Impact of biogenic very short-lived bromine on the Antarctic ozone hole during the 21st century

Active bromine released from the photochemical decomposition of biogenic very short-lived bromocarbons (VSL_Br ) enhances stratospheric ozone depletion. Based on a dual set of 1960-2100 coupled chemistry-climate simulations (i.e. with and without VSL Br ), we show that the maximum Antarctic ozone hole depletion increases by up to 14% when natural VSLBr are considered, in better agreement with ozone observations. The impact of the additional 5 pptv VSL Br on Antarctic ozone is most evident in the periphery of the ozone hole, producing an expansion of the ozone hole area of ~5 million km 2 , which is equivalent in magnitude to the recently estimated Antarctic ozone healing due to the implementation of the Montreal Protocol. We find that the inclusion of VSL Br in CAM-Chem does not introduce a significant delay of the modelled ozone return date to 1980 October levels, but instead affect the depth and duration of the simulated ozone hole. Our analysis further shows that total bromine-catalysed ozone destruction in the lower stratosphere surpasses that of chlorine by year 2070, and indicates that natural VSL Br chemistry would dominate Antarctic ozone seasonality before the end of the 21 st century. This work suggests a large influence of biogenic bromine on the future Antarctic ozone layer.Fil: Fernandez, Rafael Pedro. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; España. Universidad Tecnologica Nacional. Facultad Regional Mendoza. Secretaría de Ciencia, Tecnología y Postgrado; Argentina. 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 Francois. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Tilmes, Simone. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Saiz-lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; Españ

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

Laparoscopic radical prostatectomy with no anastomosis

From the first radical prostatectomy (RP), this kind of surgeries have always led to the need of a vesicourethral anastomosis (VUA). We present a case of a 65 year-old patient with diagnosis of prostate cancer and candidate for laparoscopic RP. The approach was a conventional extraperitoneal access with complete urethral sparing that avoids the need of VUA. Bladder catheter was removed on the third postoperative day observing immediate urinary continence. The anatomopathological analysis revealed a pT2 adenocarcinoma with negative margins. We report for the first time, a minimally invasive technique that avoids the need of VUA with favorable functional results

Chemical interactions between ship-originated air pollutants and ocean-emitted halogens

Ocean-going ships supply products from one region to another and contribute to the world's economy. Ship exhaust contains many air pollutants and results in significant changes in marine atmospheric composition. The role of Reactive Halogen Species (RHS) in the troposphere has received increasing recognition and oceans are the largest contributors to their atmospheric burden. However, the impact of shipping emissions on RHS and that of RHS on ship-originated air pollutants have not been studied in detail. Here, an updated WRF-Chem model is utilized to explore the chemical interactions between ship emissions and oceanic RHS over the East Asia seas in summer. The emissions and resulting chemical transformations from shipping activities increase the level of NO and NO2 at the surface, increase O3 in the South China Sea, but decrease O3 in the East China Sea. Such changes in pollutants result in remarkable changes in the levels of RHS as well as in their partitioning. The abundant RHS, in turn, reshape the loadings of air pollutants and those of the oxidants with marked patterns along the ship tracks. We, therefore, suggest that these important chemical interactions of ship-originated emissions with RHS should be considered in the environmental policy assessments of the role of shipping emissions in air quality and climate.Fil: Li, Qinyi. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Fernandez, Rafael P.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Mahan, Anoop. No especifíca;Fil: Lopez, Ana Isabel. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaFil: Shanshan, Wang. Key Laboratory Atmospheric Particle Pollution Research; ChinaFil: Puliafito, Salvador Enrique. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaFil: Cuevas, Carlos A.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Saiz Lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaEGU General Assembly 2021AustriaEuropean Geosciences Unio

Sub-micro- and nano-sized polyethylene terephthalate deconstruction with engineered protein nanopores

