Publications

Abstract: Terpenoids (Isoprene And Monoterpenes) Are Highly Reactive Volatile Organic Compounds (Vocs) Known For Decades For Their Biogenic Origin. Here, We Discuss The Nature And Magnitude Of Their Anthropogenic Emissions. We Compiled And Re-Analyzed 14 Data Sets Of In Situ Voc Observations Collected Over The Last Decade In Contrasting Urban Areas From Mid-Latitudes To Subtropical Regions. We Show The Systematic Presence Of Anthropogenic Terpenoids In Urban Ambient Air With Clear Covariations With Anthropogenic Compounds (R-2 > 0.50) Even During Mid-Latitude Winters. Despite The Emerging Importance Of Monoterpene Emissions From Consumer Products In North American Cities, There Is Some Evidence Of Monoterpene Emissions From Tailpipe Exhaust In Cities Of The Developing World. The Traffic-Related Fraction Of Monoterpenes Is Estimated And Can Account For Up To 40% Of Their Ambient Levels. The Anthropogenic Emission Ratios (Er) Of Some Terpenoids (Isoprene, A-Pinene And Limonene) Are Estimated And Spatially Compared. The Anthropogenic Emissions Of Terpenoids Are Indirectly Estimated From Those Er Combined To Regional And Global Emission Inventories (Cams-Glob-Ant_V4.2) At Urban And Country Scale Focusing On France, Lebanon, And Vietnam. Those Anthropogenic Emissions Do Not Represent More Than 3% Of Other Anthropogenic Voc Emissions. However, They Dominate By One To Three Orders Of Magnitude The Reactivity Of Other Anthropogenic Vocs Regarding No3 Oxidation And Ozonolysis. This Study Raises Two Questions Which Need Further Investigations In The Future: (A) The Significance Of Terpenoid Emissions From Traffic, Especially In Urban Areas Of The Developing World And (B) The Role Of Anthropogenic Terpenoids In Nighttime And Wintertime Atmospheric Chemistry At Mid-Latitudes.

Abstract: In Europe, Covid-19 Lockdown Restrictions Were First Implemented In March 2020 To Control The Spread Of The Disease From The Sars-Cov-2 Virus. Many Studies Have Focused On The Influence Of The Applied Measures On Pollution Levels During This Period, But Very Limited Information On The Oxidative Potential (Op), An Emerging Metric Of Particulate Matter (Pm) Exposure. Furthermore, Most Previous Studies Also Commonly Used Comparative Methods With Historical Datasets, Which May Not Be Estimating The Real Pollution Levels Without The Lockdown Restrictions In Place. In This Study, The Op Of Pm Collected At Urban Background (Grenoble, France) And Traffic (Bern, Switzerland) Sites Was Assessed Using Dithiothreitol (Dtt) And Ascorbic Acid (Aa) Assays. These Measurements Were Also Compared With Pm And Black Carbon (Bc) Mass Concentrations, Including The Wood Burning And Fossil Fuel Fractions Of Bc. To Obtain A More Realistic Pollution Level, Assuming There Were No Lockdown Restrictions In Place, A Machine Learning Technique Called The Random Forest (Rf) Regression Model Was Applied To Predict A Business-As-Usual (Bau) Level For Op, Pm, And Bc In Both Sites. This Model Provided A Good Estimate Of The Bau Levels, Allowing A More Realistic Assessment Of The Pollution Changes During The Lockdown Period. The Results Indicate A Clear Decrease In Op Found In The Traffic Site, While A More Modest Change In Op Was Found At The Urban Background Site, Likely Due To Sustained Contributions From Wood Burning Sources For Residential Heating. Overall, This Study Confirms The Major Roles Of Both Of These Combustion Sources In The Op Levels In Ambient Air.

Abstract: Background: Combined Effect Of Both Prenatal And Early Postnatal Exposure To Ambient Air Pollution On Child Cognition Has Rarely Been Investigated And Periods Of Sensitivity Are Unknown. This Study Explores The Temporal Relationship Between Pre- And Postnatal Exposure To Pm10, Pm2.5, No2 And Child Cognitive Function. Methods: Using Validated Spatiotemporally Resolved Exposure Models, Pre- And Postnatal Daily Pm2.5, Pm10 (Satellite Based, 1 Km Resolution) And No2 (Chemistry-Transport Model, 4 Km Resolution) Concentrations At The Mother'S Residence Were Estimated For 1271 Mother-Child Pairs From The French Eden And Pelagie Cohorts. Scores Representative Of Children'S General, Verbal And Non-Verbal Abilities At 5-6 Years Were Constructed Based On Subscale Scores From The Wppsi-Iii, Wisc-Iv Or Nepsy-Ii Batteries, Using Confirmatory Factor Analysis (Cfa). Associations Of Both Prenatal (First 35 Gestational Weeks) And Postnatal (60 Months After Birth) Exposure To Air Pollutants With Child Cognition Were Explored Using Distributed Lag Non-Linear Models Adjusted For Confounders. Results: Increased Maternal Exposure To Pm10, Pm2.5 And No2, During Sensitive Windows Comprised Between The 15Th And The 33Rd Gestational Weeks, Was Associated With Lower Males' General And Non-Verbal Abilities. Higher Postnatal Exposure To Pm2.5 Between The 35Th And 52Nd Month Of Life Was Associated With Lower Males' General, Verbal And Non-Verbal Abilities. Some Protective Associations Were Punctually Observed For The Very First Gestational Weeks Or Months Of Life For Both Males And Females And The Different Pollutants And Cognitive Scores. Discussion: These Results Suggest Poorer Cognitive Function At 5-6 Years Among Males Following Increased Maternal Exposure To Pm10, Pm2.5 And No2 During Mid-Pregnancy And Child Exposure To Pm2.5 Around 3-4 Years. Apparent Protective Associations Observed Are Unlikely To Be Causal And Might Be Due To Live Birth Selection Bias, Chance Finding Or Residual Confounding.

Abstract: From The Micro- To The Mesoscale, Water And Energy Budgets Of Mountainous Catchments Are Largely Driven By Topographic Features Such As Terrain Orientation, Slope, Steepness, And Elevation, Together With Associated Meteorological Forcings Such As Precipitation, Solar Radiation, And Wind Speed. Those Topographic Features Govern The Snow Deposition, Melting, And Transport, Which Further Impacts The Overall Water Cycle. However, This Microscale Variability Is Not Well Represented In Earth System Models Due To Coarse Resolutions. This Study Explores The Impact Of Precipitation, Shortwave Radiation, And Wind Speed On The Water Budget Distribution Over A 15.28 Ha Small, Mid-Elevation (2000-2200 M) Alpine Catchment At Col Du Lautaret (France). The Grass-Dominated Catchment Remains Covered With Snow For 5 To 6 Months Per Year. The Surface-Subsurface Coupled Distributed Hydrological Model Parflow-Clm Is Used At A Very High Resolution (10 M) To Simulate The Impacts On The Water Cycle Of Meteorological Variability At Very Small Spatial And Temporal Scales. These Include 3D Simulations Of Hydrological Fluxes With Spatially Distributed Forcing Of Precipitation, Shortwave Radiation, And Wind Speed Compared To 3D Simulations Of Hydrological Fluxes With Non-Distributed Forcing. Our Precipitation Distribution Method Encapsulates The Spatial Snow Distribution Along With Snow Transport. The Model Simulates The Dynamics And Spatial Variability Of Snow Cover Using The Common Land Model (Clm) Energy Balance Module And Under Different Combinations Of Distributed Forcing. The Resulting Subsurface And Surface Water Transfers Are Computed By The Parflow Module. Distributed Forcing Leads To Spatially Heterogeneous Snow Cover Simulation, Which Becomes Patchy At The End Of The Melt Season And Shows A Good Agreement With The Remote Sensing Images (Mean Bias Error (Mbe) = 0.22). This Asynchronous Melting Results In A Longer Melting Period Compared To The Non-Distributed Forcing, Which Does Not Generate Any Patchiness. Among The Distributed Meteorological Forcings Tested, Precipitation Distribution, Including Snow Transport, Has The Greatest Impact On Spatial Snow Cover (Mbe = 0.06) And Runoff. Shortwave Radiation Distribution Has An Important Impact, Reducing Evapotranspiration As A Function Of The Slope Orientation (Decreasing The Slope Between Observed And Simulated Evapotranspiration From 1.55 To 1.18). For The Primarily East-Facing Catchment Studied Here, Distributing Shortwave Radiation Helps Generate Realistic Timing And Spatial Heterogeneity In The Snowmelt At The Expense Of An Increase In The Mean Bias Error (From 0.06 To 0.22) For All Distributed Forcing Simulations Compared To The Simulation With Only Distributed Precipitation. Distributing Wind Speed In The Energy Balance Calculation Has A More Complex Impact On Our Catchment, As It Accelerates Snowmelt When Meteorological Conditions Are Favorable But Does Not Generate Snow Patches At The End Of Our Test Case. This Shows That Slope- And Aspect-Based Meteorological Distribution Can Improve The Spatio-Temporal Representation Of Snow Cover And Evapotranspiration In Complex Mountain Terrain.

Abstract: The Arctic Environment Is Transforming Rapidly Due To Climate Change. Aerosols' Abundance And Physicochemical Characteristics Play A Crucial, Yet Uncertain, Role In These Changes Due To Their Influence On The Surface Energy Budget Through Direct Interaction With Solar Radiation And Indirectly Via Cloud Formation. Importantly, Arctic Aerosol Properties Are Also Changing In Response To Climate Change. Despite Their Importance, Year-Round Measurements Of Their Characteristics Are Sparse In The Arctic And Often Confined To Lower Latitudes At Arctic Land-Based Stations And/Or Short High-Latitude Summertime Campaigns. Here, We Present Unique Aerosol Microphysics And Chemical Composition Datasets Collected During The Year-Long Multidisciplinary Drifting Observatory For The Study Of Arctic Climate (Mosaic) Expedition, In The Central Arctic. These Datasets, Which Include Aerosol Particle Number Concentrations, Size Distributions, Cloud Condensation Nuclei Concentrations, Fluorescent Aerosol Concentrations And Properties, And Aerosol Bulk Chemical Composition (Black Carbon, Sulfate, Nitrate, Ammonium, Chloride, And Organics) Will Serve To Improve Our Understanding Of High-Arctic Aerosol Processes, With Relevance Towards Improved Modelling Of The Future Arctic (And Global) Climate.

Abstract: Terrestrial Volcanism Is Known To Emit Mercury (Hg) Into The Atmosphere. However, Despite Many Years Of Investigation, Its Net Impact On The Atmospheric Hg Budget Remains Insufficiently Constrained, In Part Because The Transformations Of Hg In Volcanic Plumes As They Age And Mix With Background Air Are Poorly Understood. Here We Report The Observation Of Complete Gaseous Elemental Mercury (Gem) Depletion Events In Dilute And Moderately Aged (& Sim;3-7 Hours) Volcanic Plumes From Piton De La Fournaise On Reunion Island. While It Has Been Suggested That Co-Emitted Bromine Could, Once Photochemically Activated, Deplete Gem In A Volcanic Plume, We Measured Low Bromine Concentrations In Both The Gas- And Particle-Phase And Observed Complete Gem Depletion Even Before Sunrise, Ruling Out A Leading Role Of Bromine Chemistry Here. Instead, We Hypothesize That The Gem Depletions Were Mainly Caused By Gas-Particle Interactions With Sulfate-Rich Volcanic Particles (Mostly Of Submicron Size), Abundantly Present In The Dilute Plume. We Consider Heterogeneous Gem Oxidation And Gem Uptake By Particles As Plausible Manifestations Of Such A Process And Derive Empirical Rate Constants. By Extrapolation, We Estimate That Volcanic Aerosols May Scavenge 210 Mg Y(-1) (67-480 Mg Y(-1)) Of Hg From The Atmosphere Globally, Acting Effectively As Atmospheric Mercury Sink. While This Estimate Is Subject To Large Uncertainties, It Highlights That Hg Transformations In Aging Volcanic Plumes Must Be Better Understood To Determine The Net Impact Of Volcanism On The Atmospheric Hg Budget And Hg Deposition Pathways.

Abstract: Natural Aerosols And Their Interactions With Clouds Remain An Important Uncertainty Within Climate Models, Especially At The Poles. Here, We Study The Behavior Of Sea Salt Aerosols (Ssaer) In The Arctic And Antarctic Within 12 Climate Models From Cmip6. We Investigate The Driving Factors That Control Ssaer Abundances And Show Large Differences Based On The Choice Of The Source Function, And The Representation Of Aerosol Processes In The Atmosphere. Close To The Poles, The Cmip6 Models Do Not Match Observed Seasonal Cycles Of Surface Concentrations, Likely Due To The Absence Of Wintertime Ssaer Sources Such As Blowing Snow. Further Away From The Poles, Simulated Concentrations Have The Correct Seasonality, But Have A Positive Mean Bias Of Up To One Order Of Magnitude. Ssaer Optical Depth Is Derived From The Modis Data And Compared To Modeled Values, Revealing Good Agreement, Except For Winter Months. Better Agreement For Aerosol Optical Depth Than Surface Concentration May Indicate A Need For Improving The Vertical Distribution, The Size Distribution And/Or Hygroscopicity Of Modeled Polar Ssaer. Source Functions Used In Cmip6 Emit Very Different Numbers Of Small Ssaer, Potentially Exacerbating Cloud-Aerosol Interaction Uncertainties In These Remote Regions. For Future Climate Scenarios Ssp126 And Ssp585, We Show That Ssaer Concentrations Increase At Both Poles At The End Of The 21St Century, With More Than Two Times Mid-20Th Century Values In The Arctic. The Pre-Industrial Climate Cmip6 Experiments Suggest There Is A Large Uncertainty In The Polar Radiative Budget Due To Ssaer.Plain Language Summary Aerosols Emitted From The Ocean, Such As Sea Salt Particles (Aerosols), Are Critical For The Climate Of Polar Regions. However, There Is Still Uncertainty In Their Representation In Climate Models. The Purpose Of This Work Is To Evaluate The Representation Of Sea Salt Aerosols (Ssaer) In The Arctic And Antarctic In A Recent Model Inter-Comparison Initiative, And To Assess The Consequences For Our Understanding Of Present-Day And Future Polar Climate. We Find That The Models Disagree Between Them And With Observations From Ground Stations And From Space. This Suggests That The Formulation Of Sea Salt Emissions In Global Models Is Not Adapted For Polar Regions. With Sea Ice Retreat, Ssaer Will Most Likely Increase In The Future, Which Makes Addressing The Current Uncertainty An Important Next Step For The Scientific Community.

Abstract: The Minamata Convention, A Global And Legally Binding Treaty That Entered Into Force In 2017, Aims To Protect Human Health And The Environment From Harmful Mercury (Hg) Effects By Reducing Anthropogenic Hg Emissions And Environmental Levels. The Conference Of The Parties Is To Periodically Evaluate The Convention'S Effectiveness, Starting In 2023, Using Existing Monitoring Data And Observed Trends. Monitoring Atmospheric Hg Levels Has Been Proposed As A Key Indicator. However, Data Gaps Exist, Especially In The Southern Hemisphere. Here, We Present Over A Decade Of Atmospheric Hg Monitoring Data At Amsterdam Island (37.80 Degrees S, 77.55 Degrees E), In The Remote Southern Indian Ocean. Datasets Include Gaseous Elemental And Oxidised Hg Species Ambient Air Concentrations From Either Active/Continuous Or Passive/Discrete Acquisition Methods, And Annual Total Hg Wet Deposition Fluxes. These Datasets Are Made Available To The Community To Support Policy-Making And Further Scientific Advancements.

Abstract: La Paz And El Alto Are Two Fast-Growing, High-Altitude Bolivian Cities Forming The Second-Largest Metropolitan Area In The Country. Located Between 3200 And 4050 M A.S.L. (Above Sea Level), These Cities Are Home To A Burgeoning Population Of Approximately 1.8 Million Residents. The Air Quality In This Conurbation Is Heavily Influenced By Urbanization; However, There Are No Comprehensive Studies Evaluating The Sources Of Air Pollution And Their Health Impacts. Despite Their Proximity, The Substantial Variation In Altitude, Topography, And Socioeconomic Activities Between La Paz And El Alto Result In Distinct Sources, Dynamics, And Transport Of Particulate Matter (Pm). In This Investigation, Pm10 Samples Were Collected At Two Urban Background Stations Located In La Paz And El Alto Between April 2016 And June 2017. The Samples Were Later Analyzed For A Wide Range Of Chemical Species Including Numerous Source Tracers (Oc, Ec, Water-Soluble Ions, Sugar Anhydrides, Sugar Alcohols, Trace Metals, And Molecular Organic Species). The United States Environmental Protection Agency (U.S. Epa) Positive Matrix Factorization (Pmf V.5.0) Receptor Model Was Employed For The Source Apportionment Of Pm10. This Is One Of The First Source Apportionment Studies In South America That Incorporates An Extensive Suite Of Organic Markers, Including Levoglucosan, Polycyclic Aromatic Hydrocarbons (Pahs), Hopanes, And Alkanes, Alongside Inorganic Species. The Multisite Pmf Resolved 11 Main Sources Of Pm. The Largest Annual Contribution To Pm10 Came From The Following Two Major Sources: The Ensemble Of The Four Vehicular Emissions Sources (Exhaust And Non-Exhaust), Accountable For 35 % And 25 % Of The Measured Pm In La Paz And El Alto, Respectively; And Dust, Which Contributed 20 % And 32 % To The Total Pm Mass. Secondary Aerosols Accounted For 22 % (24 %) In La Paz (El Alto). Agricultural Smoke Resulting From Biomass Burning In The Bolivian Lowlands And Neighboring Countries Contributed To 9 % (8 %) Of The Total Pm10 Mass Annually, Increasing To 17 % (13 %) Between August-October. Primary Biogenic Emissions Were Responsible For 13 % (7 %) Of The Measured Pm10 Mass. Additionally, A Profile Associated With Open Waste Burning Occurring From May To August Was Identified. Although This Source Contributed Only To 2 % (5 %) Of The Total Pm10 Mass, It Constitutes The Second Largest Source Of Pahs, Which Are Compounds Potentially Hazardous To Human Health. Our Analysis Additionally Resolved Two Different Traffic-Related Factors, A Lubricant Source (Not Frequently Identified), And A Non-Exhaust Emissions Source. Overall, This Study Demonstrates That Pm10 Concentrations In La Paz And El Alto Region Are Predominantly Influenced By A Limited Number Of Local Sources. In Conclusion, To Improve Air Quality In Both Cities, Efforts Should Primarily Focus On Addressing Dust, Traffic Emissions, Open Waste Burning, And Biomass Burning.

Abstract: Past And Present Anthropogenic Mercury (Hg) Release To Ecosystems Causes Neurotoxicity And Cardiovascular Disease In Humans With An Estimated Economic Cost Of $117 Billion Usd Annually. Humans Are Primarily Exposed To Hg Via The Consumption Of Contaminated Freshwater And Marine Fish. The Unep Minamata Convention On Hg Aims To Curb Hg Release To The Environment And Is Accompanied By Global Hg Monitoring Efforts To Track Its Success. The Biogeochemical Hg Cycle Is A Complex Cascade Of Release, Dispersal, Transformation And Bio-Uptake Processes That Link Hg Sources To Hg Exposure. Global Change Interacts With The Hg Cycle By Impacting The Physical, Biogeochemical And Ecological Factors That Control These Processes. In This Review We Examine How Global Change Such As Biome Shifts, Deforestation, Permafrost Thaw Or Ocean Stratification Will Alter Hg Cycling And Exposure. Based On Past Declines In Hg Release And Environmental Levels, We Expect That Future Policy Impacts Should Be Distinguishable From Global Change Effects At The Regional And Global Scales.

Abstract: Mercury (Hg) Fate And Transport Research Requires More Effort To Obtain A Deep Knowledge Of Its Biogeochemical Cycle, Particularly In The Southern Hemisphere And Tropics That Are Still Missing Of Distributed Monitoring Sites.Continuous Monitoring Of Atmospheric Hg Concentrations And Trend Worldwide Is Relevant For The Effectiveness Evaluation Of The Minamata Convention On Mercury (Mcm) Actions. In This Context, Gaseous Elemental Mercury (Gem) And Total Mercury (Thg) In Precipitations Were Monitored From 2013 To 2019 At The Amsterdam Island Observatory (Ams -37 Degrees 48 ' S, 77 Degrees 34 ' E) To Provide Insights Into The Hg Pathway In The Remote Southern Indian Ocean, Also Considering Ancillary Dataset Of Rn-222, Co2, Co, And Ch4. Gem Average Concentration Was 1.06 +/- 0.07 Ng M- 3, With A Slight Increase During The Austral Winter Due To Both Higher Wind Speed Over The Surface Ocean And Contributions From Southern Africa. In Wet Depositions, Thg Average Concen-Tration Was 2.39 +/- 1.17 Ng L-1, Whereas The Annual Flux Averaged 2.04 +/- 0.80 Mu Gm- 2 Year -1. In General, Both Gem And Volume-Weighted Mean Concentration (Vwmc) Of Thg Did Not Show An Increasing/Decreasing Trend Over The Seven-Year Period, Suggesting A Substantial Lack Of Evolution About Emission Of Hg Reaching Ams.Air Masses Cluster Analysis And Potential Source Contribution Function Showed That Oceanic Evasion Was The Main Hg Contributor At Ams, While Further Contributions Were Attributable To Long-Range Transport Events From Southern Africa, Particularly When The Occurrence Of El Nin Similar To O Increased The Frequency Of Wildfires.

Abstract: Atmospheric Gaseous Elemental Mercury (Gem) Concentrations In The Arctic Exhibit A Clear Summertime Maximum, While The Origin Of This Peak Is Still A Matter Of Debate In The Community. Based On Summertime Observations During The Multidisciplinary Drifting Observatory For The Study Of Arctic Climate (Mosaic) Expedition And A Modeling Approach, We Further Investigate The Sources Of Atmospheric Hg In The Central Arctic. Simulations With A Generalized Additive Model (Gam) Show That Long-Range Transport Of Anthropogenic And Terrestrial Hg From Lower Latitudes Is A Minor Contribution (Similar To 2%), And More Than 50% Of The Explained Gem Variability Is Caused By Oceanic Evasion. A Potential Source Contribution Function (Pscf) Analysis Further Shows That Oceanic Evasion Is Not Significant Throughout The Ice-Covered Central Arctic Ocean But Mainly Occurs In The Marginal Ice Zone (Miz) Due To The Specific Environmental Conditions In That Region. Our Results Suggest That This Regional Process Could Be The Leading Contributor To The Observed Summertime Gem Maximum. In The Context Of Rapid Arctic Warming And The Observed Increase In Width Of The Miz, Oceanic Hg Evasion May Become More Significant And Strengthen The Role Of The Central Arctic Ocean As A Summertime Source Of Atmospheric Hg.

