Aircraft-borne spectroscopic limb measurements of trace gases absorbing in the UV-A spectral range : investigations of bromine monoxide in the Arctic troposphere

Reactive halogen species (i.e., RHS=X, XO, X2, XY, OXO, HOX, XONO2, XNO2, with X,Y being I, Br and Cl) are known to be key compounds for the oxidation capacity of the troposphere, affecting the lifetime of relevant species such as O3, HOx, NOx, hydrocarbons, dimethylsulfide and gaseous elementary mercury. Furthermore, recent observations link iodine species to the formation of new aerosol particles. This work aims at the characterization of the abundance of BrO in the Arctic troposphere during the spring season, when the auto-catalytic release of bromine species from sea ice related halides is known to cause tropospheric Ozone Depletion Events (ODEs). A novel limb scanning mini-DOAS spectrometer for the detection of UV/vis absorbing radicals (e.g., O3, BrO, IO) was deployed on the DLR-Falcon (Deutsches Zentrum für Luft- und Raumfahrt) aircraft and tested during a field campaign that took place at Svalbard (78°N) in spring 2007. Herein, a new algorithm for inferring concentration vertical profiles of tropospheric trace gases from aircraft-borne DOAS limb observations is presented, characterized and validated through the profile retrieval of the UV-A absorber O4. The method is then applied for retrieving tropospheric vertical profiles of BrO during the polar campaign. For deployments during ODEs, the retrieved BrO vertical profiles consistently indicate high BrO mixing ratios (~ 15 pptv) within the boundary layer, low BrO mixing ratios (< 1.5 pptv) in the free troposphere, occasionally enhanced BrO mixing ratios in the upper troposphere (~ 1.5 pptv), and increasing BrO mixing ratios with altitude in the lowermost stratosphere. These findings are well in agreement with satellite and balloon-borne soundings of total and partial BrO atmospheric column densities. Moreover, the capabilities of the aircraft-borne measurements are further exploited by analyzing the sources, photochemistry and transport processes of BrO in the boundary layer above the sea ice

A negative feedback between anthropogenic ozone pollution and enhanced ocean emissions of iodine

Naturally emitted from the oceans, iodine compounds efficiently destroy atmospheric ozone and reduce its positive radiative forcing effects in the troposphere. Emissions of inorganic iodine have been experimentally shown to depend on the deposition to the oceans of tropospheric ozone, whose concentrations have significantly increased since 1850 as a result of human activities. A chemistry-climate model is used herein to quantify the current ocean emissions of inorganic iodine and assess the impact that the anthropogenic increase in tropospheric ozone has had on the natural cycle of iodine in the marine environment since pre-industrial times. Our results indicate that the human-driven enhancement of tropospheric ozone has doubled the oceanic inorganic iodine emissions following the reaction of ozone with iodide at the sea surface. The consequent build-up of atmospheric iodine, with maximum enhancements of up to 70% with respect to pre-industrial times in continental pollution outflow regions, has in turn accelerated the ozone chemical loss over the oceans with strong spatial patterns. We suggest that this ocean-atmosphere interaction represents a negative geochemical feedback loop by which current ocean emissions of iodine act as a natural buffer for ozone pollution and its radiative forcing in the global marine environment.Fil: Prados Roman, C.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Cuevas, Carlos Alberto. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Fernandez, Rafael Pedro. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; España. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Kinnison, Douglas E.. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Lamarque, Jean Francoise. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Saiz-lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; Españ

COVID-19 and Pregnancy: Citation Network Analysis and Evidence Synthesis.