The identification or design of biocatalysts to mitigate the accumulation of plastics, including sub-micro- and nano-sized polyethylene terephthalate (nPET), is becoming a global challenge. Here we computationally incorporated two hydrolytic active sites with geometries similar to that of Idionella sakaiensis PET hydrolase, to fragaceatoxin C (FraC), a membrane pore-forming protein. FraCm1/m2 could be assembled into octameric nanopores (7.0 nm high × 1.6–6.0 nm entry), which deconstructed (40 °C, pH 7.0) nPET from GoodFellow, commodities and plastic bottles. FraCm1 and FraCm2 degrade nPET by endo- and exo-type chain scission. While FraCm1 produces bis(2-hydroxyethyl) terephthalate as the main product, FraCm2 yields a high diversity of oligomers and terephthalic acid. Mechanistic and biochemical differences with benchmark PET hydrolases, along with pore and nPET dynamics, suggest that these pore-forming protein catalytic nanoreactors do not deconstruct macro-PET but are promising in nanotechnology for filtering, capturing and breaking down nPET, for example, in wastewater treatment plants.This study was conducted under the auspices of the FuturEnzyme Project funded by the European Union’s Horizon 2020 Research and Innovation Programme under the auspices of the FuturEnzyme Project (grant agreement no. 101000327) and the PlasticsFatE project (grant agreement no. 95921), and Horizon Europe Research and Innovation Programme under grant agreement no. GA101060625 (Nymphe project). We also acknowledge financial support under grants PID2020-112758RB-I00 (M.F.), PDC2021-121534-I00 (M.F.), TED2021-130544B-I00 (M.F.), PID2019-106370RB-I00 (V.G.) and PID2019-105838RB-C31 (F.J.P.) from the Ministerio de Ciencia e Innovación, Agencia Estatal de Investigación (AEI) (Digital Object Identifier MCIN/AEI/10.13039/501100011033), Fondo Europeo de Desarrollo Regional (ERDF) A way of making Europe and the European Union NextGenerationEU/PRTR, UCM-Banco Santander Grants PR87/19-22556 and PR108/20-26896 and UnaEuropa (Unano) SF2106 (to A.M.P.). S.G.-L. was supported by a Real Colegio Complutense Postdoctoral Fellowship for Distinguished Junior Scholars. S.R. thanks the Spanish Ministry of Science and Innovation for a PhD fellowship (FPU19/00608). D.H.-M. thanks Complutense University of Madrid and Banco Santander for a PhD fellowship (CT82/20/CT83/20). A.R.-M. thanks the Spanish Ministry of Science and Innovation for a PhD fellowship (PRE2020-091825) and the project PID2019-106370RB-I00. We thank M. J. Vicente for the ESI–MS analysis, performed at the Servicio Interdepartamental de Investigación (SIDI) from the Autonomous University of Madrid, Spain.Peer Reviewed"Article signat per 16 autors/es: Ana Robles-Martín, Rafael Amigot-Sánchez, Laura Fernandez-Lopez, Jose L. Gonzalez-Alfonso, Sergi Roda, Víctor Alcolea-Rodriguez, Diego Heras-Márquez, David Almendral, Cristina Coscolín, Francisco J. Plou, Raquel Portela, Miguel A. Bañares, Álvaro Martínez-del-Pozo, Sara García-Linares, Manuel Ferrer & Víctor Guallar"Postprint (published version

Role of Iodine Recycling on Sea-Salt Aerosols in the Global Marine Boundary Layer

Heterogeneous uptake of hypoiodous acid (HOI), the dominant inorganic iodine species in the marine boundary layer (MBL), on sea-salt aerosol (SSA) to form iodine monobromide and iodine monochloride has been adopted in models with assumed efficiency. Recently, field measurements have reported a much faster rate of this recycling process than previously assumed in models. Here, we conduct global model simulations to quantify the range of effects of iodine recycling within the MBL, using Conventional, Updated, and Upper-limit coefficients. When considering the Updated coefficient, iodine recycling significantly enhances gaseous inorganic iodine abundance (similar to 40%), increases halogen atom production rates (similar to 40% in I, >100% in Br, and similar to 60% in Cl), and reduces oxidant levels (-7% in O-3, -2% in OH, and -4% in HO2) compared to the simulation without the process. We appeal for further direct measurements of iodine species, laboratory experiments on the controlling factors, and multiscale simulations of iodine heterogeneous recycling.Peer reviewe

Seasonal impact of biogenic very short-lived bromocarbons on lowermost stratospheric ozone between 60° N and 60° S during the 21st century