Abstract: New Particle Formation (Npf) In The Tropical Free Troposphere (Ft) Is A Globally Important Source Of Cloud Condensation Nuclei, Affecting Cloud Properties And Climate. Oxidized Organic Molecules (Ooms) Produced From Biogenic Volatile Organic Compounds Are Believed To Contribute To Aerosol Formation In The Tropical Ft, But Without Direct Chemical Observations. We Performed In Situ Molecular-Level Ooms Measurements At The Bolivian Station Chacaltaya At 5240 M Above Sea Level, On The Western Edge Of Amazonia. For The First Time, We Demonstrate The Presence Of Ooms, Mainly With 4-5 Carbon Atoms, In Both Gas-Phase And Particle-Phase (In Terms Of Mass Contribution) Measurements In Tropical Ft Air From Amazonia. These Observations, Combined With Air Mass History Analyses, Indicate That The Observed Ooms Are Linked To Isoprene Emitted From The Rainforests Hundreds Of Kilometers Away. Based On Particle-Phase Measurements, We Find That These Compounds Can Contribute To Npf, At Least The Growth Of Newly Formed Nanoparticles, In The Tropical Ft On A Continental Scale. Thus, Our Study Is A Fundamental And Significant Step In Understanding The Aerosol Formation Process In The Tropical Ft. In-Situ Molecular-Level Measurements Demonstrate The Presence Of Oxidized Organic Molecules, Mainly With 4-5 Carbon Atoms, In Both Gas-Phase And Particle-Phase In Tropical Free Troposphere Air From Amazonia. These Molecules Are Linked To Isoprene Emitted From The Rainforests Hundreds Of Kilometers Away, And Can Contribute To New Particle Formation.

Abstract: Reactive chlorine and bromine species emitted from snow and aerosols can significantly alter the oxidative capacity of the polar boundary layer. However, halogen production mechanisms from snow remain highly uncertain, making it difficult for most models to include descriptions of halogen snow emissions and to understand the impact on atmospheric chemistry. We investigate the influence of Arctic halogen emissions from snow on boundary layer oxidation processes using a one-dimensional atmospheric chemistry and transport model (PACT-1D). To understand the combined impact of snow emissions and boundary layer dynamics on atmospheric chemistry, we model Cl-2 and Br-2 primary emissions from snow and include heterogeneous recycling of halogens on both snow and aerosols. We focus on a 2-day case study from the 2009 Ocean-Atmosphere-Sea Ice-Snowpack campaign at Utqia & x121;vik, Alaska. The model reproduces both the diurnal cycle and high quantity of Cl-2 observed, along with the measured concentrations of Br-2, BrO, and HOBr. Due to the combined effects of emissions, recycling, vertical mixing, and atmospheric chemistry, reactive chlorine is typically confined to the lowest 15 m of the atmosphere, while bromine can impact chemistry up to and above the surface inversion height. Upon including halogen emissions and recycling, the concentration of HOx (HOx = OH + HO2) at the surface increases by as much as a factor of 30 at mid-day. The change in HOx due to halogen chemistry, as well as chlorine atoms derived from snow emissions, significantly reduce volatile organic compound lifetimes within a shallow layer near the surface.

Abstract: During Arctic Springtime, Halogen Radicals Oxidize Atmospheric Elemental Mercury (Hg-0), Which Deposits To The Cryosphere. This Is Followed By A Summertime Atmospheric Hg-0 Peak That Is Thought To Result Mostly From Terrestrial Hg Inputs To The Arctic Ocean, Followed By Photoreduction And Emission To Air. The Large Terrestrial Hg Contribution To The Arctic Ocean And Global Atmosphere Has Raised Concern Over The Potential Release Of Permafrost Hg, Via Rivers And Coastal Erosion, With Arctic Warming. Here We Investigate Hg Isotope Variability Of Arctic Atmospheric, Marine, And Terrestrial Hg. We Observe Highly Characteristic Hg Isotope Signatures During The Summertime Peak That Reflect Re-Emission Of Hg Deposited To The Cryosphere During Spring. Air Mass Back Trajectories Support A Cryospheric Hg Emission Source But No Major Terrestrial Source. This Implies That Terrestrial Hg Inputs To The Arctic Ocean Remain In The Marine Ecosystem, Without Substantial Loss To The Global Atmosphere, But With Possible Effects On Food Webs. Arctic Warming Thaws Permafrost, Leading To Enhanced Soil Mercury Transport To The Arctic Ocean. Mercury Isotope Signatures In Arctic Rivers, Ocean And Atmosphere Suggest That Permafrost Mercury Is Buried In Marine Sediment And Not Emitted To The Global Atmosphere

Abstract: Background: Prenatal Exposure To Fine Particulate Matter (Pm2.5) Assessed Through Its Mass Concentration Has Been Associated With Foetal Growth Restriction In Studies Based On Outdoor Levels. Oxidative Potential Of Pm2.5 (Op) Is An Emerging Metric A Priori Relevant To Mechanisms Of Action Of Pm On Health, With Very Limited Evidence To Indicate Its Role On Birth Outcomes. Objectives: We Investigated The Association Of Op With Birth Outcomes And Compared It With That Of Pm2.5 Mass Concentration. Methods: 405 Pregnant Women From Sepages Cohort (Grenoble Area) Carried Pm2.5 Personal Dosimeters For One Or Two One-Week Periods. Op Was Measured Using Dithiothreitol (Dtt) And Ascorbic Acid (Aa) Assays From The Collected Filters. Associations Of Each Exposure Metric With Offspring Weight, Height, And Head Circumference At Birth Were Estimated Adjusting For Potential Confounders. Results: The Correlation Between Pm2.5 Mass Concentration And Opvdtt Was 0.7. An Interquartile Range Increase In – Was Associated With Reduced Weight (Adjusted Change, -64 G, -166 To -11, P = 0.02) And Height (-4 Mm, -6 To -1, P = 0.01) At Birth. Pm2.5 Mass Concentration Showed Similar Associations With Weight (-53 G, -99 To -8, P = 0.02) And Height (-2 Mm, -5 To 0, P = 0.05). In Birth Height Models Mutually Adjusted For The Two Exposure Metrics, The Association With Opvdtt Was Less Attenuated Than That With Mass Concentration, While For Weight Both Effect Sizes Attenuated Similarly. There Was No Clear Evidence Of Associations With Head Circumference For Any Metric, Nor For Opvaa With Any Growth Parameter. Impact: Pm2.5 Pregnancy Exposure Assessed From Personal Dosimeters Was Associated With Altered Foetal Growth. Personal Op Exposure Was Associated With Foetal Growth Restrictions, Specifically Decreased Weight And Height At Birth, Possibly To A Larger Extent Than Pm2.5 Mass Concentration Alone. These Results Support Op Assessed From Dtt As Being A Health-Relevant Metric. Larger Scale Cohort Studies Are Recommended To Support Our Findings.

Abstract: The spatiotemporal variations in free-cellulose concentrations in atmospheric particles, as a proxy for plant debris, were investigated using an improved protocol with a high-performance liquid chromatography with pulsed amperometric detection (HPLC-PAD) method. Filter samples were taken from nine sites of varying characteristics across France and Switzerland, with sampling covering all seasons. Concentrations of cellulose, as well as carbonaceous aerosol and other source-specific chemical tracers (e.g. elemental carbon, EC; levoglucosan; polyols; trace metals; and glucose), were quantified. Annual mean free-cellulose concentrations within PM10 (particulate matter) ranged from 29 +/- 38 ng m(-3) at Basel (urban site) to 284 +/- 225 ng m(-3) at Payerne (rural site). Concentrations were considerably higher during episodes, with spikes exceeding 1150 and 2200 ng m(-3) at Payerne and ANDRA-OPE (Agence nationale pour la gestion des dechets radioactifs Observatoire Perenne de l'Environnement; rural site), respectively. A clear seasonality, with highest cellulose concentrations during summer and autumn, was observed at all rural and some urban sites. However, some urban locations exhibited a weakened seasonality. Contributions of cellulose carbon to total organic carbon are moderate on average (0.7 %-5.9 %) but much greater during “episodes”, reaching close to 20 % at Payerne. Cellulose concentrations correlated poorly between sites, even at ranges of about 10 km, indicating the localised nature of the sources of atmospheric plant debris. With regards to these sources, correlations between cellulose and typical biogenic chemical tracers (polyols and glucose) were moderate to strong (R-s = 0.28-0.78, p < 0.0001) across the nine sites. Seasonality was strongest at sites with stronger biogenic correlations, suggesting the main source of cellulose arises from biogenic origins. A second input to ambient plant debris concentrations was suggested via resuspension of plant matter at several urban sites, due to moderate cellulose correlations with mineral dust tracers, Ca2+, and Ti metal (R-s = 0.28-0.45, p < 0.007). No correlation was obtained with the biomass burning tracer (levoglucosan), an indication that this is not a source of atmospheric cellulose. Finally, an investigation into the interannual variability in atmospheric cellulose across the Grenoble metropole was completed. It was shown that concentrations and sources of ambient cellulose can vary considerably between years. All together, these results deeply improve our knowledge on the phenomenology of plant debris within ambient air.

Abstract: This Work Presents The Results From A Set Of Aerosol- And Gas-Phase Measurements Collected During The Bio-Maido Field Campaign In Reunion Between March 8And April 5, 2019. Several Offline And Online Sampling Devices Were Installed At The Maido Observatory (Mo), A Remote High-Altitude Site In The Southern Hemisphere, Allowing The Physical And Chemical Characterization Of Atmospheric Aerosols And Gases. The Evaluation Of Short-Lived Gas-Phase Measurements Allows Us To Conclude That Air Masses Sampled During This Period Contained Little Or No Anthropogenic Influence. The Dominance Of Sulfate And Organic Species In The Submicron Fraction Of The Aerosol Is Similar To That Measured At Other Coastal Sites. Carboxylic Acids On Pm10 Showed A Significant Contribution Of Oxalic Acid, A Typical Tracer Of Aqueous Processed Air Masses, Increasing At The End Of The Campaign. This Result Agrees With The Positive Matrix Factorization Analysis Of The Submicron Organic Aerosol, Where More Oxidized Organic Aerosols (Mooas) Dominated The Organic Aerosol With An Increasing Contribution Toward The End Of The Campaign. Using A Combination Of Air Mass Trajectories (Model Predictions), It Was Possible To Assess The Impact Of Aqueous Phase Processing On The Formation Of Secondary Organic Aerosols (Soas). Our Results Show How Specific Chemical Signatures And Physical Properties Of Air Masses, Possibly Affected By Cloud Processing, Can Be Identified At Reunion. These Changes In Properties Are Represented By A Shift In Aerosol Size Distribution To Large Diameters And An Increased Contribution Of Secondary Sulfate And Organic Aerosols After Cloud Processing.

Abstract: The effect of post-depositional processing on the preservation of snow nitrate isotopes at Summit, Greenland, remains a subject of debate and is relevant to the quantitative interpretation of ice-core nitrate (isotopic) records at high snow accumulation sites. Here we present the first year-round observations of atmospheric nitrate and its isotopic compositions at Summit and compare them with published surface snow and snowpack observations. The atmospheric delta N-15(NO3-) remained negative throughout the year, ranging from -3.1 parts per thousand to -47.9 parts per thousand with a mean of (-14.8 +/- 7.3)parts per thousand (n = 54), and displayed minima in spring which are distinct from the observed spring delta N-15(NO3-) maxima in snowpack. The spring average atmospheric delta N-15(NO3-) was (-17.9 +/- 8.3) parts per thousand (n = 21), significantly depleted compared to the snowpack spring average of (4.6 +/- 2.1)parts per thousand, while the surface snow delta N-15(NO3-) of (-6.8 +/- 0.5)parts per thousand was in between the atmosphere and the snowpack. The differences in atmospheric, surface snow and snowpack delta N-15(NO3-) are best explained by the photo-driven post-depositional processing of snow nitrate, with potential contributions from fractionation during nitrate deposition. In contrast to delta N-15(NO3-) the atmospheric Delta O-1(7)(NO3-) was of a similar seasonal pattern and magnitude of change to that in the snowpack, suggesting little to no changes in Delta O-1(7)(NO3-) from photolysis, consistent with previous modeling results. The atmospheric delta O-18(NO3-) varied similarly to atmospheric Delta O-1(7)(NO3-), with summer low and winter high values. However, the difference between atmospheric and snow delta O-18(NO3-) was larger than that of Delta O-17(NO3-). We found a strong correlation between atmospheric delta O-18(NO3-) and Delta O-17(NO3-) that is very similar to previous measurements for surface snow at Summit, suggesting that atmospheric delta O-18(NO3-) versus Delta O-17(NO3-) relationships were conserved during deposition. However, we found the linear relationships between delta O-18 and Delta O-17(NO3-) were significantly different for snowpack compared to atmospheric samples. This likely suggests the oxygen isotopes are also affected before preservation in the snow at Summit, but the degree of change for delta O-18(NO3-) should be larger than that of Delta O-17(NO3-). This is because photolysis is a massdependent process that would directly affect delta O-18(NO3-) in snow but not Delta O-17(NO3-) as the latter is a mass-independent signal. Although there were uncertainties associated with the complied dataset, the results suggested that post-depositional processing at Summit can induce changes in nitrate isotopes, especially delta N-15(NO3-), consistent with a previous modeling study. This reinforces the importance of understanding the effects of post-depositional processing before ice-core nitrate isotope interpretation, even for sites with relatively high snow accumulation rates.

Abstract: aerosol markers including one primary anthropogenic marker (levoglucosan) and 4 secondary anthropogenic markers (nitrophenols, nitroguaiacols, methylnitrocatechols and phthalic acid). Modelled concentrations have been compared to measurements performed at 12 locations in France for levoglucosan in winter 2014-15, and at a sub-urban station in the Paris region over the whole year 2015 for secondary molecular markers. While a good estimation of levoglucosan concentrations by the model has been obtained for a few sites, a strong underestimation was simulated for most of the stations especially for western locations due to a probable underestimation of residential wood burning emissions. The simulated ratio between wood burning organic matter and particulate phase levoglucosan is constant only at high OM values (>10 μg m-3) indicating that using marker contribution ratio may be valid only under certain conditions. Concentrations of secondary markers were well reproduced by the model for nitrophenols and nitroguaiacols but were underestimated for methylnitrocatechols and phthalic acid highlighting missing formation pathways and/or precursor emissions. By comparing modelled to measured Gas/Particle Partitioning (GPP) of markers, the simulated partitioning of Semi-Volatile Organic Compounds (SVOCs) was evaluated. Except for nitroguaiacols and nitrophenols when ideality was assumed, the GPP for all the markers was underestimated and mainly driven by the hydrophilic partitioning. SVOCs GPP, and more generally of all SVOC contributing to the formation of SOA, could therefore be significantly

Abstract: In this work, we conducted a study of the stable carbon isotope ratios of total carbon (delta C-13(TC)) for submicron aerosol particles (< 1 μm) that were collected year round (2014) at a hemiboreal forest site in Lithuania. Higher delta C-13(TC) values characterised the seasonal variation in delta C-13(TC) during the cold season (average-26.9 +/- 0.7%o) with lower values observed during the warm season (-27.6 +/- 0.6%o). The total carbon (TC) concentration was below 8 μg/m3 during the one-year measurement period. There was one pollution event in autumn when concentrations reached up to 14.8 μg/m(3). In addition to the offline analysis of the filter samples, the online measurements of aerosol physical and chemical properties were conducted from 15 May to September 27, 2014 by operating the Aethalometer AE-31 and a quadrupole-type Aerosol Chemical Speciation Monitor (ACSM). Source apportionment was conducted by analysing the ACSM mass spectra using Positive Matrix Factorisation (PMF). Three main factors were derived, pointing to primary emissions from biomass burning along with the secondary formation of less and more oxygenated organic aerosol of biogenic origin. A comparative analysis of delta C-13(TC) with organic carbon (OC), elemental carbon (EC), and organic markers justified two dominant sources (biomass burning and fossil fuel combustion) of aerosol particles at the hemiboreal forest site during the cold season.

Abstract: The Arctic is warming two to three times faster than the global average, and the role of aerosols is not well constrained. Aerosol number concentrations can be very low in remote environments, rendering local cloud radiative properties highly sensitive to available aerosol. The composition and sources of the climate-relevant aerosols, affecting Arctic cloud formation and altering their microphysics, remain largely elusive due to a lack of harmonized concurrent multi-component, multi-site, and multi-season observations. Here, we present a dataset on the overall chemical composition and seasonal variability of the Arctic total particulate matter (with a size cut at 10 μm, PM10, or without any size cut) at eight observatories representing all Arctic sectors. Our holistic observational approach includes the Russian Arctic, a significant emission source area with less dedicated aerosol monitoring, and extends beyond the more traditionally studied summer period and black carbon/sulfate or fine-mode pollutants. The major airborne Arctic PM components in terms of dry mass are sea salt, secondary (non-sea-salt, nss) sulfate, and organic aerosol (OA), with minor contributions from elemental carbon (EC) and ammonium. We observe substantial spatiotemporal variability in component ratios, such as EC/OA, ammonium/nss-sulfate and OA/nss-sulfate, and fractional contributions to PM. When combined with component-specific back-trajectory analysis to identify marine or terrestrial origins, as well as the companion study by Moschos et al 2022 Nat. Geosci. focusing on OA, the composition analysis provides policy-guiding observational insights into sector-based differences in natural and anthropogenic Arctic aerosol sources. In this regard, we first reveal major source regions of inner-Arctic sea salt, biogenic sulfate, and natural organics, and highlight an underappreciated wintertime source of primary carbonaceous aerosols (EC and OA) in West Siberia, potentially associated with the oil and gas sector. The presented dataset can assist in reducing uncertainties in modelling pan-Arctic aerosol-climate interactions, as the major contributors to yearly aerosol mass can be constrained. These models can then be used to predict the future evolution of individual inner-Arctic atmospheric PM components in light of current and emerging pollution mitigation measures and improved region-specific emission inventories.

Abstract: Year-round observations of the physical snow and ice properties and processes that govern the ice pack evolution and its interaction with the atmosphere and the ocean were conducted during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition of the research vessel Polarstern in the Arctic Ocean from October 2019 to September 2020. This work was embedded into the interdisciplinary design of the 5 MOSAiC teams, studying the atmosphere, the sea ice, the ocean, the ecosystem, and biogeochemical processes. The overall aim of the snow and sea ice observations during MOSAiC was to characterize the physical properties of the snow and ice cover comprehensively in the central Arctic over an entire annual cycle. This objective was achieved by detailed observations of physical properties and of energy and mass balance of snow and ice. By studying snow and sea ice dynamics over nested spatial scales from centimeters to tens of kilometers, the variability across scales can be considered. On-ice observations of in situ and remote sensing properties of the different surface types over all seasons will help to improve numerical process and climate models and to establish and validate novel satellite remote sensing methods; the linkages to accompanying airborne measurements, satellite observations, and results of numerical models are discussed. We found large spatial variabilities of snow metamorphism and thermal regimes impacting sea ice growth. We conclude that the highly variable snow cover needs to be considered in more detail (in observations, remote sensing, and models) to better understand snow-related feedback processes. The ice pack revealed rapid transformations and motions along the drift in all seasons. The number of coupled ice-ocean interface processes observed in detail are expected to guide upcoming research with respect to the changing Arctic sea ice.

Abstract: Documenting The Inter-Annual Variability And The Long-Term Trend Of The Glacier Snow Line Altitude Is Highly Relevant To Document The Evolution Of Glacier Mass Changes. Automatically Identifying The Snow Line On Glaciers Is Challenging; Recent Developments In Machine Learning Approaches Show Promise To Tackle This Issue. This Manuscript Presents A Proof Of Concept Of Machine Learning Approaches Applied To Multi-Spectral Images To Detect The Snow Line And Quantify Its Average Altitude. The Tested Approaches Include The Combination Of Different Image Processing And Classification Methods, And Takes Into Account Cast Shadows. The Efficiency Of These Approaches Is Evaluated On Mountain Glaciers In The European Alps By Comparing The Results With Manually Annotated Data. Solutions Provided By The Different Approaches Are Robust When Compared To The Ground Truth'S Snow Lines, With A Pearson'S Correlation Ranging From 79% To 96% Depending On The Method. However, The Tested Approaches May Fail When Snow Lines Are Not Continuous Or Exhibit A Strong Change Of Elevation. The Major Advantage Over The State Of The Art Is That The Proposed Approach Does Not Require One Calibration Per Glacier.

Abstract: Y AltiKa, first ever high frequency Ka-band altimeter on board SARAL (Satellite with ARgos and ALtiKa) has gone through different phases of operations, viz. Exact Repeat Mission, (ERM, March 2013 – July 2016), Drifting phase, (DP, July 2016 – January 2018) and then to Mispointing phase, (MP, February 2018 – till date). A detailed assessment of Sea level anomaly (SLA), Significant Wave Height (SWH) and Ocean Surface Wind Speed (WS) has been carried out during these different phases with a focus on the North Indian Ocean. Crossover analysis using the Jason series of satellites available during various phases of SARAL suggest high quality of SARAL/AltiKa data during the ERM and DP with root mean square differences of the order of 0.080 m, 0.25 m and 1 m/s for SLA, SWH and WS respectively. These differences are more during MP, being 0.095 m, 0.45 m and 1.72 m/s for SLA, SWH and WS respectively. Wavenumber Power spectrum computed from the along-track AltiKa SLA reveals that slopes in the mesoscale band (70-250 km) in different phases of operations are not very different. Errors in gridded SARAL/AltiKa SLA with respect to standard AVISO product remains unchanged during DP, but degrade by nearly 9.3% in the MP as compared to ERM. To assess the effect of assimilating along track SWH and SLA from different phases, two set of wave and circulation model simulations, with and without SARAL AltiKa data assimilation, were performed. Assimilation of SWH improved the wave height simulation by similar to 12.8% during the DP and similar to 8% during ERM and MP. As regards to circulation modeling, no significant difference of assimilating SLA from different phases was observed in the mesoscale range. These results indicate the usefulness of SLA from SARAL AltiKa during DP and MP for studying the mesoscale dynamics. (C) 2021 COSPAR. Published by Elsevier B.V. All rights reserved.

