissociation of the CH2Br radical.

Evidence of nitrate-based nighttime atmospheric nucleation driven by marine microorganisms in the South Pacific.

Our understanding of ocean-cloud interactions and their effect on climate lacks insight into a key pathway: do biogenic marine emissions form new particles in the open ocean atmosphere? Using measurements collected in ship-borne air-sea interface tanks deployed in the Southwestern Pacific Ocean, we identified new particle formation (NPF) during nighttime that was related to plankton community composition. We show that nitrate ions are the only species for which abundance could support NPF rates in our semicontrolled experiments. Nitrate ions also prevailed in the natural pristine marine atmosphere and were elevated under higher sub-10 nm particle concentrations.

Bromine, iodine and sodium along the EAIIST traverse: Bulk and surface snow latitudinal variability.

During the East Antarctic International Ice Sheet Traverse (Eaiist, december 2019), in an unexplored part of the East Antarctic Plateau, snow samples were collected to expand our knowledge of the latitudinal variability of iodine, bromine and sodium as well as their relation in connection with emission processes and photochemical activation in this unexplored area. A total of 32 surface (0-5 cm) and 32 bulk (average of 1 m depth) samples were taken and analysed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Our results show that there is no relevant latitudinal trend for bromine and sodium.

Functional Engagement of the PD-1/PD-L1 Complex But Not PD-L1 Expression Is Highly Predictive of Patient Response to Immunotherapy in Non-Small-Cell Lung Cancer.

Purpose: In many cancers, the expression of immunomodulatory ligands leads to immunoevasion, as exemplified by the interaction of PD-L1 with PD-1 on tumor-infiltrating lymphocytes. Profound advances in cancer treatments have come with the advent of immunotherapies directed at blocking these immuno-suppressive ligand-receptor interactions. However, although there has been success in the use of these immune checkpoint interventions, correct patient stratification for these therapies has been challenging.

Reply to the 'Comment on "Theoretical study of the NO radical reaction with CHClBr, CHICl, CHBrI, CHClBr, and CHClBr"' by C. J. Nielsen and Y. Tang, , 2022, , DOI: 10.1039/D2CP03013F.

In this Reply, we answer the main argument raised in the Comment about the energy of the NO radical and its influence in the reaction profiles of the reaction of the NO radical with CHClBr, CHICl, CHBrI, CHClBr, and CHClBr by C. J. Nielsen and Y.

Sea ice fluctuations in the Baffin Bay and the Labrador Sea during glacial abrupt climate changes.

Sea ice decline in the North Atlantic and Nordic Seas has been proposed to contribute to the repeated abrupt atmospheric warmings recorded in Greenland ice cores during the last glacial period, known as Dansgaard-Oeschger (D-O) events. However, the understanding of how sea ice changes were coupled with abrupt climate changes during D-O events has remained incomplete due to a lack of suitable high-resolution sea ice proxy records from northwestern North Atlantic regions. Here, we present a subdecadal-scale bromine enrichment (Br) record from the NEEM ice core (Northwest Greenland) and sediment core biomarker records to reconstruct the variability of seasonal sea ice in the Baffin Bay and Labrador Sea over a suite of D-O events between 34 and 42 ka.

Photochemical and thermochemical pathways to S and polysulfur formation in the atmosphere of Venus.

Polysulfur species have been proposed to be the unknown near-UV absorber in the atmosphere of Venus. Recent work argues that photolysis of one of the (SO) isomers, cis-OSSO, directly yields S with a branching ratio of about 10%. If correct, this pathway dominates polysulfur formation by several orders of magnitude, and by addition reactions yields significant quantities of S, S, and S.