Biogenic very short-lived bromocarbons (VSLBr) currently represent ∼25 % of the total stratospheric bromine loading. Owing to their much shorter lifetime compared to anthropogenic long-lived bromine (e.g. halons) and chlorine (e.g. chlorofluorocarbons), the impact of VSLBr on ozone peaks in the lowermost stratosphere, which is a key climatic and radiative atmospheric region. Here we present a modelling study of the evolution of stratospheric ozone and its chemical loss within the tropics and at mid-latitudes during the 21st century. Two different experiments are explored: considering and neglecting the additional stratospheric injection of 5 ppt biogenic bromine naturally released from the ocean. Our analysis shows that the inclusion of VSLBr results in a realistic stratospheric bromine loading and improves the agreement between the model and satellite observations of the total ozone column (TOC) for the 1980?2015 period at mid-latitudes. We show that the overall ozone response to VSLBr at mid-latitudes follows the stratospheric evolution of long-lived inorganic chlorine and bromine throughout the 21st century. Additional ozone loss due to VSLBr is maximized during the present-day period (1990?2010), with TOC differences of −8 DU (−3 %) and −5.5 DU (−2 %) for the Southern Hemisphere and Northern Hemisphere mid-latitudes (SH-MLs and NH-MLs), respectively. Moreover, the projected TOC differences at the end of the 21st century are ∼50 % lower than the values found for the present-day period.We find that seasonal VSLBr impact on lowermost stratospheric ozone at mid-latitude is influenced by the seasonality of the heterogeneous inorganic-chlorine reactivation processes on ice crystals. Indeed, due to the more efficient reactivation of chlorine reservoirs (mainly ClONO2 and HCl) within the colder SH-ML lowermost stratosphere, the seasonal VSLBr impact shows a small but persistent hemispheric asymmetry through the whole modelled period. Our results indicate that, although the overall VSLBr-driven ozone destruction is greatest during spring, the halogen-mediated (Halogx-Loss) ozone loss cycle in the mid-latitude lowermost stratosphere during winter is comparatively more efficient than the HOx cycle with respect to other seasons. Indeed, when VSLBr are considered, Halogx-Loss dominates wintertime lowermost stratospheric ozone loss at SH-MLs between 1985 and 2020, with a contribution of inter-halogen ClOx?BrOx cycles to Halogx-Loss of ∼50 %.Within the tropics, a small (<−2.5 DU) and relatively constant (∼−1 %) ozone depletion mediated by VSLBr is closely related to their fixed emissions throughout the modelled period. By including the VSLBr sources, the seasonal Halogx-Loss contribution to lowermost stratospheric ozone loss is practically dominated by the BrOx cycle, reflecting the low sensitivity of very short-lived (VSL) bromine to background halogen abundances to drive tropical stratospheric ozone depletion. We conclude that the link between biogenic bromine sources and seasonal changes in heterogeneous chlorine reactivation is a key feature for future projections of mid-latitude lowermost stratospheric ozone during the 21st century.Fil: Barrera, Javier Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Fernandez, Rafael Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; Argentina. Consejo Superior de Investigaciones Científicas; España. Universidad Tecnológica Nacional; ArgentinaFil: Iglesias Suarez, Fernando. Consejo Superior de Investigaciones Científicas; EspañaFil: Cuevas, Carlos Alberto. Consejo Superior de Investigaciones Científicas; EspañaFil: Lamarque, Jean Francois. National Center for Atmospheric Research; Estados UnidosFil: Saiz-lopez, Alfonso. Consejo Superior de Investigaciones Científicas; Españ

A nocturnal atmospheric loss of CH2I2 in the remote marine boundary layer

This is the final version of the article. It was first available from Springer via http://dx.doi.org/10.1007/s10874-015-9320-6Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CH?I?) and chloro-iodomethane (CH?ICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CH?I? and CH?ICl in air and of CH?I? in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CH?I? was lower in amplitude than that of CH?ICl, despite its faster photolysis rate. We speculate that night-time loss of CH?I? occurs due to reaction with NO? radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k_(CH?I?+NO?) of ?4 ? 10??? cm? molecule?? s??; a previous kinetic study carried out at ?100 Torr found k_(CH?I?+NO?) of 4 ? 10??? cm? molecule?? s??. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/? 0.8 nmol m?? d?? for CH?I? and 3.7 +/? 0.8 nmol m?? d?? for CH?ICl), we show that the model overestimates night-time CH?I? by >60 % but reaches good agreement with the measurements when the CH?I?+ NO? reaction is included at 2?4 ? 10??? cm? molecule?? s??. We conclude that the reaction has a significant effect on CH?I? and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.LJC acknowledges NERC (NE/J00619X/1) and the National Centre for Atmospheric Science (NCAS) for funding. The laboratory work was supported by the NERC React-SCI (NE/K005448/1) and RONOCO (NE/F005466/1) grants