Abstract: Urbanization and global warming are two of the major human impacts on the environment. The Urban Heat Island (UHI) effect can change precipitation patterns. Global warming also leads to changes in precipitation and especially an increase in intensity and frequency of extreme precipitation. With urbanization expected to grow in the future, the role of UHI in a warmer climate is an important research question. We present results from 20-year long regional convection-permitting model simulations that include the UHI effect, run for historical and future climates for two megacities, Paris and Shanghai. In the warmer future climate, urban-induced precipitation is found to decrease compared to the historical climate, for both mean and extreme precipitation, with large uncertainties due to natural variability. The mean precipitation increase due to UHI in Paris is 2.2 +/- 1.4% and 1.8 +/- 1.3% for historical and future conditions, respectively. Shanghai has slightly weaker mean precipitation change than Paris at present and no change in the future. The future reduction of the urban effect is found to be caused by a decrease in summer precipitation for both cities. Interannual variability in precipitation due to UHI is larger for Shanghai than Paris. The UHI effect on extreme precipitation is also reduced in the future climate and the area with precipitation increase is more concentrated. The general increase in extreme precipitation due to global warming, in combination with the precipitation redistribution due to UHI, underline the importance for future urban planning to mitigate damage caused by extreme precipitation events.

Abstract: 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 Utqiagvik, 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.

Abstract: Observations of aerosol and trace gases in the remote troposphere are vital to quantify background concentrations and identify long-term trends in atmospheric composition on large spatial scales. Measurements made at high altitude are often used to study free-tropospheric air; however such high-altitude sites can be influenced by boundary layer air masses. Thus, accurate information on air mass origin and transport pathways to high-altitude sites is required. Here we present a new method, based on the source-receptor relationship (SRR) obtained from backwards WRF-FLEXPART simulations and a k-means clustering approach, to identify source regions of air masses arriving at measurement sites. Our method is tailored to areas of complex terrain and to stations influenced by both local and long-range sources. We have applied this method to the Chacaltaya (CHC) GAW station (5240 m a.s.l.; 16.35 degrees S, 68.13 degrees W) for the 6-month duration of the “Southern Hemisphere high-altitude experiment on particle nucleation and growth” (SALILNA) to identify where sampled air masses originate and to quantify the influence of the surface and the free troposphere. A key aspect of our method is that it is probabilistic, and for each observation time, more than one air mass (cluster) can influence the station, and the percentage influence of each air mass can be quantified. This is in contrast to binary methods, which label each observation time as influenced by either boundary layer or free-troposphere air masses. Air sampled at CHC is a mix of different provenance. We find that on average 9 % of the air, at any given observation time, has been in contact with the surface within 4 d prior to arriving at CHC. Furthermore, 24 % of the air has been located within the first 1.5 km above ground level (surface included). Consequently, 76 % of the air sampled at CHC originates from the free troposphere. However, pure free-tropospheric influences are rare, and often samples are concurrently influenced by both boundary layer and free-tropospheric air masses. A clear diurnal cycle is present, with very few air masses that have been in contact with the surface being detected at night. The 6-month analysis also shows that the most dominant air mass (cluster) originates in the Amazon and is responsible for 29 % of the sampled air. Furthermore, short-range clusters (origins within 100 km of CHC) have high temporal frequency modulated by local meteorology driven by the diurnal cycle, whereas the mid- and long-range clusters' (> 200 km) variability occurs on timescales governed by synoptic-scale dynamics. To verify the reliability of our method, in situ sulfate observations from CHC are combined with the SRR clusters to correctly identify the (pre-known) source of the sulfate: the Sabancaya volcano located 400 km north-west from the station.

Abstract: A fine-scale source apportionment of PM10 was conducted in three different urban sites (background, hypercenter, and peri-urban) within 15 km of the city in Grenoble, France using Positive Matrix Factorization (PMF 5.0) on measured chemical species from collected filters (24 h) from February 2017 to March 2018. To improve the PMF solution, several new organic tracers (3-MBTCA, pinic acid, phthalic acid, MSA, and cellulose) were additionally used in order to identify sources that are commonly unresolved by classic PMF methodologies. An 11-factor solution was obtained in all sites, including commonly identified sources from primary traffic (13 %), nitrate-rich (17 %), sulfate-rich (17 %), industrial (1 %), biomass burning (22 %), aged sea salt (4 %), sea/road salt (3 %), and mineral dust (7 %), and the newly found sources from primary biogenic (4 %), secondary biogenic oxidation (10 %), and MSA-rich (3 %). Generally, the chemical species exhibiting similar temporal trends and strong correlations showed uniformly distributed emission sources in the Grenoble basin. The improved PMF model was able to obtain and differentiate chemical profiles of specific sources even at high proximity of receptor locations, confirming its applicability in a fine-scale resolution. In order to test the similarities between the PMF-resolved sources, the Pearson distance and standardized identity distance (PD-SID) of the factors in each site were compared. The PD-SID metric determined whether a given source is homogeneous (i.e., with similar chemical profiles) or heterogeneous over the three sites, thereby allowing better discrimination of localized characteristics of specific sources. Overall, the addition of the new tracers allowed the identification of substantial sources (especially in the SOA fraction) that would not have been identified or possibly mixed with other factors, resulting in an enhanced resolution and sound source profile of urban air quality at a city scale.

Abstract: Following the emergence of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) responsible for COVID-19 in December 2019 in Wuhan (China) and its spread to the rest of the world, the World Health Organization declared a global pandemic in March 2020. Without effective treatment in the initial pandemic phase, social distancing and mandatory quarantines were introduced as the only available preventative measure. In contrast to the detrimental societal impacts, air quality improved in all countries in which strict lockdowns were applied, due to lower pollutant emissions. Here we investigate the effects of the COVID-19 lockdowns in Europe on ambient black carbon (BC), which affects climate and damages health, using in situ observations from 17 European stations in a Bayesian inversion framework. BC emissions declined by 23 kt in Europe (20% in Italy, 40% in Germany, 34% in Spain, 22% in France) during lockdowns compared to the same period in the previous 5 years, which is partially attributed to COVID-19 measures. BC temporal variation in the countries enduring the most drastic restrictions showed the most distinct lockdown impacts. Increased particle light absorption in the beginning of the lockdown, confirmed by assimilated satellite and remote sensing data, suggests residential combustion was the dominant BC source. Accordingly, in central and Eastern Europe, which experienced lower than average temperatures, BC was elevated compared to the previous 5 years. Nevertheless, an average decrease of 11% was seen for the whole of Europe compared to the start of the lockdown period, with the highest peaks in France (42 %), Germany (21 %), UK (13 %), Spain (11 %) and Italy (8 %). Such a decrease was not seen in the previous years, which also confirms the impact of COVID-19 on the European emissions of BC.

Abstract: Within the framework of the AeroCom (Aerosol Comparisons between Observations and Models) initiative, the state-of-the-art modelling of aerosol optical properties is assessed from 14 global models participating in the phase III control experiment (AP3). The models are similar to CMIP6/AerChemMIP Earth System Models (ESMs) and provide a robust multi-model ensemble. Inter-model spread of aerosol species lifetimes and emissions appears to be similar to that of mass extinction coefficients (MECs), suggesting that aerosol optical depth (AOD) uncertainties are associated with a broad spectrum of parameterised aerosol processes. Total AOD is approximately the same as in AeroCom phase I (AP1) simulations. However, we find a 50% decrease in the optical depth (OD) of black carbon (BC), attributable to a combination of decreased emissions and lifetimes. Relative contributions from sea salt (SS) and dust (DU) have shifted from being approximately equal in AP1 to SS contributing about 2/3 of the natural AOD in AP3. This shift is linked with a decrease in DU mass burden, a lower DU MEC, and a slight decrease in DU lifetime, suggesting coarser DU particle sizes in AP3 compared to AP1. Relative to observations, the AP3 ensemble median and most of the participating models underestimate all aerosol optical properties investigated, that is, total AOD as well as fine and coarse AOD (AOD(f), AOD(c)), Angstrom exponent (AE), dry surface scattering (SCdry), and absorption (AC(dry)) coefficients. Compared to AERONET, the models underestimate total AOD by ca. 21% +/- 20% (as inferred from the ensemble median and interquartile range). Against satellite data, the ensemble AOD biases range from -37% (MODIS-Terra) to -16% (MERGED-FMI, a multi-satellite AOD product), which we explain by differences between individual satellites and AERONET measurements themselves. Correlation coefficients (R) between model and observation AOD records are generally high (R > 0.75), suggesting that the models are capable of capturing spatiotemporal variations in AOD. We find a much larger underestimate in coarse AOD(c) (similar to-45% +/- 25 %) than in fine AOD(f) (similar to-15% +/- 25 %) with slightly increased inter-model spread compared to total AOD. These results indicate problems in the modelling of DU and SS. The AOD(c) bias is likely due to missing DU over continental land masses (particularly over the United States, SE Asia, and S. America), while marine AERONET sites and the AATSR SU satellite data suggest more moderate oceanic biases in AOD(c). Column AEs are underestimated by about 10% +/- 16 %. For situations in which measurements show AE > 2, models underestimate AERONET AE by ca. 35 %. In contrast, all models (but one) exhibit large overestimates in AE when coarse aerosol dominates (bias ca. +140% if observed AE < 0.5). Simulated AE does not span the observed AE variability. These results indicate that models overestimate particle size (or underestimate the fine-mode fraction) for fine-dominated aerosol and underestimate size (or overestimate the fine-mode fraction) for coarse-dominated aerosol. This must have implications for lifetime, water uptake, scattering enhancement, and the aerosol radiative effect, which we can not quantify at this moment. Comparison against Global Atmosphere Watch (GAW) in situ data results in mean bias and inter-model variations of -35% +/- 25% and -20% +/- 18% for SCdry and AC(dry), respectively. The larger underestimate of SCdry than AC(dry) suggests the models will simulate an aerosol single scattering albedo that is too low. The larger underestimate of SCdry than ambient air AOD is consistent with recent findings that models overestimate scattering enhancement due to hygroscopic growth. The broadly consistent negative bias in AOD and surface scattering suggests an underestimate of aerosol radiative effects in current global aerosol models. Considerable inter-model diversity in the simulated optical properties is often found in regions that are, unfortunately, not or only sparsely covered by ground-based observations. This includes, for instance, the Sahara, Amazonia, central Australia, and the South Pacific. This highlights the need for a better site coverage in the observations, which would enable us to better assess the models, but also the performance of satellite products in these regions. Using fine-mode AOD as a proxy for present-day aerosol forcing estimates, our results suggest that models underestimate aerosol forcing by ca. -15 %, however, with a considerably large interquartile range, suggesting a spread between -35% and +10 %.

Abstract: High-quality atmospheric mercury (Hg) data are rare for South America, especially for its tropical region. As a consequence, mercury dynamics are still highly uncertain in this region. This is a significant deficiency, as South America appears to play a major role in the global budget of this toxic pollutant. To address this issue, we performed nearly 2 years (July 2014-February 2016) of continuous high-resolution total gaseous mercury (TGM) measurements at the Chacaltaya (CHC) mountain site in the Bolivian Andes, which is subject to a diverse mix of air masses coming predominantly from the Altiplano and the Amazon rainforest. For the first 11 months of measurements, we obtained a mean TGM concentration of 0 :89 +/- 0 :01 ngm(-3), which is in good agreement with the sparse amount of data available from the continent. For the remaining 9 months, we obtained a significantly higher TGM concentration of 1 :34 +/- 0 :01 ngm(-3), a difference which we tentatively attribute to the strong El Nino event of 2015-2016. Based on HYSPLIT (Hybrid SingleParticle Lagrangian Integrated Trajectory) back trajectories and clustering techniques, we show that lower mean TGM concentrations were linked to either westerly Altiplanic air masses or those originating from the lowlands to the southeast of CHC. Elevated TGM concentrations were related to northerly air masses of Amazonian or southerly air masses of Altiplanic origin, with the former possibly linked to artisanal and small-scale gold mining (ASGM), whereas the latter might be explained by volcanic activity. We observed a marked seasonal pattern, with low TGM concentrations in the dry season (austral winter), rising concentrations during the biomass burning (BB) season, and the highest concentrations at the beginning of the wet season (austral summer). With the help of simultaneously sampled equivalent black carbon (eBC) and carbon monoxide (CO) data, we use the clearly BB-influenced signal during the BB season (August to October) to derive a mean TGM = CO emission ratio of (2.3 +/- 0.6 x 10(-7) ppbvTGM ppbv (-1)(CO), which could be used to constrain South American BB emissions. Through the link with CO2 measured in situ and remotely sensed solarinduced fluorescence (SIF) as proxies for vegetation activity, we detect signs of a vegetation sink effect in Amazonian air

Abstract: Primary Biogenic Organic Aerosols (PBOA) were recently shown to be produced by only a few types of microorganisms, emitted by the surrounding vegetation in the case of a regionally homogeneous field site. This study presents the first comprehensive description of the structure and main sources of airborne microbial communities associated with temporal trends in Sugar Compounds (SC) concentrations of PM10 in 3 sites under a climatic gradient in France. By combining sugar chemistry and DNA Metabarcoding approaches, we intended to identify PM10-associated microbial communities and their main sources at three sampling-sites in France, under different climates, during the summer of 2018. This study accounted also for the interannual variability in summer airborne microbial community structure (bacteria and fungi only) associated with PM10-SC concentrations during a 2 consecutive years' survey at one site. Our results showed that temporal changes in PM10-SC in the three sites are associated with the abundance of only a few specific taxa of airborne fungi and bacterial. These taxa differ significantly between the 3 climatic regions studied. The microbial communities structure associated with SC concentrations of PM10 during a consecutive 2-year study remained stable in the rural area. Atmospheric concentration levels of PM10-SC species varied significantly between the 3 study sites, but with no clear difference according to site typology (rural vs. urban), suggesting that SC emissions are related to regional rather than local climatic characteristics. The overall microbial beta diversity in PM10 samples is significantly different from that of the main vegetation around the urban sites studied. This indicates that the airborne microorganisms at these urban sites are not solely from the immediate surrounding vegetation, which contrasts with observations at the scale of a regionally homogeneous rural site in 2017. These results improve our understanding of the spatial behavior of tracers of PBOA emission sources, which need to be better characterized to further implement this important mass fraction of Organic Matter (OM) in Chemical Transport models (CTM).

Abstract: This study systematically investigates the mineralogical and geochemical variations in parent coal, coal gangue (roof, parting, and floor), deposited coal mine dust (DD), and respirable fractions of DD (RD) in an underground coal mine using the blasting mining method in China to evaluate the major sources of DD. The emission of dust in this study is affected by coal gangue sources during the mining process, which causes different geochemical patterns in the DD samples. Moreover, weathering of the cement gunite walls plays an important role in the enrichment of specific elements in the DD from air uptake and air out galleries. Furthermore, the spatial variation in RD characteristics, including mineralogy, geochemistry, and oxidative potential (OP), is discussed, with emphasis on the major health-relevant species and elements. Organic species from coal dust seem to be the essential components contributing to OP rather than metals, although some metals (e.g., Cr, Co, Ge, Se, Zn, Ba, Rb, Cs, Sn, and Pb) influence OP to some degree.

Abstract: Anthropogenic activities on the Indo-Gangetic Plain emit vast amounts of light-absorbing particles (LAPs) into the atmosphere, modifying the atmospheric radiation state. With transport to the nearby Himalayas and deposition to its surfaces the particles contribute to glacier melt and snowmelt via darkening of the highly reflective snow. The central Himalayas have been identified as a region where LAPs are especially pronounced in glacier snow but still remain a region where measurements of LAPs in the snow are scarce. Here we study the deposition of LAPs in five snow pits sampled in 2016 (and one from 2015) within 1 km from each other from two glaciers in the Sunderdhunga Valley, in the state of Uttarakhand, India, in the central Himalayas. The snow pits display a distinct enriched LAP layer interleaved by younger snow above and older snow below. The LAPs exhibit a distinct vertical distribution in these different snow layers. For the analyzed elemental carbon (EC), the younger snow layers in the different pits show similarities, which can be characterized by a deposition constant of about 50 μg m(-2) mm(-1) snow water equivalent (SWE), while the old-snow layers also indicate similar values, described by a deposition constant of roughly 150 μg m(-2) mm(-1) SWE. The enriched LAP layer, contrarily, displays no similar trends between the pits. Instead, it is characterized by very high amounts of LAPs and differ in orders of magnitude for concentration between the pits. The enriched LAP layer is likely a result of strong melting that took place during the summers of 2015 and 2016, as well as possible lateral transport of LAPs. The mineral dust fractional absorption is slightly below 50% for the young- and old-snow layers, whereas it is the dominating light-absorbing constituent in the enriched LAP layer, thus, highlighting the importance of dust in the region. Our results indicate the problems with complex topography in the Himalayas but, nonetheless, can be useful in large-scale assessments of LAPs in Himalayan snow.

Abstract: For the last 25 years, CO-PDD (Cezeaux-Aulnat-Opme-puy de Dome) has evolved to become a full instrumented platform for atmospheric research. It has received credentials as a national observing platform in France and is internationally recognized as a global station in the GAW (Global Atmosphere Watch) network. It is a reference site of European and national research infrastructures ACTRIS (Aerosol Cloud and Trace gases Research Infrastructure) and ICOS (Integrated Carbon Observing System). The site located on top of the puy de Dome mountain (1465 m a.s.l.) is completed by additional sites located at lower altitudes and adding the vertical dimension to the atmospheric observations: Opme (660 m a.s.l.), Cezeaux (410 m), and Aulnat (330 m). The integration of different sites offers a unique combination of in situ and remote sensing measurements capturing and documenting the variability of particulate and gaseous atmospheric composition, but also the optical, biochemical, and physical properties of aerosol particles, clouds, and precipitations. Given its location far away from any major emission sources, its altitude, and the mountain orography, the puy de Dome station is ideally located to sample different air masses in the boundary layer or in the free troposphere depending on time of day and seasons. It is also an ideal place to study cloud properties with frequent presence of clouds at the top in fall and winter. As a result of the natural conditions prevailing at the site and of the very exhaustive instrumental deployment, scientific studies at the puy de Dome strongly contribute to improving knowledge in atmospheric sciences, including the characterization of trends and variability, the understanding of complex and interconnected processes (microphysical, chemical, biological, chemical and dynamical), and the provision of reference information for climate/chemistry models. In this context, CO-PDD is a pilot site to conduct instrumental development inside its wind tunnel for testing liquid and ice cloud probes in natural conditions, or in situ systems to collect aerosol and cloud. This paper reviews 25 years (1995-2020) of atmospheric observation at the station and related scientific research contributing to atmospheric and climate science.

Abstract: For decades, oil extraction in rural sites in the North Amazon Region (NAR) in Ecuador, have generated mixtures of potentially toxic compounds, such as polycyclic aromatic hydrocarbons (PAHs) and metal(loid)s. The main national refinery and the thermal power plant located in Esmeraldas, on the North Pacific Coast (NPC), are also considered as important sources of air contamination. Particulate matter (PM10) emitted at both sites could induce the formation of reactive oxygen species (ROS) in the lungs upon inhalation and could be associated with respiratory diseases. In this study, PM10 mass composition was monitored over a two-year period in both regions: NAR (close to oil platforms and open flares) and NPC (in a public school close to the refinery). PM10 composition was assessed in terms of metal(loid)s, organic and elementary carbon (OC, EC), monosaccharides (levoglucosan, mannosan, galactosan), glucose, polyols (sorbitol, mannitol, arabitol), water soluble ions and polycyclic aromatic compounds (PAHs, oxy-PAHs and nitro-PAHs). Additionally, three complementary biochemical and acellular tests were performed to evaluate the oxidative potential (OP). Results show that the PM10 mass and elemental concentrations were higher in NPC than in NAR. Barium and Mo concentrations, commonly used in oil operations, were up to 1000-fold higher than values recorded in other regions of Ecuador. OC/EC ratios and polyols concentrations were higher in NAR than in NPC, indicating a larger biogenic contribution to the PM mass in this region. In NAR, the main sources associated with ROS burden were biogenic emissions and oil production, as indicated by positive correlations between OP, sugars, Ba, some PAHs and oxy-PAHs. On the other hand, in NPC, associations between NH4+, Ba, As and Ni imply that oil refining and industrial activities are the main contributors to the OP of PM10.

Abstract: Air pollution is of major concern throughout the world and the use of modeling tools to analyze and forecast the pollutant concentrations in complex orographic areas remains challenging. This work proposes an exhaustive framework to analyze the ability of models to simulate the air quality over the French Alps up to 1.2 km resolution over Grenoble and the Arve Valley. The on-line coupled suite of models CHIMERE-WRF is used in its recent version to analyze a 1 month episode in November-December 2013. As expected, an improved resolution increases the concentrations close to the emission areas and reduced the negative bias for Particulate Matter that is the usual weakness of air quality models. However, the nitrate concentrations seem overestimated with at the same time an overestimation of surface temperature in the morning by WRF. Different WRF settings found in the literature are tested to improve the results, particularly the ability of the meteorological model to simulate the strong thermal inversions in the morning. Wood burning is one of the main contributor of air pollution during the period ranging from 80 to 90% of the Organic Matter. The activation of the on-line coupling has a moderate impact on the background concentrations but surprisingly a change of Particulate Matter (PM) concentrations in the valley will affect more the meteorology nearby high altitude areas than in the valley. This phenomenon is the result of a chain of processes involving the radiative effects and the water vapor column gradients in complex orographic areas. At last, the model confirms that the surrounding glaciers are largely impacted by long range transport of desert dust. However, in wintertime some outbreaks of anthropogenic pollution from the valley when the synoptic situation changes can be advected up to the nearby high altitude areas, then deposited.

Abstract: Like many western boundary currents, the East Australian Current (EAC) extension is projected to get stronger and warmer in the future. The CMIP5 multimodel mean (MMM) projection suggests up to 5 degrees C of warming under an RCP85 scenario by 2100. Previous studies employed Sverdrup balance to associate a trend in basin wide zonally integrated wind stress curl (resulting from the multidecadal poleward intensification in the westerly winds over the Southern Ocean) with enhanced transport in the EAC extension. Possible regional drivers are yet to be considered. Here we introduce the NEMO-OASIS-WRF coupled regional climate model as a framework to improve our understanding of CMIP5 projections. We analyze a hierarchy of simulations in which the regional atmosphere and ocean circulations are allowed to freely evolve subject to boundary conditions that represent present-day and CMIP5 RCP8.5 climate change anomalies. Evaluation of the historical simulation shows an EAC extension that is stronger than similar ocean-only models and observations. This bias is not explained by a linear response to differences in wind stress. The climate change simulations show that regional atmospheric CMIP5 MMM anomalies drive 73% of the projected 12 Sv increase in EAC extension transport whereas the remote ocean boundary conditions and regional radiative forcing (greenhouse gases within the domain) play a smaller role. The importance of regional changes in wind stress curl in driving the enhanced EAC extension is consistent with linear theory where the NEMO-OASIS-WRF response is closer to linear transport estimates compared to the CMIP5 MMM.