Background: COVID-19 spread quickly around the world shortly after the first outbreaks of the new coronavirus disease at the end of December 2019, affecting all populations, including pregnant women. Objective: The aim of this study was to analyze the relationship between different publications on COVID-19 in pregnancy and their authors through citation networks, as well as to identify the research areas and to determine the publication that has been the most highly cited. Methods: The search for publications was carried out through the Web of Science database using terms such as “pregnancy,” “SARS-CoV-2,” “pregnant,” and “COVID-19” for the period between January and December 2020. Citation Network Explorer software was used for publication analysis and VOSviewer software was used to construct the figures. This approach enabled an in-depth network analysis to visualize the connections between the related elements and explain their network structure. Results: A total of 1330 publications and 5531 citation networks were identified in the search, with July being the month with the largest number of publications, and the United States, China, and England as the countries with the greatest number of publications. The most cited publication was “Clinical characteristics and intrauterine vertical transmission potential of COVID-19 infection in nine pregnant women: a retrospective review of medical records” by Chen and colleagues, which was published in March 2020. Six groups identified as being close in the citation network reflect multidisciplinary research, including clinical characteristics and outcomes in pregnancy, vertical transmission, delivery mode, and psychological impacts of the pandemic on pregnant women. Conclusions: Thousands of articles on COVID-19 have been published in several journals since the disease first emerged. Identifying relevant publications and obtaining a global view of the main papers published on COVID-19 and pregnancy can lead to a better understanding of the topic. With the accumulation of scientific knowledge, we now know that the clinical features of COVID-19 during pregnancy are generally similar to those of infected nonpregnant women. There is a small increase in frequency of preterm birth and cesarean birth, related to severe maternal illness. Vaccination for all pregnant women is recommended. Several agents are being evaluated for the treatment of COVID-19, but with minimal or no information on safety in pregnancy. These results could form the basis for further research. Future bibliometric and scientometric studies on COVID-19 should provide updated information to analyze other relevant indicators in this field.post-print1277 K

Enhanced production of oxidised mercury over the tropical Pacific Ocean: A key missing oxidation pathway

Mercury is a contaminant of global concern. It is transported in the atmosphere primarily as gaseous elemental mercury, but its reactivity and deposition to the surface environment, through which it enters the aquatic food chain, is greatly enhanced following oxidation. Measurements and modelling studies of oxidised mercury in the polar to sub-tropical marine boundary layer (MBL) have suggested that photolytically produced bromine atoms are the primary oxidant of mercury. We report year-round measurements of elemental and oxidised mercury, along with ozone, halogen oxides (IO and BrO) and nitrogen oxides (NO2), in the MBL over the Galápagos Islands in the equatorial Pacific. Elemental mercury concentration remained low throughout the year, while higher than expected levels of oxidised mercury occurred around midday. Our results show that the production of oxidised mercury in the tropical MBL cannot be accounted for by bromine oxidation only, or by the inclusion of ozone and hydroxyl. As a two-step oxidation mechanism, where the HgBr intermediate is further oxidised to Hg(II), depends critically on the stability of HgBr, an additional oxidant is needed to react with HgBr to explain more than 50% of the observed oxidised mercury. Based on best available thermodynamic data, we show that atomic iodine, NO2, or HO2 could all play the potential role of the missing oxidant, though their relative importance cannot be determined explicitly at this time due to the uncertainties associated with mercury oxidation kinetics. We conclude that the key pathway that significantly enhances atmospheric mercury oxidation and deposition to the tropical oceans is missing from the current understanding of atmospheric mercury oxidation

Global impacts of tropospheric halogens (Cl, Br, I) on oxidants and composition in GEOS-Chem [Discussion paper]

We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I). Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016) we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO) are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O3) concentrations, except in polar regions where the model now underestimates O3 concentrations. Halogen chemistry reduces the global tropospheric O3 burden by 18.6 %, with the O3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28  ×  106 molecules cm−3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH4 lifetime (10.8 %) due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH4 by Cl is small (∼  2 %) but Cl oxidation of other VOCs (ethane, acetone, and propane) can be significant (∼  15–27 %). Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde

Iodine oxide in the global marine boundary layer

Prados-Roman, C. ... et. al.-- 11 pages, 7 figures, 2 tables, The Supplement related to this article is available online at https://doi.org/10.5194/acp-15-583-2015-supplementEmitted mainly by the oceans, iodine is a halogen compound important for atmospheric chemistry due to its high ozone depletion potential and effect on the oxidizing capacity of the atmosphere. Here we present a comprehensive data set of iodine oxide (IO) measurements in the open marine boundary layer (MBL) made during the Malaspina 2010 circumnavigation. Results show IO mixing ratios ranging from 0.4 to 1 pmol mol-1 (30% uncertainty) and, complemented with additional field campaigns, this data set confirms through observations the ubiquitous presence of reactive iodine chemistry in the global marine environment. We use a global model with organic (CH3I, CH2ICl, CH2I2 and CH2IBr) and inorganic (HOI and I2) iodine ocean emissions to investigate the contribution of the different iodine source gases to the budget of IO in the global MBL. In agreement with previous estimates, our results indicate that, globally averaged, the abiotic precursors contribute about 75 % to the IO budget. However, this work reveals a strong geographical pattern in the contribution of organic vs. inorganic precursors to reactive iodine in the global MBL. © Author(s) 2015The Indian Institute of Tropical Meteorology is supported by the Ministry of Earth Sciences, Government of India. R. P. Fernandez would like to thank ANPCyT (PICT-PRH 2009-0063) for financial supportPeer Reviewe