The added value of 18f-FDG PET/CT in the assessment of onset and steroid resistant polimyalgia rheumatica

PMR is a common inflammatory rheumatic disease. Although its clinical characteristics are fully recognized, no specific test for its diagnosis has been established to date. Several studies have described a wide variety of diseases that present with polymyalgic symptoms. A 18FDG-PET/CT scan could help to deal with these differential diagnoses. The goal of our study is to describe the findings of the 18FDG-PET/CT scan in a cohort of PMR patients and to detail how the 18FDG-PET/CT scan improves accuracy when diagnosing other underlying conditions. This cross-sectional study enrolled patients with a diagnosis of PMR who underwent to a 18FDG-PET/CT scan to rule out other diagnosis. The 18FDG-PET/CT scan was performed either following clinical criteria at the onset of clinical symptoms or when the patient became PMR steroid resistant. Patients' demographic, clinical and analytical data at the moment of the 18FDG-PET/CT scan were recorded. The final diagnosis was confirmed according to clinical judgement. A total of 103 patients with PMR were included. In 49.51% of patients, the 18FDG-PET/CT scan was ordered to study resistance to steroid therapy. The final diagnoses of patients were PMR in 70.9% patients, large vessel vasculitis in 15.5%, neoplasms 4.8% and another diagnosis in the rest. The 18FDG-PET/CT scan is a very useful technique for the study of Polymyalgia Rheumatica, not only to help in the diagnostic process, but also due to its role in the identification of a variety of PMR-like patrons

Evaluation of CAM-CHEM VSL model performance during Southtrac campaign

In the framework of the SouthTRAC Campaign (Transport and Composition of the Southern Hemisphere Upper Troposphere and Lower Stratosphere) based on Rio Grande, Argentina, a local research group from CONICET (Argentine National Research Council) joined the German consortium maintaining the HALO research aircraft (High-Altitude and LOng-range aircraft) to help with the flight planning and evaluation of the chemical composition of the upper troposphere and lower stratosphere within the ozone hole periphery. The SouthTRAC aircraft campaign was carried out in two phases which took place in September and November 2019, respectively. With the purpose of providing additional information of the atmospheric composition of brominated Very Short-Lived (VSLBr) species and compare with HALO observations during the transfer and campaign flights, a CAM-Chem (Community Atmosphere Model with Chemistry) global chemistry-climate simulation was conducted. The model setup used in the halogenated CAM-Chem simulation had a 1° x 1.25° lat-lon resolution, 56 hybrid vertical levels from the surface to the middle stratosphere and considered assimilated meteorology from MERRA, including an explicit treatment of VSLBr sources and chemistry. Model output of VSLBr, long-lived bromine and chlorine (LLBr and LLCl) species and ozone mixing ratios, as well as the main inorganic halogen reactive and reservoir species and gas/heterogeneous phase reaction rates affecting lowermost stratospheric ozone were analyzed in horizontal domains and vertical cross-sections across each flightpath. The model performance with respect to the HALO observations has a general good agreement, presenting better results for mid latitudes (between 30º S and 50º S) than for southern latitudes (>50º S). In particular, CAM-Chem timeseries consistently reproduced the spatio-temporal variation of the main VSLBr species (CH2Br2 and CHBr3), including the sharp variations observed across the tropopause. For both VSLBr as well as for LLCl compounds such as CFC-12, the Pearson correlation coefficient r obtained during each of the flights ranged between 0.7 and 0.9, while the Normalized Mean Bias (NMB) was smaller than 8% for almost every flight. Regarding LLBr CH3Br, the correlation with the aircraft observations is high (r>0.9) but the inter-hemispheric variability during transfer flights is not fully captured. For Ozone, the model presents mid to high correlation with respect to measures (0.5Fil: Berná Peña, Lucas Luciano. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaFil: Lopez Noreña, Ana Isabel. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Puliafito, Salvador Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentina. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaFil: Barreras, Javier Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Engel, Andreas. Goethe Universitat Frankfurt; AlemaniaFil: Jesswein, Markus. Goethe Universitat Frankfurt; AlemaniaFil: Cuevas, Carlos A.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Saiz Lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Fernandez, Rafael Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaEGU General Assembly 2021AustriaEuropean Geosciences Unio