Abstract: Particulate matter is a component of ambient air pollution that has been linked to millions of annual premature deaths globally(1-3). Assessments of the chronic and acute effects of particulate matter on human health tend to be based on mass concentration, with particle size and composition also thought to play a part(4). Oxidative potential has been suggested to be one of the many possible drivers of the acute health effects of particulate matter, but the link remains uncertain(5-8). Studies investigating the particulate-matter components that manifest an oxidative activity have yielded conflicting results(7). In consequence, there is still much to be learned about the sources of particulate matter that may control the oxidative potential concentration(7). Here we use field observations and air-quality modelling to quantify the major primary and secondary sources of particulate matter and of oxidative potential in Europe. We find that secondary inorganic components, crustal material and secondary biogenic organic aerosols control the mass concentration of particulate matter. By contrast, oxidative potential concentration is associated mostly with anthropogenic sources, in particular with fine-mode secondary organic aerosols largely from residential biomass burning and coarse-mode metals from vehicular non-exhaust emissions. Our results suggest that mitigation strategies aimed at reducing the mass concentrations of particulate matter alone may not reduce the oxidative potential concentration. If the oxidative potential can be linked to major health impacts, it may be more effective to control specific sources of particulate matter rather than overall particulate mass. Observations and air-quality modelling reveal that the sources of particulate matter and oxidative potential in Europe are different, implying that reducing mass concentrations of particulate matter alone may not reduce oxidative potential.

Abstract: The Observatoire Perenne de l'Environnement (OPE) station is a rural background site located in North-Eastern France. Besides emissions from agricultural activities, the site is located far from local emissions but at an even distance from the intense emission zones of Western Germany to the north-east and the Paris area to the south-west. In the paper, we report and analyze almost six years of measurements (1 May 2012 to 31 December 2018) of the optical and physical properties of aerosol particles. Based on aerosol optical and physical measurements combined with air mass back-trajectories, we investigate the dependence of these properties on air mass type. Two distinct equivalent black carbon (EBC) sources-origins-fossil fuel (FF) and biomass burning (BB)- were identified. FF was the dominant source of EBC (>70%) but showed a very marked seasonal variation. BB fraction is found higher during the cold seasons in the order of 35% (0.1 μg m(-3)) against 17% (0.05 μg m(-3)) during the warm seasons. The highest EBC and N0.54-1.15 (particles whose diameter ranged from 0.54 to 1.15 μm) median concentrations were observed during the night time and during the cold seasons compared to the warmer seasons, indicating primary sources trapped within a thin boundary layer (BL). A different behavior is found for N10-550 (particles whose diameter ranged from 10 to 550 nm) and coarse mode particles (N1.15-4.5, i.e., particles whose diameter ranged from 1.15 to 4.5 μm) median concentrations, which were observed during the warm seasons compared to the cold seasons, indicating rather biogenic secondary sources for the smaller particles, and potentially primary biogenic sources for the coarse mode particles. The scattering and absorption coefficients and single scattering albedo (SSA) show the same seasonal variations like the ones of N0.54-1.15 concentrations, indicating that particles larger than 500 nm seemed to contribute the most to the optical properties of the aerosol.

Abstract: Ambient air pollution is one of the leading five health risks worldwide. One of the most harmful air pollutants is particulate matter (PM), which has different physical characteristics (particle size and number, surface area and morphology) and a highly complex and variable chemical composition. Our goal was first to comparatively assess the effects of exposure to PM regarding cytotoxicity, release of pro-inflammatory mediators and gene expression in human bronchial epithelia (HBE) reflecting normal and compromised health status. Second, we aimed at evaluating the impact of various PM components from anthropogenic and biogenic sources on the cellular responses. Air-liquid interface (ALI) cultures of fully differentiated HBE derived from normal and cystic fibrosis (CF) donor lungs were exposed at the apical cell surface to water-soluble PM filter extracts for 4 h. The particle dose deposited on cells was 0.9-2.5 and 8.8-25.4 μg per cm(2) of cell culture area for low and high PM doses, respectively. Both normal and CF HBE show a clear dose-response relationship with increasing cytotoxicity at higher PM concentrations. The concurrently enhanced release of pro-inflammatory mediators at higher PM exposure levels links cytotoxicity to inflammatory processes. Further, the PM exposure deregulates genes involved in oxidative stress and inflammatory pathways leading to an imbalance of the antioxidant system. Moreover, we identify compromised defense against PM in CF epithelia promoting exacerbation and aggravation of disease. We also demonstrate that the adverse health outcome induced by PM exposure in normal and particularly in susceptible bronchial epithelia is magnified by anthropogenic PM components. Thus, including health-relevant PM components in regulatory guidelines will result in substantial human health benefits and improve protection of the vulnerable population.

Abstract: More than half of the world's population lives in urban areas (UN Population Division 2018 The World's cities in 2018 (UN: New York)), which are especially vulnerable to climate extremes (Field et al 2012 Managing the Risks of Extreme Events and Disasters to Advance Climate Change Adaptation: Special Report of the Intergovernmental Panel on Climate Change (Cambridge: Cambridge University Press)). Urbanization itself is known to increase surface temperatures, but its quantitative effect on extreme precipitation remains very uncertain. Using decadal convection-permitting climate simulations in four midlatitude megacities (Paris, France; New York City, USA; Tokyo, Japan; Shanghai, China), we show that urbanization can strongly increase the frequency and intensity of extreme urban precipitation. Frequency increases far more than intensity, by +16% (11%-22%) (95% confidence interval) for 1 year daily extremes, and +26% (11%-41%) for 1 year hourly extremes, downwind of city centers. Intensities of the same events increase by +5% (3.2%-6.4%) (daily extremes) and +6% (3.2%-9.8%) (hourly extremes), respectively. The intensity and frequency of extremes increases more for the rarest, most extreme events considered, and there is some indication that hourly extremes increase more than daily extremes. Our simulations also show that direct urban anthropogenic emissions of heat could be an important factor driving these changes. Urbanization is expected to continue in the future, and our results indicate that these effects should be considered in urban planning decisions to make cities more resilient to extreme precipitation.

Abstract: Direct measurements of the net ecosystem exchange (NEE) of gaseous elemental mercury (Hg-0) are important to improve our understanding of global Hg cycling and, ultimately, human and wildlife Hg exposure. The lack of long-term, ecosystem-scale measurements causes large uncertainties in Hg-0 flux estimates. It currently remains unclear whether terrestrial ecosystems are net sinks or sources of atmospheric Hg-0. Here, we show a detailed validation of direct Hg-0 flux measurements based on the eddy covariance technique (Eddy Mercury) using a Lumex RA-915 AM mercury monitor. The flux detection limit derived from a zero-flux experiment in the laboratory was 0.22 ng m(-2) h(-1) (maximum) with a 50% cutoff at 0.074 ng m(-2) h(-1). We present eddy covariance NEE measurements of Hg-0 over a low-Hg soil (41-75 ng Hg g(-1) in the topsoil, referring to a depth of 0-10 cm), conducted in summer 2018 at a managed grassland at the Swiss FluxNet site in Chamau, Switzerland (CH-Cha). The statistical estimate of the Hg-0 flux detection limit under outdoor conditions at the site was 5.9 ng m(-2) h(-1') (50% cutoff). We measured a net summertime emission over a period of 34 d with a median Hg-0 flux of 2.5 ng m(-2) h(-1) (with a -0.6 to 7.4 ng m(-2) h(-1) range between the 25th and 75th percentiles). We observed a distinct diel cycle with higher median daytime fluxes (8.4 ng m(-2) h(-1)) than night-time fluxes (1.0 ng m(-2) h(-1)). Drought stress during the measurement campaign in summer 2018 induced partial stomata closure of vegetation. Partial stomata closure led to a midday depression in CO2 uptake, which did not recover during the afternoon. The median CO2 flux was only 24% of the median CO2 flux measured during the same period in the previous year (2017). We suggest that partial stomata closure also dampened Hg-0 uptake by vegetation, resulting in a NEE of Hg-0 that was dominated by soil emission. Finally, we provide suggestions to further improve the precision and handling of the “Eddy Mercury” system in order to assure its suitability for long-term NEE measurements of Hg-0 over natural background surfaces with low soil Hg concentrations (< 100 ng g(-1)). With these improvements, Eddy Mercury has the potential to be integrated into global networks of micrometeorological tower sites (FluxNet) and to provide the long-term observations on terrestrial atmosphere Hg-0 exchange necessary to validate regional and global mercury models.

Abstract: The aerosol mass spectrometer (AMS), combined with statistical methods such as positive matrix factorization (PMF), has greatly advanced the quantification of primary organic aerosol (POA) sources and total secondary organic aerosol (SOA) mass. However, the use of thermal vaporization and electron ionization yields extensive thermal decomposition and ionization-induced fragmentation, which limit chemical information needed for SOA source apportionment. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) provides mass spectra of the organic aerosol fraction with a linear response to mass and no thermal decomposition or ionization-induced fragmentation. However, the costs and operational requirements of online instruments make their use impractical for long-term or spatially dense monitoring applications. This challenge was overcome for AMS measurements by measuring re-nebulized water extracts from ambient filter samples. Here, we apply the same strategy for EESI-TOF measurements of 1 year of 24 h filter samples collected approximately every fourth day throughout 2013 at an urban site. The nebulized water extracts were measured simultaneously with an AMS. The application of positive matrix factorization (PMF) to EESI-TOF spectra resolved seven factors, which describe water-soluble OA: less and more aged biomass burning aerosol (LABB(EESI) and MABB(EESI), respectively), cigarette-smoke-related organic aerosol, primary biological organic aerosol, biogenic secondary organic aerosol, and a summer mixed oxygenated organic aerosol factor. Seasonal trends and relative contributions of the EESI-TOF OA sources were compared with AMS source apportionment factors, measured water-soluble ions, cellulose, and meteorological data. Cluster analysis was utilized to identify key factor-specific ions based on PMF. Both LABB and MABB contribute strongly during winter. LABB is distinguished by very high signals from C6H10O5 (levoglucosan and isomers) and C8H12O6, whereas MABB is characterized by a large number of CxHyOz and CxHyOzN species of two distinct populations: one with low H : C and high O : C and the other with high H : C and low O : C. Two oxygenated summertime SOA sources were attributed to terpene-derived biogenic SOA, a major summertime aerosol source in central Europe. Furthermore, a primary biological organic aerosol factor was identified, which was dominated by plant-derived fatty acids and correlated with free cellulose. The cigarette-smoke-related factor contained a high contribution of nicotine and high abundance of organic nitrate ions with low m/z.

Abstract: Primary biogenic organic aerosols (PBOAs) represent a major fraction of coarse organic matter (OM) in air. Despite their implication in many atmospheric processes and human health problems, we surprisingly know little about PBOA characteristics (i.e., composition, dominant sources, and contribution to airborne particles). In addition, specific primary sugar compounds (SCs) are generally used as markers of PBOAs associated with bacteria and fungi, but our knowledge of microbial communities associated with atmospheric particulate matter (PM) remains incomplete. This work aimed at providing a comprehensive understanding of the microbial fingerprints associated with SCs in PM10 (particles smaller than 10 μm) and their main sources in the surrounding environment (soils and vegetation). An intensive study was conducted on PM10 collected at a rural background site located in an agricultural area in France. We combined high-throughput sequencing of bacteria and fungi with detailed physicochemical characterizations of PM10, soil, and plant samples and monitored meteorological and agricultural activities throughout the sampling period. Results show that in summer SCs in PM10 are a major contributor of OM in air, representing 0.8 % to 13.5 % of OM mass. SC concentrations are clearly determined by the abundance of only a few specific airborne fungal and bacterial taxa. The temporal fluctuations in the abundance of only four predominant fungal genera, namely Cladosporium, Alternaria, Sporobolomyces, and Dioszegia, reflect the temporal dynamics in SC concentrations. Among bacterial taxa, the abundance of only Massilia, Pseudomonas, Frigoribacterium, and Sphingomonas is positively correlated with SC species. These microbes are significantly enhanced in leaf over soil samples. Interestingly, the overall community structure of bacteria and fungi are similar within PM10 and leaf samples and significantly distinct between PM10 and soil samples, indicating that surrounding vegetation is the major source of SC-associated microbial taxa in PM10 in this rural area of France.

Abstract: The atmosphere is the major transport pathway for distribution of mercury (Hg) globally. Gaseous elemental mercury (GEM, hereafter Hg0) is the predominant form in both anthropogenic and natural emissions. Evaluation of the efficacy of reductions in emissions set by the UN's Minamata Convention (UN-MC) is critically dependent on the knowledge of the dynamics of the global Hg cycle. Of these dynamics including e.g. red-ox reactions, methylation-demethylation and dry-wet deposition, poorly constrained atmosphere-surface Hg-0 fluxes especially limit predictability of the timescales of its global biogeochemical cycle. This review focuses on Hg-0 flux field observational studies, namely the theory, applications, strengths, and limitations of the various experimental methodologies applied to gauge the exchange flux and decipher active sub-processes. We present an in-depth review, a comprehensive literature synthesis, and methodological and instrumentation advances for terrestrial and marine Hg0 flux studies in recent years. In particular, we outline the theory of a wide range of measurement techniques and detail the operational protocols. Today, the most frequently used measurement techniques to determine the net Hg-0 flux (>95% of the published flux data) are dynamic flux chambers for small-scale and micrometeorological approaches for large-scale measurements. Furthermore, top-down approaches based on Hg-0 concentration measurements have been applied as tools to better constrain Hg emissions as an independent way to e.g. challenge emission inventories. This review is an up-dated, thoroughly revised edition of Sommar et al. 2013 (DOI: 10.1080/10643389.2012.671733). To the tabulation of >100 cited flux studies 1988-2009 given in the former publication, we have here listed corresponding studies published during the last decade with a few exceptions (2008-2019). During that decade, Hg stable isotope ratios of samples involved in atmosphere-terrestrial interaction is at hand and provide in combination with concentration and/or flux measurements novel constraints to quantitatively and qualitatively assess the bi-directional Hg-0 flux. Recent efforts in the development of relaxed eddy accumulation and eddy covariance Hg-0 flux methods bear the potential to facilitate long-term, ecosystem-scale flux measurements to reduce the prevailing large uncertainties in Hg-0 flux estimates. Standardization of methods for Hg-0 flux measurements is crucial to investigate how land-use change and how climate warming impact ecosystem-specific Hg-0 sink-source characteristics and to validate frequently applied model parameterizations describing the regional and global scale Hg cycle. (C) 2020 Elsevier B.V. All rights reserved.

Abstract: Microorganisms are ubiquitous in the atmosphere, and some airborne microbial cells were shown to be particularly resistant to atmospheric physical and chemical conditions (e.g., ultraviolet – UV – radiation, desiccation and the presence of radicals). In addition to surviving, some cultivable microorganisms of airborne origin were shown to be able to grow on atmospheric chemicals in laboratory experiments. Metagenomic investigations have been used to identify specific signatures of microbial functional potential in different ecosystems. We conducted a comparative metagenomic study on the overall microbial functional potential and specific metabolic and stress-related microbial functions of atmospheric microorganisms in order to determine whether airborne microbial communities possess an atmosphere-specific functional potential signature as compared to other ecosystems (i.e., soil, sediment, snow, feces, surface seawater etc.). In the absence of a specific atmospheric signature, the atmospheric samples collected at nine sites around the world were similar to their underlying ecosystems. In addition, atmospheric samples were characterized by a relatively high proportion of fungi. The higher proportion of sequences annotated as genes involved in stress-related functions (i.e., functions related to the response to desiccation, UV radiation, oxidative stress etc.) resulted in part from the high concentrations of fungi that might resist and survive atmospheric physical stress better than bacteria.

Abstract: Aerobiology is a growing research area that covers the study of aerosols with a biological origin from the air that surrounds us to space through the different atmospheric layers. Bioaerosols have captured a growing importance in atmospheric process-related fields such as meteorology and atmospheric chemistry. The potential dissemination of pathogens and allergens through the air has raised public health concern and has highlighted the need for a better prediction of airborne microbial composition and dynamics. In this review, we focused on the sources and processes that most likely determine microbial community composition and dynamics in the air that directly surrounds us, the planetary boundary layer. Planetary boundary layer microbial communities are a mix of microbial cells that likely originate mainly from local source ecosystems (as opposed to distant sources). The adverse atmospheric conditions (i.e., UV radiation, desiccation, presence of radicals, etc.) might influence microbial survival and lead to the physical selection of the most resistant cells during aerosolization and/or aerial transport. Future work should further investigate how atmospheric chemicals and physics influence microbial survival and adaptation in order to be able to model the composition of planetary boundary layer microbial communities based on the surrounding landscapes and meteorology.

Abstract: Indoor air pollution can be a major health risk because urban populations spend up to 90% of their time in closed rooms. Gaseous elemental mercury (GEM) has not been measured as routinely as other indoor air pollutants due to the high costs and limited mobility of active Hg analyzers. However, household GEM concentrations may exceed Hg air quality guidelines as a result of potential indoor GEM sources like broken Hg thermometers. Here we deploy novel low-cost mercury passive air samplers (MerPAS) in 27 households (7 days) and at 14 outdoor locations (29-31 days) in Basel, Switzerland. Average Hg concentrations ranged from 2.0 to 10.8 ng m(-3) indoors and from 1.8 to 2.5 ng m(-3) outdoors. These results reveal that households are a net source of Hg to the urban atmosphere and exceed outdoor Hg levels by a factor of 2 on average. We estimated an average weekly intake rate of 0.01 μg of Hg/kg of body weight for adult residents in Basel, which is usually lower than Hg exposure of people with dental amalgam fillings. Our campaign demonstrates that air monitoring programs can easily be complemented by straightforward Hg measurements using MerPAS.

Abstract: Concentrations of 9 organophosphate esters (OPEs), 16 perfluoroalkylated substances (PFASs) and 17 polycyclic aromatic hydrocarbons (PAHs) were investigated in surface snow samples collected at Dome C on the Antarctic Plateau in summer 2016. Tris(1-chloro-2-propyl) phosphate (TCPP), tris-(2-chloroethyl) phosphate (TCEP) and tri-n-butylphosphate (TnBP) were the dominant compounds of OPEs, with mean concentrations of 8157 +/- 4860, 1128 +/- 928 and 1232 +/- 1147 pg/L. Perfluorooctanoic acid (PFOA, mean: 358 +/- 71 pg/L) was the dominant compound of PFASs, and following by perfluoro-n-hexanoic acid (PFHxA, mean: 222 +/- 97 pg/L), perfluoro-n-heptanoic acid (PFHpA, 183 +/- 60 pg/L) and perfluoro-n-pentanoic acid (PFPeA, 175 +/- 105 pg/L). 2-(Heptafluoropropoxy)propanoic acid (HFPO-DA, mean: 9.2 +/- 2.6 pg/L) was determined in the Antarctic for the first time. Significantly positive correlations were observed between HFPO-DA and the short-chain PFASs, implying they have similar emission sources and long-range transport potential. High levels of 2-methylnaphthalene and 1-methylnaphthalene, as well as the ratios of PAH congeners indicated PAHs were attributable mostly to combustion origin. Occurrence and profiles of the indicators of OPEs, PFASs and PAHs, as well as air mass back-trajectory analysis provided direct evidences of human activities on Concordia station and posed obvious impacts on local environments in the Antarctic. Nevertheless, the exchange processes among different environmental matrices may drive the long-range transport and redistribution of the legacy and emerging Organic contaminants from coast to inland in the Antarctic. (C) 2020 The Authors. Published by Elsevier B.V.

Abstract: Motivated by the need to predict how the Arctic atmosphere will change in a warming world, this article summarizes recent advances made by the research consortium NETCARE (Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments) that contribute to our fundamental understanding of Arctic aerosol particles as they relate to climate forcing. The overall goal of NETCARE research has been to use an interdisciplinary approach encompassing extensive field observations and a range of chemical transport, earth system, and biogeochemical models. Several major findings and advances have emerged from NETCARE since its formation in 2013. (1) Unexpectedly high summertime dimethyl sulfide (DMS) levels were identified in ocean water (up to 75 nM) and the overlying atmosphere (up to 1 ppbv) in the Canadian Arctic Archipelago (CAA). Furthermore, melt ponds, which are widely prevalent, were identified as an important DMS source (with DMS concentrations of up to 6nM and a potential contribution to atmospheric DMS of 20% in the study area). (2) Evidence of widespread particle nucleation and growth in the marine boundary layer was found in the CAA in the summertime, with these events observed on 41% of days in a 2016 cruise. As well, at Alert, Nunavut, particles that are newly formed and grown under conditions of minimal anthropogenic influence during the months of July and August are estimated to contribute 20% to 80% of the 30-50 nm particle number density. DMS-oxidation-driven nucleation is facilitated by the presence of atmospheric ammonia arising from seabird-colony emissions, and potentially also from coastal regions, tundra, and biomass burning. Via accumulation of secondary organic aerosol (SOA), a significant fraction of the new particles grow to sizes that are active in cloud droplet formation. Although the gaseous precursors to Arctic marine SOA remain poorly defined, the measured levels of common continental SOA precursors (isoprene and monoterpenes) were low, whereas elevated mixing ratios of oxygenated volatile organic compounds (OVOCs) were inferred to arise via processes involving the sea surface microlayer. (3) The variability in the vertical distribution of black carbon (BC) under both springtime Arctic haze and more pristine summertime aerosol conditions was observed. Measured particle size distributions and mixing states were used to constrain, for the first time, calculations of aerosol-climate interactions under Arctic conditions. Aircraft- and ground-based measurements were used to better establish the BC source regions that supply the Arctic via long-range transport mechanisms, with evidence for a dominant springtime contribution from eastern and southern Asia to the middle troposphere, and a major contribution from northern Asia to the surface. (4) Measurements of ice nucleating particles (INPs) in the Arctic indicate that a major source of these particles is mineral dust, likely derived from local sources in the summer and long-range transport in the spring. In addition, INPs are abundant in the sea surface microlayer in the Arctic, and possibly play a role in ice nucleation in the atmosphere when mineral dust concentrations are low. (5) Amongst multiple aerosol components, BC was observed to have the smallest effective deposition velocities to high Arctic snow (0.03 cm s(-1)).