Latitudinal distribution of reactive iodine in the Eastern Pacific and its link to open ocean sources

Ship-based Multi-Axis Differential Optical Absorption Spectroscopy measurements of iodine monoxide (IO) and atmospheric and seawater Gas Chromatography-Mass Spectrometer observations of methyl iodide (CH3I) were made in the Eastern Pacific marine boundary layer during April 2010 as a part of the HaloCarbon Air Sea Transect-Pacific (HaloCAST-P) scientific cruise. The presence of IO in the open ocean environment was confirmed, with a maximum differential slant column density of 5 × 1013 molecules cm−2 along the 1° elevation angle (corresponding to approximately 1 pptv) measured in the oligotrophic region of the Southeastern Pacific. Such low IO mixing ratios and their observed geographical distribution are inconsistent with satellite estimates and with previous understanding of oceanic sources of iodine. A strong correlation was observed between reactive iodine (defined as IO + I) and CH3I, suggesting common sources

Glyoxal observations in the global marine boundary layer

Glyoxal is an important intermediate species formed by the oxidation of common biogenic and anthropogenic volatile organic compounds such as isoprene, toluene and acetylene. Although glyoxal has been shown to play an important role in urban and forested environments, its role in the open ocean environment is still not well understood, with only a few observations showing evidence for its presence in the open ocean marine boundary layer (MBL). In this study, we report observations of glyoxal from ten field campaigns in different parts of the world's oceans. These observations together represent the largest database of glyoxal in the MBL. The measurements are made with similar instruments that have been used in the past, although the open ocean values reported here, average of about 25 pptv with an upper limit of 40 pptv, are much lower than previously reported observations that were consistently higher than 40 pptv and had an upper limit of 140 pptv, highlighting the uncertainties in the Differential Optical Absorption Spectroscopy (DOAS) method for the retrieval of glyoxal. Despite retrieval uncertainties, the results reported in this work support previous suggestions that the currently known sources of glyoxal are insufficient to explain the average MBL concentrations. This suggests that there is an additional missing source, more than a magnitude larger than currently known sources, which is necessary to account for the observed atmospheric levels of glyoxal. Therefore it could play a more important role in the MBL than previously considered

Constraining the N2O5 UV absorption cross section from spectroscopic trace gas measurements in the tropical mid-stratosphere

The absorption cross section of N2O5, σN2O5(λ, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in (Jet Propulsion Laboratory) JPL-2011; the spread in laboratory data, however, points to an uncertainty in the range of 25 to 30%, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 by limb scanning DOAS (differential optical absorption spectroscopy) measurements (Weidner et al., 2005; Kritten et al., 2010), supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 + BrONO2 + HNO3) photochemistry and a non-linear least square fitting of the model result to the NO2 observations. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding – Balloon-borne version) observations in similar air masses at night-time, and all other relevant species from simulations of the SLIMCAT (Single Layer Isentropic Model of Chemistry And Transport) chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the σN2O5(λ, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200–260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260–350 nm), compared to current recommendations. As a consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended σN2O5(λ, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2–0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone

Evidence of atmospheric nanoparticle formation from emissions of marine microorganisms

International audienceEarth, as a whole, can be considered as a living organism emitting gases and particles into its atmosphere, in order to regulate its own temperature. In particular, oceans may respond to climate change by emitting particles that ultimately will influence cloud coverage. At the global scale, a large fraction of the aerosol number concentration is formed by nucleation of gas-phase species, but this process has never been directly observed above oceans. Here we present, using semicontrolled seawater-air enclosures, evidence that nucleation may occur from marine biological emissions in the atmosphere of the open ocean. We identify iodine-containing species as major precursors for new particle clusters’ formation, while questioning the role of the commonly accepted dimethyl sulfide oxidation products, in forming new particle clusters in the region investigated and within a time scale on the order of an hour. We further show that amines would sustain the new particle formation process by growing the new clusters to larger sizes. Our results suggest that iodine-containing species and amines are correlated to different biological tracers. These observations, if generalized, would call for a substantial change of modeling approaches of the sea-to-air interactions