Abstract: The significance of foliar uptake of nitrogen (N) compounds in natural conditions is not well understood, despite growing evidence of its importance to plant nutrition. In subalpine meadows, N-limitation fosters the dominance of specific subalpine plant species, which in turn ensures the provision of essential ecosystems services. Understanding how these plants absorb N and from which sources is important in predicting ecological consequences of increasing N deposition. Here, we investigate the sources of N to plants from subalpine meadows with distinct land-use history in the French Alps, using the triple isotopes (Delta O-17, delta O-18, and delta N-15) of plant tissue nitrate (NO3-). We use this approach to evaluate the significance of foliar uptake of atmospheric NO3- (NO3atm-). The foliar uptake of NO3atm- accounted for 4-16% of the leaf NO3- content, and contributed more to the leaf NO3- pool after peak biomass. Additionally, the gradual N-15 enrichment of NO3- from the soil to the leaves reflected the contribution of NO3atm- assimilation to plants' metabolism. The present study confirms that foliar uptake is a potentially important pathway for NO3atm- into subalpine plants. This is of major significance as N emissions (and deposition) are predicted to increase globally in the future.

Abstract: In order to identify and quantify key species associated with non-exhaust emissions and exhaust vehicular emissions, a large comprehensive dataset of particulate species has been obtained thanks to simultaneous near-road and urban background measurements coupled with detailed traffic counts and chassis dynamometer measurements of exhaust emissions of a few in-use vehicles well-represented in the French fleet. Elemental carbon, brake-wear metals (Cu, Fe, Sb, Sn, Mn), n-alkanes (C19-C26), light-molecular-weight polycyclic aromatic hydrocarbons (PAHs; pyrene, fluoranthene, anthracene) and two hopanes (17 alpha 21 beta norhopane and 17 alpha 21 beta hopane) are strongly associated with the road traffic. Traffic-fleet emission factors have been determined for all of them and are consistent with most recent published equivalent data. When possible, light-duty- and heavy-duty-traffic emission factors are also determined In the absence of significant non-combustion emissions, light-duty-traffic emissions are in good agreement with emissions from chassis dynamometer measurements. Since recent measurements in Europe including those from this study are consistent, ratios involving copper (Cu/Fe and Cu/Sn) could be used as brake-wear emissions tracers as long as brakes with Cu remain in use. Near the Grenoble ring road, where the traffic was largely dominated by diesel vehicles in 2011 (70 %), the OC/EC ratio estimated for traffic emissions was around 0.4. Although the use of quantitative data for source apportionment studies is not straightforward for the identified organic molecular markers, their presence seems to well-characterize fresh traffic emissions.

Abstract: Chronologies of lake-sediment records covering the last centuries to millennia are usually based on both short-lived radionuclides and radiocarbon dating. However, beyond the range of short-lived radionuclides, age model accuracy often suffers from large radiocarbon uncertainties. For high-altitude records, this issue is even more prominent as terrestrial plant fragments for radiocarbon dating are often lacking due to the sparse vegetation in such environments. In this study, we evaluate the potential of the geomagnetic field secular variations as a complementary tool to establish more robust age-depth relationships. Our palaeomagnetic study, applied to five high-altitude lakes from the western European Alps, first shows that recent unconsolidated sediments can carry stable remanent magnetization. The analysis of the magnetic parameters indicates that low-coercivity pseudo-single domain magnetite grains carry the natural magnetization. Nevertheless, the quality of palaeomagnetic secular variation records varies from one lake to another. This quality can be illustrated through the calculation of the declination/inclination maximum angular variations and their comparison to the expected value. Compared with available models, the declination variations are usually too large and the inclination too high. We discuss the validity of palaeosecular variation (PSV) of the Earth's magnetic field regarding rock magnetism, magnetization processes and possible deformation during coring. From a magnetic point of view, the quality of data is variable, but the characteristic remanent magnetization direction is consistent at site level between neighbouring lakes and with the reference curve, suggesting that geomagnetic field secular variations are approximately recorded. Finally, we attempt to correlate the declination/inclination variations of the characteristic remanent magnetization measured in the five records to the reference geomagnetic model to provide additional chronological markers for age-depth modelling. These stratigraphic chrono-markers appear in systematic agreement with our previous chronological data and enable a reduction of dating uncertainties up to 30% when including these chrono-markers in the age-depth modelling. This agreement supports the interpretation that PSV may have been recorded more or less accurately depending on the studied lake. Therefore, coupled with a comprehensive understanding through other analysis (sedimentology, dating, geochemistry), PSV can be used to improve the age models in the more favourable cases.

Abstract: The interplay between microbes and atmospheric physical and chemical conditions is an open field of research that can only be fully addressed using multidisciplinary approaches. The lack of coordinated efforts to gather data at representative temporal and spatial scales limits aerobiology to help understand large scale patterns of global microbial biodiversity and its causal relationships with the environmental context. This paper presents the sampling strategy and analytical protocols developed in order to integrate different fields of research such as microbiology, -omics biology, atmospheric chemistry, physics and meteorology to characterize atmospheric microbial life. These include control of chemical and microbial contaminations from sampling to analysis and identification of experimental procedures for characterizing airborne microbial biodiversity and its functioning from the atmospheric samples collected at remote sites from low cell density environments. We used high-volume sampling strategy to address both chemical and microbial composition of the atmosphere, because it can help overcome low aerosol and microbial cell concentrations. To account for contaminations, exposed and unexposed control filters were processed along with the samples. We present a method that allows for the extraction of chemical and biological data from the same quartz filters. We tested different sampling times, extraction kits and methods to optimize DNA yield from filters. Based on our results, we recommend supplementary sterilization steps to reduce filter contamination induced by handling and transport. These include manipulation under laminar flow hoods and UV sterilization. In terms of DNA extraction, we recommend a vortex step and a heating step to reduce binding to the quartz fibers of the filters. These steps have led to a 10-fold increase in DNA yield, allowing for downstream omics analysis of air samples. Based on our results, our method can be integrated into pre-existing long-term monitoring field protocols for the atmosphere both in terms of atmospheric chemistry and biology. We recommend using standardized air volumes and to develop standard operating protocols for field users to better control the operational quality.

Abstract: High quality records of stratospheric volcanic eruptions, required to model past climate variability, have been constructed by identifying synchronous (bipolar) volcanic sulfate horizons in Greenland and Antarctic ice cores. Here we present a new 2600-year chronology of stratospheric volcanic events using an independent approach that relies on isotopic signatures (Delta S-33 and in some cases Delta O-17) of ice core sulfate from five closely-located ice cores from Dome C, Antarctica. The Dome C stratospheric reconstruction provides independent validation of prior reconstructions. The isotopic approach documents several high-latitude stratospheric events that are not bipolar, but climatically-relevant, and diverges deeper in the record revealing tropospheric signals for some previously assigned bipolar events. Our record also displays a collapse of the Delta O-17 anomaly of sulfate for the largest volcanic eruptions, showing a further change in atmospheric chemistry induced by large emissions. Thus, the refinement added by considering both isotopic and bipolar correlation methods provides additional levels of insight for climate-volcano connections and improves ice core volcanic reconstructions.

Abstract: Despite widespread applications of sulfur isotope mass-independent fractionation (MIF) signals for probing terrestrial and extra-terrestrial environments, there has been no international sulfur isotope reference material available for normalization of Delta S-33 and Delta S-36 data. International reference materials to anchor isotope values are useful for interlaboratory data comparisons and are needed to evaluate, e.g., whether issues exist associated with blanks and mass spectrometry when using different analytical approaches. We synthesized two sodium sulfate samples enriched in S-33 with different magnitudes, and termed them S-MIF-1 and S-MIF-2, respectively. The sulfur isotopic compositions of these two samples were measured in five different laboratories using two distinct techniques to place them on the V-CDT scale for delta S-34 and a provisional V-CDT scale for Delta S-33 and Delta S-36. We obtained average delta S-34 values of S-MIF-1 = 10.26 +/- 0.22 parts per thousand and S-MIF-2 = 21.53 +/- 0.26 parts per thousand (1 sigma, versus V-CDT). The average Delta S-33 and Delta S-36 values of S-MIF-1 were determined to be 9.54 +/- 0.09 parts per thousand and -0.11 +/- 0.25 parts per thousand, respectively, while the average Delta S-33 and Delta S-36 values of S-MIF-2 are 11.39 +/- 0.08 parts per thousand and -0.33 +/- 0.13 parts per thousand (1 sigma, versus V-CDT). The lack of variation among the interlaboratory isotopic values suggests sufficient homogeneity of S-MIF-1 and S-MIF-2, especially for Delta S-33. Although additional measurements may be needed to ensure the accuracy of the isotopic compositions of S-MIF-1 and S-MIF-2, they can serve as working standards for routine Delta S-33 analysis to improve data consistency, and have the potential to serve as secondary sulfur isotope reference materials to address issues such as scale contraction/expansion and for normalization and reporting of Delta S-33 and Delta S-36 between laboratories. For the same reasons as listed for sulfur isotopes, the same standards were also artificially enriched in O-17. The calibration is still in progress but first estimations gave Delta O-17 = 3.3 +/- 0.3 parts per thousand with unassigned delta O-18.

Abstract: The deposition of light-absorbing particles (LAPs) such as mineral dust and black carbon on snow is responsible for a highly effective climate forcing, through darkening of the snow surface and associated feedbacks. The interplay between post-depositional snow transformation (metamorphism) and the dynamics of LAPs in snow remains largely unknown. We obtained time series of X-ray tomography images of dust-contaminated samples undergoing dry snow metamorphism at around -2 degrees C. They provide the first observational evidence that temperature gradient metamorphism induces dust particle motion in snow, while no movement is observed under isothermal conditions. Under temperature gradient metamorphism, dust particles can enter the ice matrix due to sublimation-condensation processes and spread down mainly by falling into the pore space. Overall, such motions might reduce the radiative impact of dust in snow, in particular in arctic regions where temperature gradient metamorphism prevails.

Abstract: Ice nucleating particles (INPs) in the Arctic can influence climate and precipitation in the region; yet our understanding of the concentrations and sources of INPs in this region remain uncertain. In the following, we (1) measured concentrations of INPs in the immersion mode in the Canadian Arctic marine boundary layer during summer 2014 on board the CCGS Amundsen, (2) determined ratios of surface areas of mineral dust aerosol to sea spray aerosol, and (3) investigated the source region of the INPs using particle dispersion modelling. Average concentrations of INPs at 15, -20, and 25 degrees C were 0.005, 0.044, and 0.154 L-1, respectively. These concentrations fall within the range of INP concentrations measured in other marine environments. For the samples investigated the ratio of mineral dust surface area to sea spray surface area ranged from 0.03 to 0.09. Based on these ratios and the ice active surface site densities of mineral dust and sea spray aerosol determined in previous laboratory studies, our results suggest that mineral dust is a more important contributor to the INP population than sea spray aerosol for the samples analysed. Based on particle dispersion modelling, the highest concentrations of INPs were often associated with lower-latitude source regions such as the Hudson Bay area, eastern Greenland, or north-western continental Canada. On the other hand, the lowest concentrations were often associated with regions further north of the sampling sites and over Baffin Bay. A weak correlation was observed between INP concentrations and the time the air mass spent over bare land, and a weak negative correlation was observed between INP concentrations and the time the air mass spent over ice and open water. These combined results suggest that mineral dust from local sources is an important contributor to the INP population in the Canadian Arctic marine boundary layer during summer 2014.

Abstract: In a context of climate change and water demand growth, understanding the origin of water flows in the Himalayas is a key issue for assessing the current and future water resource availability and planning the future uses of water in downstream regions. Two of the main issues in the hydrology of high-altitude glacierized catchments are (i) the limited representation of cryospheric processes controlling the evolution of ice and snow in distributed hydrological models and (ii) the difficulty in defining and quantifying the hydrological contributions to the river outflow. This study estimates the relative contribution of rainfall, glaciers, and snowmelt to the Khumbu River streamflow (Upper Dudh Koshi, Nepal, 146 km(2), 43% glacierized, elevation range from 4260 to 8848 ma.s.l.) as well as the seasonal, daily, and sub-daily variability during the period 2012-2015 by using the DHSVM-GDM (Distributed Hydrological Soil Vegetation Model – Glaciers Dynamics Model) physically based glacio-hydrological model. The impact of different snow and glacier parameterizations was tested by modifying the snow albedo parameterization, adding an avalanche module, adding a reduction factor for the melt of debris-covered glaciers, and adding a conceptual englacial storage. The representation of snow, glacier, and hydrological processes was evaluated using three types of data (MODIS satellite images, glacier mass balances, and in situ discharge measurements). The relative flow components were estimated using two different definitions based on the water inputs and contributing areas. The simulated hydrological contributions differ not only depending on the used models and implemented processes, but also on different definitions of the estimated flow components. In the presented case study, ice melt and snowmelt contribute each more than 40% to the annual water inputs and 69% of the annual stream flow originates from glacierized areas. The analysis of the seasonal contributions highlights that ice melt and snowmelt as well as rain contribute to monsoon flows in similar proportions and that winter outflow is mainly controlled by the release from the englacial water storage. The choice of a given parametrization for snow and glacier processes, as well as their relative parameter values, has a significant impact on the simulated water balance: for instance, the different tested parameterizations led to ice melt contributions ranging from 42% to 54 %. The sensitivity of the model to the glacier inventory was also tested, demonstrating that the uncertainty related to the glacierized surface leads to an uncertainty of 20% for the simulated ice melt component.

Abstract: The effect of nutrients on microbial interactions, including competition and collaboration, has mainly been studied in laboratories, but their potential application to complex ecosystems is unknown. Here, we examined the effect of changes in organic acids among other parameters on snow microbial communities in situ over 2 months. We compared snow bacterial communities from a low organic acid content period to that from a higher organic acid period. We hypothesized that an increase in organic acids would shift the dominant microbial interaction from collaboration to competition. To evaluate microbial interactions, we built taxonomic co-variance networks from OTUs obtained from 16S rRNA gene sequencing. In addition, we tracked marker genes of microbial cooperation (plasmid backbone genes) and competition (antibiotic resistance genes) across both sampling periods in metagenomes and metatranscriptomes. Our results showed a decrease in the average connectivity of the network during late spring compared to the early spring that we interpreted as a decrease of cooperation. This observation was strengthened by the significantly more abundant plasmid backbone genes in the metagenomes from the early spring. The modularity of the network from the late spring was also found to be higher than the one from the early spring, which is another possible indicator of increased competition. Antibiotic resistance genes were significantly more abundant in the late spring metagenomes. In addition, antibiotic resistance genes were also positively correlated to the organic acid concentration of the snow across both seasons. Snow organic acid content might be responsible for this change in bacterial interactions in the Arctic snow community.

Abstract: The primary sugar compounds (SCs, defined as glucose, arabitol, and mannitol) are widely recognized as suitable molecular markers to characterize and apportion primary biogenic organic aerosol emission sources. This work improves our understanding of the spatial behavior and distribution of these chemical species and evidences their major effective environmental drivers. We conducted a large study focusing on the daily (24 h) PM10 SC concentrations for 16 increasing space scale sites (local to nationwide), over at least 1 complete year. These sites are distributed in several French geographic areas of different environmental conditions. Our analyses, mainly based on the examination of the short-term evolutions of SC concentrations, clearly show distance-dependent correlations. SC concentration evolutions are highly synchronous at an urban city scale and remain well correlated throughout the same geographic regions, even if the sites are situated in different cities. However, sampling sites located in two distinct geographic areas are poorly correlated. Such a pattern indicates that the processes responsible for the evolution of the atmospheric SC concentrations present a spatial homogeneity over typical areas of at least tens of kilometers. Local phenomena, such as the resuspension of topsoil and associated microbiota, do no account for the major emissions processes of SC in urban areas not directly influenced by agricultural activities. The concentrations of SC and cellulose display remarkably synchronous temporal evolution cycles at an urban site in Grenoble, indicating a common source ascribed to vegetation. Additionally, higher concentrations of SC at another site located in a crop field region occur during each harvest periods, indicating resuspension processes of plant materials (crop detritus, leaf debris) and associated microbiota for agricultural and nearby urbanized areas. Finally, ambient air temperature, relative humidity, and vegetation density constitute the main effective drivers of SC atmospheric concentrations.

Abstract: Sunlit snow is highly photochemically active and plays a key role in the exchange of gas phase species between the cryosphere and the atmosphere. Here, we investigate the behaviour of two selected species in surface snow: mercury (Hg) and iodine (I). Hg can deposit year-round and accumulate in the snowpack. However, photo-induced re-emission of gas phase Hg from the surface has been widely reported. Iodine is active in atmospheric new particle formation, especially in the marine boundary layer, and in the destruction of atmospheric ozone. It can also undergo photochemical re-emission. Although previous studies indicate possible post-depositional processes, little is known about the diurnal behaviour of these two species and their interaction in surface snow. The mechanisms are still poorly constrained, and no field experiments have been performed in different seasons to investigate the magnitude of re-emission processes Three sampling campaigns conducted at an hourly resolution for 3 d each were carried out near Ny-Alesund (Svalbard) to study the behaviour of mercury and iodine in surface snow under different sunlight and environmental conditions (24 h darkness, 24 h sunlight and day-night cycles). Our results indicate a different behaviour of mercury and iodine in surface snow during the different campaigns. The day-night experiments demonstrate the existence of a diurnal cycle in surface snow for Hg and iodine, indicating that these species are indeed influenced by the daily solar radiation cycle. Differently, bromine did not show any diurnal cycle. The diurnal cycle also disappeared for Hg and iodine during the 24 h sunlight period and during 24 h darkness experiments supporting the idea of the occurrence (absence) of a continuous recycling or exchange at the snow-air interface. These results demonstrate that this surface snow recycling is seasonally dependent, through sunlight. They also highlight the non-negligible role that snowpack emissions have on ambient air concentrations and potentially on iodine-induced atmospheric nucleation processes.

Abstract: The cryosphere, which comprises a large portion of Earth's surface, is rapidly changing as a consequence of global climate change. Ice, snow, and frozen ground in the polar and alpine regions of the planet are known to directly impact atmospheric composition, which for example is observed in the large influence of ice and snow on polar boundary layer chemistry. Atmospheric inputs to the cryosphere, including aerosols, nutrients, and contaminants, are also changing in the anthropocene thus driving cryosphere-atmosphere feedbacks whose understanding is crucial for understanding future climate. Here, we present the Cryosphere and ATmospheric Chemistry initiative (CATCH) which is focused on developing new multidisciplinary research approaches studying interactions of chemistry, biology, and physics within the coupled cryosphere – atmosphere system and their sensitivity to environmental change. We identify four key science areas: (1) micro-scale processes in snow and ice, (2) the coupled cryosphere-atmosphere system, (3) cryospheric change and feedbacks, and (4) improved decisions and stakeholder engagement. To pursue these goals CATCH will foster an international, multidisciplinary research community, shed light on new research needs, support the acquisition of new knowledge, train the next generation of leading scientists, and establish interactions between the science community and society.

Abstract: Light-absorbing particles (LAPs) such as black carbon or mineral dust are some of the main drivers of snow radiative transfer. Small amounts of LAPs significantly increase snowpack absorption in the visible wavelengths where ice absorption is particularly weak, impacting the surface energy budget of snow-covered areas. However, linking measurements of LAP concentration in snow to their actual radiative impact is a challenging issue which is not fully resolved. In the present paper, we point out a new method based on spectral irradiance profile (SIP) measurements which makes it possible to identify the radiative impact of LAPs on visible light extinction in homogeneous layers of the snowpack. From this impact on light extinction it is possible to infer LAP concentrations present in each layer using radiative transfer theory. This study relies on a unique dataset composed of 26 spectral irradiance profile measurements in the wavelength range 350-950 nm with concomitant profile measurements of snow physical properties and LAP concentrations, collected in the Alps over two snow seasons in winter and spring conditions. For 55 homogeneous snow layers identified in our dataset, the concentrations retrieved from SIP measurements are compared to chemical measurements of LAP concentrations. A good correlation is observed for measured concentrations higher than 5 ng g(-1) (r(2) = 0.81) despite a clear positive bias. The potential causes of this bias are discussed, underlining a strong sensitivity of our method to LAP optical properties and to the relationship between snow microstructure and snow optical properties used in the theory. Additional uncertainties such as artefacts in the measurement technique for SIP and chemical contents along with LAP absorption efficiency may explain part of this bias. In addition, spectral information on LAP absorption can be retrieved from SIP measurements. We show that for layers containing a unique absorber, this absorber can be identified in some cases (e.g. mineral dust vs. black carbon). We also observe an enhancement of light absorption between 350 and 650 nm in the presence of liquid water in the snow-pack, which is discussed but not fully elucidated. A single SIP acquisition lasts approximately 1 min and is hence much faster than collecting a profile of chemical measurements. With the recent advances in modelling LAP-snow interactions, our method could become an attractive alternative to estimate vertical profiles of LAP concentrations in snow.

Abstract: Receptor-oriented models, including positive matrix factorization (PMF) analyses, are now commonly used to elaborate and/or evaluate action plans to improve air quality. In this context, the SOURCES project has been set-up to gather and investigate in a harmonized way 15 datasets of chemical compounds from PM10 collected for PMF studies during a five-year period (2012-2016) in France. The present paper aims at giving an overview of the results obtained within this project, notably illustrating the behavior of key primary sources as well as focusing on their statistical robustness and representativeness. Overall, wood burning for residential heating as well as road transport were confirmed to be the two main primary sources strongly influencing PM10 loadings across the country. While wood burning profiles, as well as those dominated by secondary inorganic aerosols, present a rather good homogeneity among the sites investigated, some significant variabilities were observed for primary traffic factors, illustrating the need to better characterize the diversity of the various vehicle exhaust and non-exhaust emissions. Finally, natural sources, such as sea salts (widely observed in internal mixing with anthropogenic compounds), primary biogenic aerosols and/or terrigenous particles, were also found as non-negligible PM10 components at every investigated site.

Abstract: Nitrogen is an essential nutrient for life on Earth, but in excess, it can lead to environmental issues (e.g., N saturation, loss of biodiversity, acidification of lakes, etc.). Understanding the nitrogen budget (i.e., inputs and outputs) is essential to evaluate the prospective decay of the ecosystem services (e.g., freshwater quality, erosion control, loss of high patrimonial-value plant species, etc.) that subalpine headwater catchments provide, especially as these ecosystems experience high atmospheric nitrogen deposition. Here, we use a multi-isotopic tracer (Delta O-17, delta N-15 and delta O-18) of nitrate in aerosols, snow, and streams to assess the fate of atmospherically deposited nitrate in the subalpine watershed of the Lautaret Pass (French Alps). We show that atmospheric N deposition contributes significantly to stream nitrate pool year-round, either by direct inputs (up to 35%) or by in situ nitrification of atmospheric ammonium (up to 35%). Snowmelt in particular leads to high exports of atmospheric nitrate, most likely fast enough to impede assimilation by surrounding ecosystems. Yet, in a context of climate change, with shorter snow seasons, and increasing nitrogen emissions, our results hint at possibly stronger ecological consequences of nitrogen atmospheric deposition in the close future.

Abstract: Many studies have demonstrated associations between exposure to ambient particulate matter (PM) and adverse health outcomes in humans that can be explained by PM capacity to induce oxidative stress in vivo. Thus, assays have been developed to quantify the oxidative potential (OP) of PM as a more refined exposure metric than PM mass alone. Only a small number of studies have compared different acellular OP measurements for a given set of ambient PM samples. Yet, fewer studies have compared different assays over a year-long period and with detailed chemical characterization of ambient PM. In this study, we report on seasonal variations of the dithiothreitol (DTT), ascorbic acid (AA), electron spin resonance (ESR) and the respiratory tract lining fluid (RTLF, composed of the reduced glutathione (GSH) and ascorbic acid (ASC)) assays over a 1-year period in which 100 samples were analyzed. A detailed PM10 characterization allowed univariate and multivariate regression analyses in order to obtain further insight into groups of chemical species that drive OP measurements. Our results show that most of the OP assays were strongly intercorrelated over the sampling year but also these correlations differed when considering specific sampling periods (cold vs. warm). All acellular assays are correlated with a significant number of chemical species when considering univariate correlations, especially for the DTT assay. Evidence is also presented of a seasonal contrast over the sampling period with significantly higher OP values during winter for the DTT, AA, GSH and ASC assays, which were assigned to biomass burning species by the multiple linear regression models. The ESR assay clearly differs from the other tests as it did not show seasonal dynamics and presented weaker correlations with other assays and chemical species.

Abstract: We discuss remote terrestrial influences on boundary layer air over the Southern Ocean and Antarctica, and the mechanisms by which they arise, using atmospheric radon observations as a proxy. Our primary motivation was to enhance the scientific community's ability to understand and quantify the potential effects of pollution, nutrient or pollen transport from distant land masses to these remote, sparsely instrumented regions. Seasonal radon characteristics are discussed at 6 stations (Macquarie Island, King Sejong, Neumayer, Dumont d'Urville, Jang Bogo and Dome Concordia) using 1-4 years of continuous observations. Context is provided for differences observed between these sites by Southern Ocean radon transects between 45 and 67 degrees S made by the Research Vessel Investigator. Synoptic transport of continental air within the marine boundary layer (MBL) dominated radon seasonal cycles in the mid-Southern Ocean site (Macquarie Island). MBL synoptic transport, tropospheric injection, and Antarctic outflow all contributed to the seasonal cycle at the sub-Antarctic site (King Sejong). Tropospheric subsidence and injection events delivered terrestrially influenced air to the Southern Ocean MBL in the vicinity of the circumpolar trough (or “Polar Front”). Katabatic outflow events from Antarctica were observed to modify trace gas and aerosol characteristics of the MBL 100-200 km off the coast. Radon seasonal cycles at coastal Antarctic sites were dominated by a combination of local radon sources in summer and subsidence of terrestrially influenced tropospheric air, whereas those on the Antarctic Plateau were primarily controlled by tropospheric subsidence. Separate characterization of long-term marine and katabatic flow air masses at Dumont d'Urville revealed monthly mean differences in summer of up to 5 ppbv in ozone and 0.3 ng m(-3) in gaseous elemental mercury. These differences were largely attributed to chemical processes on the Antarctic Plateau. A comparison of our observations with some Antarctic radon simulations by global climate models over the past two decades indicated that: (i) some models overestimate synoptic transport to Antarctica in the MBL, (ii) the seasonality of the Antarctic ice sheet needs to be better represented in models, (iii) coastal Antarctic radon sources need to be taken into account, and (iv) the underestimation of radon in subsiding tropospheric air needs to be investigated.

Abstract: We assess the benefits of offline laser-desorption/ionization mass spectrometry in understanding ambient particulate matter (PM) sources. The technique was optimized for measuring PM collected on quartz-fiber filters using silver nitrate as an internal standard for m/z calibration. This is the first application of this technique to samples collected at nine sites in central Europe throughout the entire year of 2013 (819 samples). Different PM sources were identified by positive matrix factorization (PMF) including also concomitant measurements (such as NOx, levoglucosan, and temperature). By comparison to reference mass spectral signatures from laboratory wood burning experiments as well as samples from a traffic tunnel, three biomass burning factors and two traffic factors were identified. The wood burning factors could be linked to the burning conditions; the factors related to inefficient burns had a larger impact on air quality in southern Alpine valleys than in northern Switzerland. The traffic factors were identified as primary tailpipe exhaust and most possibly aged/secondary traffic emissions. The latter attribution was supported by radiocarbon analyses of both the organic and elemental carbon. Besides these sources, factors related to secondary organic aerosol were also separated. The contribution of the wood burning emissions based on LDI-PMF (laser-desorption/ionization PMF) correlates well with that based on AMS-PMF (aerosol mass spectrometer PMF) analyses, while the comparison between the two techniques for other components is more complex.

Abstract: Particulate matter (PM) emitted by human activities presents a significant risk for human health, especially through inhalation. In this work, coarse and ultrafine particles (PM10 and PM1) were collected near a lead battery recycling facility, recognized as an emission source of hazardous particles. These particles were previously found to have adverse health effects. Our multiple imaging analyses by SEM-EDX and Raman microspectrometry showed that Pb-rich particles constituted the major portion of the fine size fractions (PM1). The surface analysis of particles performed by ToF-SIMS evidenced soluble Pb-Cl rich species on the particle surface. The particle composition and chemical mixing state differed from PM at source emission. Although the annual mean lead concentration near the plant meets E.U. air quality standards, the size of the Pb-rich particles and the presence of soluble metal compounds on the particle surface may also induce harmful outcomes. The current risk assessment models only consider the total concentration of the element without dealing with speciation, morphology or surface composition of the particles. Single particle analysis could become useful in providing a more accurate assessment of human health risk and in developing more comprehensive regulations on air quality.

Abstract: Derivatization techniques based on alpha-effect amines and H+ catalysis are commonly used for the measurement of carbonyl compounds (CCs), whether in environmental, food, or biological samples. Here, we investigated the potential of aniline-based catalysts to improve derivatization rates of selected carbonyls by using dansylacetamidooxyamine (DNSAOA) as a reagent. Kinetic experiments were performed in aqueous solutions by varying catalyst and CC concentrations and delivered insights into the reaction mechanism. Using anilinium acetate (AnAc), rate constants varied linearly with the catalyst concentration with rate enhancements toward H+-catalyzed reactions as high as ca. 90 and 200 for acetone and benzaldehyde, respectively. Owing to contamination problems when using AnAc, anilinium chloride (AnCl) was chosen for the optimized analysis of real samples at low concentration. Rate enhancements for derivatization reaction of 4.4 (methylglyoxal), 6.0 (glyoxal), 12 (acetone), 20 (formaldehyde), and 47 (hydroxyacetaldehyde) were obtained using 0.1 M AnCl. The optimized method was successfully applied to the determination of the above compounds in natural snow and meltwater samples. Limits of detection (LODs) and limits of quantification (LOQs) were in the 2-14 and 7-41 nM range, respectively, i.e., low enough to allow for the analysis of most natural samples. Satisfactory relative recoveries (92.8 +/- 3.8-118.3 +/- 4.4%) and intra-day precision (2.7-11.3%) were achieved. Finally, we think that this approach could be applied not only to every alpha-effect nitrogen reagent-with the most evident profit of lowering derivatization times and particularly those required for low-reactive ketones-but also to the derivatization of CCs onto coated solid sorbents.

Abstract: Results from ground-penetrating radar (GPR) measurements and shallow ice cores carried out during a scientific traverse between Dome Concordia (DC) and Vostok stations are presented in order to infer both spatial and temporal characteristics of snow accumulation over the East Antarctic Plateau. Spatially continuous accumulation rates along the traverse are computed from the identification of three equally spaced radar reflections spanning about the last 600 years. Accurate dating of these internal reflection horizons (IRHs) is obtained from a depth-age relationship derived from volcanic horizons and bomb testing fallouts on a DC ice core and shows a very good consistency when tested against extra ice cores drilled along the radar profile. Accumulation rates are then inferred by accounting for density profiles down to each IRH. For the latter purpose, a careful error analysis showed that using a single and more accurate density profile along a DC core provided more reliable results than trying to include the potential spatial variability in density from extra (but less accurate) ice cores distributed along the profile. The most striking feature is an accumulation pattern that remains constant through time with persistent gradients such as a marked decrease from 26 mm w.e. yr(-1) at DC to 20 mm w.e. yr(-1) at the south-west end of the profile over the last 234 years on average (with a similar decrease from 25 to 19 mm w.e. yr(-1) over the last 592 years). As for the time dependency, despite an overall consistency with similar measurements carried out along the main East Antarctic divides, interpreting possible trends remains difficult. Indeed, error bars in our measurements are still too large to unambiguously infer an apparent time increase in accumulation rate. For the proposed absolute values, maximum margins of error are in the range 4 mm w.e. yr(-1) (last 234 years) to 2 mm w.e. yr(-1) (last 592 years), a decrease with depth mainly resulting from the time-averaging when computing accumulation rates.

Abstract: We conducted a model-based assessment of changes in permafrost area and carbon storage for simulations driven by RCP4.5 and RCP8.5 projections between 2010 and 2299 for the northern permafrost region. All models simulating carbon represented soil with depth, a critical structural feature needed to represent the permafrost carbon-climate feedback, but that is not a universal feature of all climate models. Between 2010 and 2299, simulations indicated losses of permafrost between 3 and 5 million km(2) for the RCP4.5 climate and between 6 and 16 million km(2) for the RCP8.5 climate. For the RCP4.5 projection, cumulative change in soil carbon varied between 66-Pg C (10(15)-g carbon) loss to 70-Pg C gain. For the RCP8.5 projection, losses in soil carbon varied between 74 and 652 Pg C (mean loss, 341 Pg C). For the RCP4.5 projection, gains in vegetation carbon were largely responsible for the overall projected net gains in ecosystem carbon by 2299 (8- to 244-Pg C gains). In contrast, for the RCP8.5 projection, gains in vegetation carbon were not great enough to compensate for the losses of carbon projected by four of the five models; changes in ecosystem carbon ranged from a 641-Pg C loss to a 167-Pg C gain (mean, 208-Pg C loss). The models indicate that substantial net losses of ecosystem carbon would not occur until after 2100. This assessment suggests that effective mitigation efforts during the remainder of this century could attenuate the negative consequences of the permafrost carbon-climate feedback.

Abstract: Impacted by a complex mixture of urban, industrial, shipping and also natural emissions, Marseille, the second most populated city in France, represents a very interesting case study for the apportionment of PM(2.5 )sources in a Mediterranean urban environment. In this study, daily PM2.5 samples were collected over a one-year period (2011 -2012) at an urban background site, and were comprehensively analyzed for the determination of organic carbon (OC), elemental carbon (EC), major ions, trace elements/metals and specific organic markers. A constrained positive matrix factorization (PMF) analysis using the ME-2 (multilinear engine-2) solver was applied to this dataset. PMF results highlighted the presence of two distinct fingerprints for biomass burning (BB1 and BB2). BB1, assigned to open green waste burning peaks in fall (33%; 7.4 μg m(-3)) during land clearing periods, is characterized by a higher levoglucosan/OC ratio, while BB2, assigned to residential heating, shows the highest contribution during the cold period in winter (14%; 3.3 μg m(-3)) and it is characterized by high proportions from lignin pyrolysis products from the combustion of hardwood. Another interesting feature lies in the separation of two fossil fuel combustion processes (FF1 and FF2): FF1 likely dominated by traffic emissions, while FF2 likely linked with the harbor/industrial activities. On annual average, the major contributors to PM2.5 mass correspond to the ammonium sulfate-rich aerosol (AS-rich, 30%) and to the biomass burning emissions (BB1 + BB2, 23%). This study also outlined that during high PM pollution episodes (PM2.5 > 25 μg m(-3) ), the largest contributing sources to PM2.5 were biomass burning (33%) and FF1 (23%). Moreover, 28% of the ambient mass concentration of OC is apportioned by the AS-rich factor, which is representative of an aged secondary aerosol, reflecting thus the importance of the oxidative processes occurring in a Mediterranean environment.

Abstract: Distinct diurnal and seasonal variations of mercury (Hg) have been observed in near-surface air at Concordia Station on the East Antarctic Plateau, but the processes controlling these characteristics are not well understood. Here, we use a box model to interpret the Hg-0 (gaseous elemental mercury) measurements in thes year 2013. The model includes atmospheric Hg-0 oxidation (by OH, O-3, or bromine), surface snow Hg-II (oxidized mercury) reduction, and air-snow exchange, and is driven by meteorological fields from a regional climate model. The simulations suggest that a photochemically driven mercury diurnal cycle occurs at the air-snow interface in austral summer. The fast oxidation of Hg-0 in summer may be provided by a two-step bromine-initiated scheme, which is favored by low temperature and high nitrogen oxides at Concordia. The summertime diurnal variations of Hg-0 (peaking during daytime) may be confined within several tens of meters above the snow surface and affected by changing mixed layer depths. Snow re-emission of Hg-0 is mainly driven by photoreduction of snow HgII in summer. Intermittent warming events and a hypothesized reduction of Hg-II occurring in snow in the dark may be important processes controlling the mercury variations in the non-summer period, although their relative importance is uncertain. The Br-initiated oxidation of Hg-0 is expected to be slower at Summit Station in Greenland than at Concordia (due to their difference in temperature and levels of nitrogen oxides and ozone), which may contribute to the observed differences in the summertime diurnal variations of Hg-0 between these two polar inland stations.

Abstract: PM10 source apportionment was performed by positive matrix factorization (PMF) using specific primary and secondary organic molecular markers on samples collected over a one year period (2013) at an urban station in Grenoble (France). The results provided a 9-factor optimum solution, including sources rarely apportioned in the literature, such as two types of primary biogenic organic aerosols (fungal spores and plant debris), as well as specific biogenic and anthropogenic secondary organic aerosols (SOA). These sources were identified thanks to the use of key organic markers, namely, polyols, odd number higher alkanes, and several SOA markers related to the oxidation of isoprene, alpha-pinene, toluene and polycyclic aromatic hydrocarbons (PAHs). Primary and secondary biogenic contributions together accounted for at least 68% of the total organic carbon (OC) in the summer, while anthropogenic primary and secondary sources represented at least 71% of OC during winter-time. A very significant contribution of anthropogenic SOA was estimated in the winter during an intense PM pollution event (PM10 > 50 μg m(-3) for several days: 18% of PM10 and 42% of OC). Specific meteorological conditions with a stagnation of pollutants over 10 days and possibly Fenton-like chemistry and self-amplification cycle of SOA formation could explain such high anthropogenic SOA concentrations during this period. Finally, PMF outputs were also used to investigate the origins of humic-like substances (HuLiS), which represented 16% of OC on an annual average basis. The results indicated that HuLiS were mainly associated with biomass burning (22%), secondary inorganic (22%). mineral dust (15%) and biogenic SOA (14%) factors. This study is probably the first to state that HuLiS are significantly associated with mineral dust. (C) 2017 Elsevier B.V. All rights rights reserved.

Abstract: Inhaled aerosolized particulate matter (PM) induces cellular oxidative stress in vivo, leading to adverse health outcomes. The oxidative potential (OP) of PM appears to be a more relevant proxy of the health impact of the aerosol rather than the total mass concentration. However, the relative contributions of the aerosol sources to the OP are still poorly known. In order to better quantify the impact of different PM sources, we sampled aerosols in a French city for one year (2014, 115 samples). A coupled analysis with detailed chemical speciation (more than 100 species, including organic and carbonaceous compounds, ions, metals and aethalometer measurements) and two OP assays (ascorbic acid, AA, and dithiothreitiol, DTT) in a simulated lung fluid (SLF) were performed in these samples. We present in this study a statistical framework using a coupled approach with positive matrix factorization (PMF) and multiple linear regression to attribute a redox-activity to PM sources. Our results highlight the importance of the biomass burning and vehicular sources to explain the observed OP for both assays. In general, we see a different contribution of the sources when considering the OP AA, OP DTT or the mass of the PM10. Moreover, significant differences are observed between the DTT and AA tests which emphasized chemical specificities of the two tests and the need of a standardized approach for the future studies on epidemiology or toxicology of the PM.

Abstract: Urban development, growing industrialization, and increasing demand for mobility have led to elevated levels of air pollution in many large cities in Latin America, where air quality standards and WHO guidelines are frequently exceeded. The conurbation of the metropolitan area of La Paz/El Alto is one of the fastest growing urban settlements in South America with the particularity of being located in a very complex terrain at a high altitude. As many large cities or metropolitan areas, the metropolitan area of La Paz/El Alto and the Altiplano region are facing air quality deterioration. Long-term measurement data of the equivalent black carbon (eBC) mass concentrations and particle number size distributions (PNSD) from the Global Atmosphere Watch Observatory Chacaltaya (CHC; 5240 m a.s.l., above sea level) indicated a systematic transport of particle matter from the metropolitan area of La Paz/El Alto to this high altitude station and subsequently to the lower free troposphere. To better understand the sources and the transport mechanisms, we conducted eBC and PNSDs measurements during an intensive campaign at two locations in the urban area of La Paz/El Alto from September to November 2012. While the airport of El Alto site (4040 m a.s.l.) can be seen as representative of the urban and Altiplano background, the road site located in Central La Paz (3590 m a.s.l.) is representative for heavy traffic-dominated conditions. Peaks of eBC mass concentrations up to 5 μg m(-3) were observed at the El Alto background site in the early morning and evening, while minimum values were detected in the early afternoon, mainly due to thermal convection and change of the planetary boundary layer height. The traffic-related eBC mass concentrations at the road site reached maximum values of 10-20 μg m(-3). A complete traffic ban on the specific Bolivian Day of Census (November 21, 2012) led to a decrease of eBC below 1 μg m(-3) at the road site for the entire day. Compared to the day before and after, particle number concentrations decreased by a factor between 5 and 25 over the particle size range from 10 to 800 nm, while the submicrometer particle mass concentration dropped by approximately 80%. These results indicate that traffic is the dominating source of BC and particulate air pollution in the metropolitan area of La Paz/El Alto. In general, the diurnal cycle of eBC mass concentration at the Chacaltaya observatory is anti-correlated to the observations at the El Alto background site. This pattern indicates that the traffic-related particulate matter, including BC, is transported to higher altitudes with the developing of the boundary layer during daytime. The metropolitan area of La Paz/El Alto seems to be a significant source for BC of the regional lower free troposphere. From there, BC can be transported over long distances and exert impact on climate and composition of remote southern hemisphere.

Abstract: We investigated the seasonal trends of OA sources affecting the air quality of Marseille (France), which is the largest harbor of the Mediterranean Sea. This was achieved by measurements of nebulized filter extracts using an aerosol mass spectrometer (offline-AMS). In total 216 PM2.5 (particulate matter with an aerodynamic diameter < 2.5 μm) filter samples were collected over 1 year from August 2011 to July 2012. These filters were used to create 54 composite samples which were analyzed by offline-AMS. The same samples were also analyzed for major water-soluble ions, metals, elemental and organic carbon (EC / OC), and organic markers, including n-alkanes, hopanes, polycyclic aromatic hydrocarbons (PAHs), lignin and cellulose pyrolysis products, and nitrocatechols. The application of positive matrix factorization (PMF) to the water-soluble AMS spectra enabled the extraction of five factors, related to hydrocarbonlike OA (HOA), cooking OA (COA), biomass burning OA (BBOA), oxygenated OA (OOA), and an industry-related OA (INDOA). Seasonal trends and relative contributions of OA sources were compared with the source apportionment of OA spectra collected from the AMS field deployment at the same station but in different years and for shorter monitoring periods (February 2011 and July 2008). Online-and offline-AMS source apportionment revealed comparable seasonal contribution of the different OA sources. Results revealed that BBOA was the dominant source during winter, representing on average 48% of the OA, while during summer the main OA component was OOA (63% of OA mass on average). HOA related to traffic emissions contributed on a yearly average 17% to the OA mass, while COA was a minor source contributing 4 %. The contribution of INDOA was enhanced during winter (17% during winter and 11% during summer), consistent with an increased contribution from light alkanes, light PAHs (fluoranthene, pyrene, phenanthrene), and selenium, which is commonly considered as a unique coal combustion and coke production marker. Online-and offline-AMS source apportionments revealed evolving levoglucosan : BBOA ratios, which were higher during late autumn and March. A similar seasonality was observed in the ratios of cellulose combustion markers to lignin combustion markers, highlighting the contribution from cellulose-rich biomass combustion, possibly related to agricultural activities.

Abstract: Particulate matter (PM) induces oxidative stress in vivo, leading to adverse health effects. Oxidative potential (OP) of PM is increasingly studied as a relevant metric for health impact (instead of PM mass concentration) as much of the ambient particle mass do not contribute to PM toxicity. Several assays have been developed to quantify PM oxidative potential and a widely used one is the acellular dithiothreitol (DTT) assay. However in such assays, particles are usually extracted with methanol or Milli-Q water which is unrepresentative of physiological conditions. For this purpose, OPDTT measurements after simulated lung fluids (SLF) extraction, in order to look at the impact of simulated lung fluid constituents, were compared to Milli-Q water extraction measurements. Our major finding is a significant decrease of the OPDTT when the artificial lysosomal fluid (ALF) solution was used. Indeed, ligand compounds are present in the SLF solutions and some induce a decrease of the OP when compared to water extraction. Our results suggest that the effect of ligands and complexation in lining fluids towards PM contaminants probably has been underestimated and should be investigated further.

Abstract: Mercury (Hg) emissions from biomass burning (BB) are an important source of atmospheric Hg and a major factor driving the interannual variation of Hg concentrations in the troposphere. The greatest fraction of Hg from BB is released in the form of elemental Hg (Hg-(g)(0)). However, little is known about the fraction of Hg bound to particulate matter (Hg-P) released from BB, and the factors controlling this fraction are also uncertain. In light of the aims of the Minamata Convention to reduce intentional Hg use and emissions from anthropogenic activities, the relative importance of Hg emissions from BB will have an increasing impact on Hg deposition fluxes. Hg speciation is one of the most important factors determining the redistribution of Hg in the atmosphere and the geographical distribution of Hg deposition. Using the latest version of the Global Fire Emissions Database (GFEDv4.1s) and the global Hg chemistry transport model, ECHMERIT, the impact of Hg speciation in BB emissions, and the factors which influence speciation, on Hg deposition have been investigated for the year 2013. The role of other uncertainties related to physical and chemical atmospheric processes involving Hg and the influence of model parametrisations were also investigated, since their interactions with Hg speciation are complex. The comparison with atmospheric Hg-P concentrations observed at two remote sites, Amsterdam Island (AMD) and Manaus (MAN), in the Amazon showed a significant improvement when considering a fraction of Hg-P from BB. The set of sensitivity runs also showed how the quantity and geographical distribution of Hg-P emitted from BB has a limited impact on a global scale, although the inclusion of increasing fractions Hg-P does limit Hg-(g)(0) availability to the global atmospheric pool. This reduces the fraction of Hg from BB which deposits to the world's oceans from 71 to 62 %. The impact locally is, however, significant on northern boreal and tropical forests, where fires are frequent, uncontrolled and lead to notable Hg inputs to local ecosystems. In the light of ongoing climatic changes this effect could be potentially be exacerbated in the future.

Abstract: Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth's changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring, in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25-32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15-20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

Abstract: Polar ice cores are unique climate archives. Indeed, most of them have a continuous stratigraphy and present high temporal resolution of many climate variables in a single archive. While water isotopic records (delta D or delta O-18) in ice cores are often taken as references for past atmospheric temperature variations, their relationship to temperature is associated with a large uncertainty. Several reasons are invoked to explain the limitation of such an approach; in particular, post-deposition effects are important in East Antarctica because of the low accumulation rates. The strong influence of post-deposition processes highlights the need for surface polar research programs in addition to deep drilling programs. We present here new results on water isotopes from several recent surface programs, mostly over East Antarctica. Together with previously published data, the new data presented in this study have several implications for the climatic reconstructions based on ice core isotopic data: (1) The spatial relationship between surface mean temperature and mean snow isotopic composition over the first meters in depth can be explained quite straightforwardly using simple isotopic models tuned to d-excess vs. delta O-18 evolution in transects on the East Antarctic sector. The observed spatial slopes are significantly higher (similar to 0.7-0.8 parts per thousand. degrees C (1) for delta O-18 vs. temperature) than seasonal slopes inferred from precipitation data at Vostok and Dome C (0.35 to 0.46 parts per thousand. degrees C (1)). We explain these differences by changes in condensation versus surface temperature between summer and winter in the central East Antarctic plateau, where the inversion layer vanishes in summer. (2) Post-deposition effects linked to exchanges between the snow surface and the atmospheric water vapor lead to an evolution of delta O-18 in the surface snow, even in the absence of any precipitation event. This evolution preserves the positive correlation between the delta O-18 of snow and surface temperature, but is associated with a much slower delta O-18-vs-temperature slope than the slope observed in the seasonal precipitation. (3) Post-deposition effects clearly limit the archiving of high-resolution (seasonal) climatic variability in the polar snow, but we suggest that sites with an accumulation rate of the order of 40 kg.m (2).yr (1) may record a seasonal cycle at shallow depths. (C) 2017 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Abstract: Global models predict that new particle formation (NPF) is, in some environments, responsible for a substantial fraction of the total atmospheric particle number concentration and subsequently contributes significantly to cloud condensation nuclei (CCN) concentrations. NPF events were frequently observed at the highest atmospheric observatory in the world, on Chacaltaya (5240 m a.s.l.), Bolivia. The present study focuses on the impact of NPF on CCN population. Neutral cluster and Air Ion Spectrometer and mobility particle size spectrometer measurements were simultaneously used to follow the growth of particles from cluster sizes down to similar to 2 nm up to CCN threshold sizes set to 50, 80 and 100 nm. Using measurements performed between 1 January and 31 December 2012, we found that 61% of the 94 analysed events showed a clear particle growth and significant enhancement of the CCN-relevant particle number concentration. We evaluated the contribution of NPF, relative to the transport and growth of pre-existing particles, to CCN size. The averaged production of 50 nm particles during those events was 5072, and 1481 cm(-3) for 100 nm particles, with a larger contribution of NPF compared to transport, especially during the wet season. The data set was further segregated into boundary layer (BL) and free troposphere (FT) conditions at the site. The NPF frequency of occurrence was higher in the BL (48 %) compared to the FT (39 %). Particle condensational growth was more frequently observed for events initiated in the FT, but on average faster for those initiated in the BL, when the amount of condensable species was most probably larger. As a result, the potential to form new CCN was higher for events initiated in the BL (67% against 53% in the FT). In contrast, higher CCN number concentration increases were found when the NPF process initially occurred in the FT, under less polluted conditions. This work highlights the competition between particle growth and the removal of freshly nucleated particles by coagulation processes. The results support model predictions which suggest that NPF is an effective source of CCN in some environments, and thus may influence regional climate through cloud-related radiative processes.

Abstract: While primary marine aerosol (PMA) is an important part of global aerosol total emissions, its chemical composition and physical flux as a function of the biogeo-chemical properties of the seawater still remain highly un-characterized due to the multiplicity of physical, chemical and biological parameters that are involved in the emission process. Here, two nutrient-enriched mesocosms and one control mesocosm, both filled with Mediterranean seawater, were studied over a 3-week period. PMA generated from the mesocosm waters were characterized in term of chemical composition, size distribution and size-segregated cloud condensation nuclei (CCN), as a function of the seawater chlorophyll a (Chl a) concentration, pigment composition, virus and bacteria abundances. The aerosol number size distribution flux was primarily affected by the seawater temperature and did not vary significantly from one mesocosm to the other. The aerosol number size distribution flux was primarily affected by the seawater temperature and did not vary significantly from one mesocosm to the other. Particle number and CCN aerosol fluxes increase by a factor of 2 when the temperature increases from 22 to 32 degrees C, for all particle submicron sizes. This effect, rarely observed in previous studies, could be specific to oligotrophic waters and/or to this temperature range. In all mesocosms (enriched and control mesocosms), we detected an enrichment of calcium (+ 500 %) and a deficit in chloride (36 %) in the submicron PMA mass compared to the literature inorganic composition of the seawater. There are indications that the chloride deficit and calcium enrichment are linked to biological processes, as they are found to be stronger in the enriched mesocosms. This implies a non-linear transfer function between the seawater composition and PMA composition, with complex processes taking place at the interface during the bubble bursting. We found that the artificial phytoplankton bloom did not affect the CCN activation diameter (D-p,D- 50,D- (average) = 59.85 +/- 3.52 nm and D-p,D-50,D- average = 93.42 +/- 5.14 nm for supersaturations of 0.30 and 0.15% respectively) or the organic fraction of the submicron PMA (average organic to total mass = 0.31 +/- 0.07) compared to the control mesocosm. Contrary to previous observations in natural bloom mesocosm experiments, the correlation between the particle organic fraction and the seawater Chl a was poor, indicating that Chl a is likely not a straightforward proxy for predicting, on a daily scale, PMA organi
c fraction in models for all types of sea and ocean waters. Instead, the organic fraction of the Aitken mode particles were more significantly linked to heterotrophic flagellates, viruses and dissolved organic carbon (DOC). We stress that different conclusions may be obtained in natural (non-enriched) or non-oligotrophic systems.

Abstract: Industrial sources are among the least documented PM (Particulate Matter) source in terms of chemical composition, which limits our understanding of their effective impact on ambient PM concentrations. We report 4 chemical emission profiles of PM2.5 for multiple activities located in a vast metallurgical complex. Emissions profiles were calculated as the difference of species concentrations between an upwind and a downwind site normalized by the absolute PM2.5 enrichment between both sites. We characterized the PM2.5 emissions profiles of the industrial activities related to the cast iron (complex 1) and the iron ore conversion processes (complex 2), as well as 2 storage areas: a blast furnace slag area (complex 3) and an ore terminal (complex 4). PM2.5 major fractions (Organic Carbon (OC) and Elemental Carbon (EC), major ions), organic markers as well as metals/trace elements are reported for the 4 industrial complexes. Among the trace elements, iron is the most emitted for the complex 1 (146.0 mg g(-1) of PM2.5), the complex 2 (70.07 mg g(-1)) and the complex 3 (124.4 mg g(-1)) followed by Al, Mn and Zn. A strong emission of Polycyclic Aromatic Hydrocarbons (PAH), representing 1.3% of the Organic Matter (OM), is observed for the iron ore transformation complex (complex 2) which merges the activities of coke and iron sinter production and the blast furnace processes. In addition to unsubstituted PAHs, sulfur containing PAHs (SPAHs) are also significantly emitted (between 0.011 and 0.068 mg g(-1)) by the complex 2 and could become very useful organic markers of steel industry activities. For the complexes 1 and 2 (cast iron and iron ore converters), a strong fraction of sulfate ranging from 0.284 to 0336 g g(-1)) and only partially neutralized by ammonium, is observed indicating that sulfates, if not directly emitted by the industrial activity, are formed very quickly in the plume. Emission from complex 4 (Ore terminal) are characterized by high contribution of Al (125.7 mg g(-1) of PM2.5) but also, in a lesser extent, of Fe, Mn, Ti and Zn. We also highlighted high contribution of calcium ranging from 0.123 to 0.558 g g(-1) for all of the industrial complexes under study. Since calcium is also widely used as a proxy of the dust contributions in source apportionment studies, our results suggest that this assumption should be reexamined in environments impacted by industrial emissions. (C) 2016 Elsevier Ltd. All rights reserved.

Abstract: Current understanding of mercury (Hg) behavior in the atmosphere contains significant gaps. Some key characteristics of Hg processes, including anthropogenic and geogenic emissions, atmospheric chemistry, and air-surface exchange, are still poorly known. This study provides a complex analysis of processes governing Hg fate in the atmosphere involving both measured data from ground-based sites and simulation results from chemical transport models. A variety of long-term measurements of gaseous elemental Hg (GEM) and reactive Hg (RM) concentration as well as Hg wet deposition flux have been compiled from different global and regional monitoring networks. Four contemporary global-scale transport models for Hg were used, both in their state-of-the-art configurations and for a number of numerical experiments to evaluate particular processes. Results of the model simulations were evaluated against measurements. As follows from the analysis, the interhemispheric GEM gradient is largely formed by the prevailing spatial distribution of anthropogenic emissions in the Northern Hemisphere. The contributions of natural and secondary emissions enhance the south-to-north gradient, but their effect is less significant. Atmospheric chemistry has a limited effect on the spatial distribution and temporal variation of GEM concentration in surface air. In contrast, RM air concentration and wet deposition are largely defined by oxidation chemistry. The Br oxidation mechanism can reproduce successfully the observed seasonal variation of the RM/GEM ratio in the near-surface layer, but it predicts a wet deposition maximum in spring instead of in summer as observed at monitoring sites in North America and Europe. Model runs with OH chemistry correctly simulate both the periods of maximum and minimum values and the amplitude of observed seasonal variation but shift the maximum RM/GEM ratios from spring to summer. O-3 chemistry does not predict significant seasonal variation of Hg oxidation. Hence, the performance of the Hg oxidation mechanisms under study differs in the extent to which they can reproduce the various observed parameters. This variation implies possibility of more complex chemistry and multiple Hg oxidation pathways occurring concurrently in various parts of the atmosphere.

Abstract: Realistic projection of future climate-carbon (C) cycle feedbacks requires better understanding and an improved representation of the C cycle in permafrost regions in the current generation of Earth system models. Here we evaluated 10 terrestrial ecosystem models for their estimates of net primary productivity (NPP) and responses to historical climate change in permafrost regions in the Northern Hemisphere. In comparison with the satellite estimate from the Moderate Resolution Imaging Spectroradiometer (MODIS; 246 +/- 6gCm(-2) yr (-1)), most models produced higher NPP (309 +/- 12 g Cm-2 yr(-1)) over the permafrost region during 2000-2009. By comparing the simulated gross primary productivity (GPP) with a flux tower-based database, we found that although mean GPP among the models was only overestimated by 10% over 1982-2009, there was a twofold discrepancy among models (380 to 800 g Cm-2 yr(-1)), which mainly resulted from differences in simulated maximum monthly GPP (GPP(max)). Most models overestimated C use efficiency (CUE) as compared to observations at both regional and site levels. Further analysis shows that model variability of GPP and CUE are nonlinearly correlated to variability in specific leaf area and the maximum rate of carboxylation by the enzyme Rubisco at 25 degrees C (V-cmax_(25)), respectively. Themodels also varied in their sensitivities of NPP, GPP, and CUE to historical changes in climate and atmospheric CO2 concentration. These results indicate that model predictive ability of the C cycle in permafrost regions can be improved by better representation of the processes controlling CUE and GPP(max) as well as their sensitivity to climate change.

Abstract: Mercury (Hg) is a worldwide contaminant that can cause adverse health effects to wildlife and humans. While atmospheric modeling traces the link from emissions to deposition of Hg onto environmental surfaces, large uncertainties arise from our incomplete understanding of atmospheric processes (oxidation pathways, deposition, and re-emission). Atmospheric Hg reactivity is exacerbated in high latitudes and there is still much to be learned from polar regions in terms of atmospheric processes. This paper provides a synthesis of the atmospheric Hg monitoring data available in recent years (2011-2015) in the Arctic and in Antarctica along with a comparison of these observations with numerical simulations using four cutting-edge global models. The cycle of atmospheric Hg in the Arctic and in Antarctica presents both similarities and differences. Coastal sites in the two regions are both influenced by springtime atmospheric Hg depletion events and by summertime snowpack re-emission and oceanic evasion of Hg. The cycle of atmospheric Hg differs between the two regions primarily because of their different geography. While Arctic sites are significantly influenced by northern hemispheric Hg emissions especially in winter, coastal Antarctic sites are significantly influenced by the reactivity observed on the East Antarctic ice sheet due to katabatic winds. Based on the comparison of multi-model simulations with observations, this paper discusses whether the processes that affect atmospheric Hg seasonality and inter-annual variability are appropriately represented in the models and identifies research gaps in our understanding of the atmospheric Hg cycling in high latitudes.

Abstract: Under the framework of the GMOS project (Global Mercury Observation System) atmospheric mercury monitoring has been implemented at Concordia Station on the high-altitude Antarctic plateau (75 degrees 06'S, 123 degrees 20'E, 3220m above sea level). We report here the first year-round measurements of gaseous elemental mercury (Hg(0)) in the atmosphere and in snowpack interstitial air on the East Antarctic ice sheet. This unique data set shows evidence of an intense oxidation of atmospheric Hg(0) in summer (24-hour daylight) due to the high oxidative capacity of the Antarctic plateau atmosphere in this period of the year. Summertime Hg(0) concentrations exhibited a pronounced daily cycle in ambient air with maximal concentrations around midday. Photochemical reactions and chemical exchange at the air-snow interface were prominent, highlighting the role of the snowpack on the atmospheric mercury cycle. Our observations reveal a 20 to 30% decrease of atmospheric Hg(0) concentrations from May to mid-August (winter, 24 h darkness). This phenomenon has not been reported elsewhere and possibly results from the dry deposition of Hg(0) onto the snowpack. We also reveal the occurrence of multi-day to weeklong atmospheric Hg(0) depletion events in summer, not associated with depletions of ozone, and likely due to a stagnation of air masses above the plateau triggering an accumulation of oxidants within the shallow boundary layer. Our observations suggest that the inland atmospheric reservoir is depleted in Hg(0) in summer. Due to katabatic winds flowing out from the Antarctic plateau down the steep vertical drops along the coast and according to observations at coastal Antarctic stations, the striking reactivity observed on the plateau most likely influences the cycle of atmospheric mercury on a continental scale.

Abstract: Although particulate organic and elemental carbon (OC and EC) are important constituents of the suspended atmospheric particulate matter (PM), measurements of OC and EC are much less common and More uncertain than measurements of e.g. the ionic components of PM. In the framework of atmospheric research infrastructures supported by the European Union, actions have been undertaken to determine and mitigate sampling artefacts, and assess the comparability of OC and EC data obtained in a network of 10 atmospheric observatories across Europe. Positive sampling artefacts (from 0:4 to 2.8 μg C/m(3)) and analytical discrepancies (between -50% and +40% for the EC/TC ratio) have been taken into account to generate a robust data set, from which we established the phenomenology of carbonaceous aerosols at regional background sites in Europe. Across the network, TC and EC annual average concentrations range from 0.4 to 9 μg C/m(3), and from 0.1 to 2 μg C/m(3), respectively. TC/PM10 annual mean ratios range from 0.11 at a Mediterranean site to 0.34 at the most polluted continental site, and TC/PM2.5 ratios are slightly greater at all sites (0.15-0.42). EC/TC annual mean ratios range from 0.10 to 0.22, and do not depend much on PM concentration levels, especially in winter. Seasonal variations in PM and TC concentrations, and in TC/PM and EC/TC ratios, differ across the network, which can be explained by seasonal changes in PM source contributions at some sites. (C) 2016 The Authors. Published by Elsevier Ltd.

Abstract: In 2011 four ice cores were extracted from the summit of Alto dell'Ortles (3859 m), the highest glacier of South Tyrol in the Italian Alps. This drilling site is located only 37 km southwest from where the Tyrolean Iceman, similar to 5.3 kyrs old, was discovered emerging from the ablating ice field of Tisenjoch (3210 m, near the Italian-Austrian border) in 1991. The excellent preservation of this mummy suggested that the Tyrolean Iceman was continuously embedded in prehistoric ice and that additional ancient ice was likely preserved elsewhere in South Tyrol. Dating of the ice cores from Alto dell'Ortles based on Pb-210, tritium, beta activity and C-14 determinations, combined with an empirical model (COPRA), provides evidence for a chronologically ordered ice stratigraphy from the modern glacier surface down to the bottom ice layers with an age of similar to 7 kyrs, which confirms the hypothesis. Our results indicate that the drilling site has continuously been glaciated on frozen bedrock since similar to 7 kyrs BP. Absence of older ice on the highest glacier of South Tyrol is consistent with the removal of basal ice from bedrock during the Northern Hemisphere Climatic Optimum (6-9 kyrs BP), the warmest interval in the European Alps during the Holocene. Borehole inclinometric measurements of the current glacier flow combined with surface ground penetration radar (GPR) measurements indicate that, due to the sustained atmospheric warming since the 1980s, an acceleration of the glacier Alto dell'Ortles flow has just recently begun. Given the stratigraphic-chronological continuity of the Mt. Ortles cores over millennia, it can be argued that this behaviour has been unprecedented at this location since the Northern Hemisphere Climatic Optimum.

Abstract: Ice residual (IR) and total aerosol properties were measured in mixed-phase clouds (MPCs) at the high-alpine Jungfraujoch research station. Black carbon (BC) content and coating thickness of BC-containing particles were determined using single-particle soot photometers. The ice activated fraction (IAF), derived from a comparison of IR and total aerosol particle size distributions, showed an enrichment of large particles in the IR, with an increase in the IAF from values on the order of 10(-4) to 10(-3) for 100nm (diameter) particles to 0.2 to 0.3 for 1m (diameter) particles. Nonetheless, due to the high number fraction of submicrometer particles with respect to total particle number, IR size distributions were still dominated by the submicrometer aerosol. A comparison of simultaneously measured number size distributions of BC-free and BC-containing IR and total aerosol particles showed depletion of BC by number in the IR, suggesting that BC does not play a significant role in ice nucleation in MPCs at the Jungfraujoch. The potential anthropogenic climate impact of BC via the glaciation effect in MPCs is therefore likely to be negligible at this site and in environments with similar meteorological conditions and a similar aerosol population. The IAF of the BC-containing particles also increased with total particle size, in a similar manner as for the BC-free particles, but on a level 1 order of magnitude lower. Furthermore, BC-containing IR were found to have a thicker coating than the BC-containing total aerosol, suggesting the importance of atmospheric aging for ice nucleation.

Abstract: During atmospheric mercury and ozone depletion events in the springtime in polar regions gaseous elemental mercury and ozone undergo rapid declines. Mercury is quicldy transformed into oxidation products, which are subsequently removed by deposition. Here we show that such events also occur during Antarctic winter over sea ice areas, leading to additional deposition of mercury. Over four months in the Weddell Sea we measured gaseous elemental, oxidized, and particulate-bound mercury, as well as ozone in the troposphere and total and elemental mercury concentrations in snow, demonstrating a series of depletion and deposition events between July and September. The winter depletions in July were characterized by stronger correlations between mercury and ozone and larger formation of particulate-bound mercury in air compared to later spring events. It appears that light at large solar zenith angles is sufficient to initiate the photolytic formation of halogen radicals. We also propose a dark mechanism that could explain observed events in air masses coming from dark regions. Br-2 that could be the main actor in dark conditions was possibly formed in high concentrations in the marine boundary layer in the dark. These high concentrations may also have caused the formation of high concentrations of CHBr3 and CH2I2 in the top layers of the Antarctic sea ice observed during winter. These new findings show that the extent of depletion events is larger than previously believed and that winter depletions result in additional deposition of mercury that could be transferred to marine and terrestrial ecosystems. (C) 2016 Elsevier Ltd. All rights reserved.

Abstract: The ability of seven state-of-the-art chemistry-aerosol models to reproduce distributions of tropospheric ozone and its precursors, as well as aerosols over eastern Asia in summer 2008, is evaluated. The study focuses on the performance of models used to assess impacts of pollutants on climate and air quality as part of the EU ECLIPSE project. Models, run using the same ECLIPSE emissions, are compared over different spatial scales to in situ surface, vertical profiles and satellite data. Several rather clear biases are found between model results and observations, including overestimation of ozone at rural locations downwind of the main emission regions in China, as well as downwind over the Pacific. Several models produce too much ozone over polluted regions, which is then transported downwind. Analysis points to different factors related to the ability of models to simulate VOC-limited regimes over polluted regions and NOx limited regimes downwind. This may also be linked to biases compared to satellite NO2, indicating overestimation of NO2 over and to the north of the northern China Plain emission region. On the other hand, model NO2 is too low to the south and west of this region and over South Korea/Japan. Overestimation of ozone is linked to systematic underestimation of CO particularly at rural sites and downwind of the main Chinese emission regions. This is likely to be due to enhanced destruction of CO by OH. Overestimation of Asian ozone and its transport downwind implies that radiative forcing from this source may be overestimated. Model-observation discrepancies over Beijing do not appear to be due to emission controls linked to the Olympic Games in summer 2008. With regard to aerosols, most models reproduce the satellite-derived AOD patterns over eastern China. Our study nevertheless reveals an overestimation of ECLIPSE model mean surface BC and sulphate aerosols in urban China in summer 2008. The effect of the short-term emission mitigation in Beijing is too weak to explain the differences between the models. Our results rather point to an overestimation of SO2 emissions, in particular, close to the surface in Chinese urban areas. However, we also identify a clear underestimation of aerosol concentrations over northern India, suggesting that the rapid recent growth of emissions in India, as well as their spatial extension, is underestimated in emission inventories. Model deficiencies in the representation of pollution accumulation due to the Indian monsoon may also be playing a role. Comparison with vertical aerosol lidar measurements highlights a general underestimation of scattering aerosols in the boundary layer associated with overestimation in the free troposphere pointing to modelled aerosol lifetimes that are too long. This is likely linked to too strong vertical transport and/or insufficient deposition efficiency during transport or export from the boundary layer, rather than chemical processing (in the case of sulphate aerosols). Underestimation of sulphate in the boundary layer implies potentially large errors in simulated aerosol-cloud interactions, via impacts on boundary-layer clouds. This evaluation has important implications for accurate assessment of air pollutants on regional air quality and global climate based on global model calculations. Ideally, models should be run at higher resolution over source regions to better simulate urban-rural pollutant gradients and/or chemical regimes, and also to better resolve pollutant processing and loss by wet deposition as well as vertical transport. Discrepancies in vertical distributions require further quantification and improvement since these are a key factor in the determination of radiative forcing from short-lived pollutants.

Abstract: 21 PAHs, 27 oxy-PAHs and 32 nitro-PAHs were measured every third day over a year in both gaseous (G) and particulate PM10 (P) phases in ambient air of Grenoble (France). Mean total concentrations (G + P) of PAHs and oxy-PAHs were in the same range and about 10 ng m(-3). Nitro-PAHs were 50 to 100 times less concentrated averaging 100 pg m(-3). Polycyclic aromatic compound (PAC) concentrations were 5 to 7 times higher in “cold” period (October to March) than in “warm” period (April to September). Seasonal variations may be explained by higher primary emissions from residential heating, especially biomass burning in “cold” season. Meteorological conditions and influence of the geomorphology around Grenoble, with the formation of thermal inversion layers leading to the stagnation of pollutants, were additional key parameters. Maximum individual PAC concentrations were observed during two PM10 pollution events in December and February-March. Chemical processes and secondary formation of oxy-and nitro-PAH were probably enhanced by the accumulation of the pollutants during these events. PAC gas/particle partitioning depended on compound molecular weight and vapour pressure. Gas/particle partitioning of oxy- and nitro-PAHs were evaluated using a multi-phase poly-parameter linear free energy relationship model. The PAC cancer risk was assessed using toxic equivalency factors available in the literature (19 PAHs, 10 nitro-PAHs and 1 oxy- PAH). Overall, particle-bound PACs contributed about 76% of the cancer risk. While PAHs accounted for most of the total PAC cancer risk, oxy- and nitro-PAHs could account for up to 24%. The risk quantification across substance classes is limited by toxicological data availability. (C) 2016 Elsevier B.V. All rights reserved.

Abstract: A reliable assessment of the optical properties of atmospheric black carbon is of crucial importance for an accurate estimation of radiative forcing. In this study we investigated the spatio-temporal variability of the mass absorption cross-section (MAC) of atmospheric black carbon, defined as light absorption coefficient (σap) divided by elemental carbon mass concentration (mEC). σap and mEC have been monitored at supersites of the ACTRIS network for a minimum period of one year. The 9 rural background sites considered in this study cover southern Scandinavia, central Europe and the Mediterranean. σap was determined using filter based absorption photometers and mEC using a thermal-optical technique. Homogeneity of the data-set was ensured by harmonization of all involved methods and instruments during extensive intercomparison exercises at the European Center for Aerosol Calibration (ECAC). Annual mean values of σap at a wavelength of 637 nm vary between 0.66 and 1.3 Mm-1 in southern Scandinavia, 3.7-11 Mm-1 in Central Europe and the British Isles, and 2.3-2.8 Mm-1 in the Mediterranean. Annual mean values of mEC vary between 0.084 and 0.23 μg m-3 in southern Scandinavia, 0.28-1.1 in Central Europe and the British Isles, and 0.22-0.26 in the Mediterranean. Both σap and mEC in southern Scandinavia and Central Europe have a distinct seasonality with maxima during the cold season and minima during summer, whereas at the Mediterranean sites an opposite trend was observed. Annual mean MAC values were quite similar across all sites and the seasonal variability was small at most sites. Consequently, a MAC value of 10.0 m2 g-1 (geometric standard deviation = 1.33) at a wavelength of 637 nm can be considered to be representative of the mixed boundary layer at European background sites, where BC is expected to be internally mixed to a large extent. The observed spatial variability is rather small compared to the variability of values in previous literature, indicating that the harmonization efforts resulted in substantially increased precision of the reported MAC. However, absolute uncertainties of the reported MAC values remain as high as ± 30-70% due to the lack of appropriate reference methods and calibration materials. The mass ratio between elemental carbon and non-light-absorbing matter was used as a proxy for the thickness of coatings around the BC cores, in order to assess the influence of the mixing state on the MAC of BC. Indeed, the MAC was found to increase with increasing values of the coating thickness proxy. This provides evidence that coatings do increase the MAC of atmospheric BC to some extent, which is commonly referred to as lensing effect.

Abstract: Although polar regions are considered isolated and pristine areas, the organisms that inhabit these zones are exposed to global pollution. Heavy metals, such as mercury, are global pollutants and can reach almost any location on Earth. Mercury may come from natural, volcanic or geological sources, or result from anthropogenic sources, in particular industrial or mining activities. In this study, we have investigated one of the most prominent biological non-marine communities in both polar regions, microbial mats, in terms of their Hg and methyl-mercury (MeHg) concentrations and accumulation capacities. The main hypotheses posed argued on the importance of different factors, and to test them, we have measured Hg concentrations in microbial mats that were collected from 6 locations in different ecological situations. For this purpose, the direct anthropogenic impacts, volcanic influences, proximity to the seashore, latitudinal gradient and C contents were investigated. Our results show that, other than the direct anthropogenic influence, none of the other hypotheses alone satisfactorily explains the Hg content in microbial mats. In contrast, the MeHg contents were noticeably different between the investigated locations, with a higher proportion of MeHg on the McMurdo Ice Shelf (Antarctica) and a lower proportion on Ward Hunt Island (High Arctic). Furthermore, our results from in situ experiments indicated that the microbial mats from South Shetland Islands could quickly accumulate (48 h) Hg when Hg dissolved salts were supplied. Over short-term periods, these mats do not transform Hg into MeHg under field conditions. (C) 2014 Elsevier B.V. All rights reserved.

Abstract: New efficient approaches to the characterization of fly ash and particulate matter (PM) have to be developed in order to better understand their impacts on environment and health. Polycyclic aromatic hydrocarbons (PAH) contained in PM from biomass burning have been identified as genotoxic and cytotoxic, and some tools already exist to quantify their contribution to PM. Optical fluorescence microscopy is proposed as a rapid and relatively economical method to allow the quantification of PAH in different particles emitted from biomass combustion. In this study samples were collected in the flue gas of biomass-combustion facilities with nominal output ranging from 40 kW to 17.3 MW. The fly ash samples were collected with various flue gas treatment devices (multicyclone, baghouse filter, electrostatic precipitator); PM samples were fractionated from the flue gas with a DEKATI (R) DGI impactor. A method using fluorescence observations (at 470nm), white-light observations and image processing has been developed with the aim of quantifying fluorescence per sample. Organic components of PM and fly ash, such as PAH, humic-like substances (HULIS) and water-soluble organic carbon (WSOC) were also quantified. Fluorescence microscopy analysis method assessment was first realized with fly ash that was artificially coated with PAH and HULIS. Total amounts of PAH in the three size fractions of actual PM from biomass burning strongly correlated with the intensities of fluorescence. These encouraging results contribute to the development of a faster and cheaper method of quantifying particle-bound PAH.Copyright 2015 American Association for Aerosol Research

Abstract: Black carbon (BC) in snow in the Himalayas has recently attracted considerable interest due to its impact on snow albedo, snow and glacier melting, regional climate and water resources. A single particle soot photometer (SP2) instrument was used to measure refractory BC (rBC) in a series of surface snow samples collected in the upper Khumbu Valley, Nepal between November 2009 and February 2012. The obtained time series indicates annual cycles with maximum rBC concentrations before the onset of the monsoon season and fast decreases during the monsoon period. Detected concentrations ranged from a few up to 70 ppb with rather large uncertainties due to the handling of the samples. Detailed modeling of the snowpack, including the detected range and an estimated upper limit of BC concentrations, was performed to study the role of BC in the seasonal snowpack. Simulations were performed for three winter seasons with the snowpack model Crocus, including a detailed description of the radiative transfer inside the snowpack. While the standard Crocus model strongly overestimates the height and the duration of the seasonal snowpack, a better calculation of the snow albedo with the new radiative transfer scheme enhanced the representation of the snow. However, the period with snow on the ground without BC in the snow was still overestimated between 37 and 66 days, which was further diminished by 8 to 15% and more than 40% in the presence of 100 or 300 ppb of BC. Compared to snow without BC, the albedo is reduced on average by 0.027 and 0.060 in the presence of 100 and 300 ppb BC. While the impact of increasing BC in the snow on the albedo was largest for clean snow, the impact on the local radiative forcing is the opposite. Here, increasing BC caused an even larger impact at higher BC concentrations. This effect is related to an accelerated melting of the snowpack caused by a more efficient metamorphism of the snow due to an increasing size of the snow grains with increasing BC concentrations. The melting of the winter snowpack was shifted by 3 to 10 and 17 to 27 days during the three winter seasons in the presence of 100 and 300 ppb BC compared to clean snow, while the simulated annual local radiative forcing corresponds to 3 to 4.5 and 10.5 to 13.0 W m(-2). An increased sublimation or evaporation of the snow reduces the simulated radiative forcing, leading to a net forcing that is lower by 0.5 to 1.5 W m(-2), while the addition of 10 ppm dust causes an increase of the radiative forcing between 2.5 and 3 W m(-2). According to the simulations, 7.5 ppm of dust has an effect equivalent to 100 ppb of BC concerning the impact on the melting of the snowpack and the local radiative forcing.

Abstract: A comparison exercise on thermal-optical elemental carbon/organic carbon (ECOC) analysers was carried out among 17 European laboratories. Contrary to previous comparison exercises, the 17 participants made use of an identical instrument set-up, after correcting for temperature offsets with the application of a recently developed temperature calibration kit (Sunset Laboratory Inc, OR, US). Temperature offsets reported by participants ranged from -93 to +100 degrees C per temperature step. Five filter samples and two su-crose solutions were analysed with both the EUSAAR2 and NIOSH870 thermal protocols. z scores were calculated for total carbon (TC); nine outliers and three stragglers were identified. Three outliers and eight stragglers were found for EC. Overall, the participants provided results between the warning levels with the exception of two laboratories that showed poor performance, the causes of which were identified and corrected through the course of the comparison exercise. The TC repeatability and reproducibility (expressed as relative standard deviations) were 11 and 15% for EUSAAR2 and 9.2 and 12% for NIOSH870; the standard deviations for EC were 15 and 20% for EUSAAR2 and 20 and 26% for NIOSH870. TC was in good agreement between the two protocols, T-CNIOSH870 = 0.98 x TCEUSAAR2 (R-2 = 1.00, robust means). Transmittance (TOT) calculated EC for NIOSH870 was found to be 20% lower than for EU-SAAR2, E-CNIOSH870 = 0.80 x ECEUSAAR2 (R-2 = 0.96, robust means). The thermograms and laser signal values were compared and similar peak patterns were observed per sample and protocol for most participants. Notable deviations from the typical patterns indicated either the absence or inaccurate application of the temperature calibration procedure and/or pre-oxidation during the inert phase of the analysis. Low or zero pyrolytic organic carbon (POC), as reported by a few participants, is suggested as an indicator of an instrument-specific pre-oxidation. A sample-specific preoxidation effect was observed for filter G, for all participants and both thermal protocols, indicating the presence of oxygen donors on the suspended particulate matter. POC (TOT) levels were lower for NIOSH870 than for EUSAAR2, which is related to the heating profile differences of the two thermal protocols.

Abstract: While nucleation may represent one of the major processes responsible for the total aerosol number burden in the atmosphere, and especially at high altitude, new particle formation (NPF) events occurring in the upper part of the troposphere are poorly documented in the literature, particularly in the southern hemisphere. NPF events were detected and analyzed at the highest measurement site in the world, Chacaltaya (5240 m a.s.l.), Bolivia between January 1 and December 31 2012, using a Neutral Aerosol and Ion Spectrometer (NAIS) that detects clusters down to 0.4 nm. NPF frequency at Chacaltaya is one of the highest reported so far (63.9%) and shows a clear seasonal dependency with maximum up to 100% during the dry season. This high seasonality of the NPF events frequency was found to be likely linked to the presence of clouds in the vicinity of the station during the wet season. Multiple NPF events are seen on almost 50% of event days and can reach up to 6 events per day, increasing the potential of nucleation to be the major contributor to the particle number concentrations in the upper troposphere. Ion-induced nucleation (IIN) was 14.8% on average, which is higher than the IIN fractions reported for boundary layer stations. The median formation rate of 2 nm particles computed for first position events is increased during the dry season (1.90 cm(-3) s(-1)) compared to the wet season (1.02 cm(-3) s(-1)), showing that events are more intense, on top of being more frequent during the dry season. On the contrary, particle growth rates (GRs) are on average enhanced during the wet season, which could be explained by higher amount of biogenic volatile organic compounds transported from the Amazon rainforest. The NPF events frequency is clearly enhanced when air masses originate from the oceanic sector, with a frequency of occurrence close to 1. However, based on the particle GRs, we calculate that particles most likely nucleate after the oceanic air masses reach the land and are presumably not originating from the marine free troposphere. The high frequency of NPF events, the occurrence of multiple events per day, and the relatively high formation rates observed at Chacaltaya imply that nucleation and growth are likely to be the major mechanism feeding the upper atmosphere with aerosol particles in this part of the continent. (C) 2014 Elsevier Ltd. All rights reserved.

Abstract: Atmospheric pollutant dispersion near sources is typically simulated by Gaussian models because of their efficient compromise between reasonable accuracy and manageable computational time. However, the standard Gaussian dispersion formula applies downwind of a source under advective conditions with a well-defined wind direction and cannot calculate air pollutant concentrations under calm conditions with fluctuating wind direction and/or upwind of the emission source. Attempts have been made to address atmospheric dispersion under such conditions. This work evaluates the performance of standard and modified Gaussian plume models using measurements of NO2, PM10, PM2.5, five inorganic ions and seven metals conducted near a freeway in Grenoble, France, during 11-27 September 2011. The formulation for calm conditions significantly improves model performance. However, it appears that atmospheric dispersion due to vehicle-induced turbulence is still underestimated. Furthermore, model performance is poor for particulate species unless road dust resuspension by traffic is explicitly taken into account. (C) 2014 Elsevier Ltd. All rights reserved.

Abstract: We perform global-scale inverse modeling to constrain present-day atmospheric mercury emissions and relevant physiochemical parameters in the GEOS-Chem chemical transport model. We use Bayesian inversion methods combining simulations with GEOS-Chem and ground-based Hg-0 observations from regional monitoring networks and individual sites in recent years. Using optimized emissions/parameters, GEOS-Chem better reproduces these ground-based observations and also matches regional over-water Hg-0 and wet deposition measurements. The optimized global mercury emission to the atmosphere is 5.8 Gg yr(-1). The ocean accounts for 3.2 Gg yr(-1) (55 % of the total), and the terrestrial ecosystem is neither a net source nor a net sink of Hg-0. The optimized Asian anthropogenic emission of Hg-0 (gas elemental mercury) is 650-1770 Mg yr(-1), higher than its bottom-up estimates (550-800 Mg yr(-1)). The ocean parameter inversions suggest that dark oxidation of aqueous elemental mercury is faster, and less mercury is removed from the mixed layer through particle sinking, when compared with current simulations. Parameter changes affect the simulated global ocean mercury budget, particularly mass exchange between the mixed layer and subsurface waters. Based on our inversion results, we re-evaluate the long-term global biogeochemical cycle of mercury, and show that legacy mercury becomes more likely to reside in the terrestrial ecosystem than in the ocean. We estimate that primary anthropogenic mercury contributes up to 23 % of present-day atmospheric deposition.

Abstract: The monosaccharide anhydrides (MAs) levoglucosan, galactosan and mannosan are products of incomplete combustion and pyrolysis of cellulose and hemicelluloses, and are found to be major constituents of biomass burning (BB) aerosol particles. Hence, ambient aerosol particle concentrations of levoglucosan are commonly used to study the influence of residential wood burning, agricultural waste burning and wildfire emissions on ambient air quality. A European-wide intercomparison on the analysis of the three monosaccharide anhydrides was conducted based on ambient aerosol quartz fiber filter samples collected at a Norwegian urban background site during winter. Thus, the samples' content of MAs is representative for BB particles originating from residential wood burning. The purpose of the intercomparison was to examine the comparability of the great diversity of analytical methods used for analysis of levoglucosan, mannosan and galactosan in ambient aerosol filter samples. Thirteen laboratories participated, of which three applied high-performance anion-exchange chromatography (HPAEC), four used high-performance liquid chromatography (HPLC) or ultra-performance liquid chromatography (UPLC) and six resorted to gas chromatography (GC). The analytical methods used were of such diversity that they should be considered as thirteen different analytical methods. All of the thirteen laboratories reported levels of levoglucosan, whereas nine reported data for mannosan and/or galactosan. Eight of the thirteen laboratories reported levels for all three isomers. The accuracy for levoglucosan, presented as the mean percentage error (PE) for each participating laboratory, varied from -63 to 20 %; however, for 62% of the laboratories the mean PE was within +/- 10 %, and for 85% the mean PE was within +/- 20 %. For mannosan, the corresponding range was 60 to 69 %, but as for levoglucosan, the range was substantially smaller for a subselection of the laboratories; i.e. for 33% of the laboratories the mean PE was within +/- 10 %. For galactosan, the mean PE for the participating laboratories ranged from 84 to 593 %, and as for mannosan 33% of the laboratories reported a mean PE within +/- 10 %. The variability of the various analytical methods, as defined by their minimum and maximum PE value, was typically better for levoglucosan than for mannosan and galactosan, ranging from 3.2 to 41% for levoglucosan, from 10 to 67% for mannosan and from 6 to 364% for galactosan. For the levoglucosan to mannosan ratio, which may be used to assess the relative importance of softwood versus hardwood burning, the variability only ranged from 3.5 to 24 %. To our knowledge, this is the first major intercomparison on analytical methods used to quantify monosaccharide anhydrides in ambient aerosol filter samples conducted and reported in the scientific literature. The results show that for levoglucosan the accuracy is only slightly lower than that reported for analysis of SO42- (sulfate) on filter samples, a constituent that has been analysed by numerous laboratories for several decades, typically by ion chromatography and which is considered a fairly easy constituent to measure. Hence, the results obtained for levoglucosan with respect to accuracy are encouraging and suggest that levels of levoglucosan, and to a lesser extent mannosan and galactosan, obtained by most of the analytical methods currently used to quantify monosaccharide anhydrides in ambient aerosol filter samples, are comparable. Finally, the various analytical methods used in the current study should be tested for other aerosol matrices and concentrations as well, the most obvious being summertime aerosol samples affected by wildfires and/or agricultural fires.

Abstract: Snow in the environment acts as a host to rich chemistry and provides a matrix for physical exchange of contaminants within the ecosystem. The goal of this review is to summarise the current state of knowledge of physical processes and chemical reactivity in surface snow with relevance to polar regions. It focuses on a description of impurities in distinct compartments present in surface snow, such as snow crystals, grain boundaries, crystal surfaces, and liquid parts. It emphasises the microscopic description of the ice surface and its link with the environment. Distinct differences between the disordered air-ice interface, often termed quasi-liquid layer, and a liquid phase are highlighted. The reactivity in these different compartments of surface snow is discussed using many experimental studies, simulations, and selected snow models from the molecular to the macro-scale. Although new experimental techniques have extended our knowledge of the surface properties of ice and their impact on some single reactions and processes, others occurring on, at or within snow grains remain unquantified. The presence of liquid or liquid-like compartments either due to the formation of brine or disorder at surfaces of snow crystals below the freezing point may strongly modify reaction rates. Therefore, future experiments should include a detailed characterisation of the surface properties of the ice matrices. A further point that remains largely unresolved is the distribution of impurities between the different domains of the condensed phase inside the snowpack, i.e. in the bulk solid, in liquid at the surface or trapped in confined pockets within or between grains, or at the surface. While surface-sensitive laboratory techniques may in the future help to resolve this point for equilibrium conditions, additional uncertainty for the environmental snowpack may be caused by the highly dynamic nature of the snowpack due to the fast metamorphism occurring under certain environmental conditions. Due to these gaps in knowledge the first snow chemistry models have attempted to reproduce certain processes like the long-term incorporation of volatile compounds in snow and firn or the release of reactive species from the snowpack. Although so far none of the models offers a coupled approach of physical and chemical processes or a detailed representation of the different compartments, they have successfully been used to reproduce some field experiments. A fully coupled snow chemistry and physics model remains to be developed.

Abstract: Cloud water was sampled during 8 months, in 2008 and 2009, at the puy de Dome high-altitude atmospheric research station (France). The concentrations of 7Be and 210Pb, both naturally occurring radionuclides, and 137Cs of anthropogenic origin, were determined. Those values are useful for a better knowledge of the aftermath cloud deposition and more generally for wet deposition assessment of radionuclides. This is of primary interest in case of a nuclear accident, especially considering 137Cs deposition, both for high-altitude locations that are regularly embedded by clouds and also for lowlands where fog can occur. The 7Be and 210Pb average activity concentrations in cloud water found were 1.9±0.11mBqm-3 air and 140±10μBqm-3 air, respectively. For 137Cs, the average concentration was 0.14±0.02μBqm-3 air. This very low-level is representative of the long term post-accidental background level. Indeed, for the studied period, the last accidental 137Cs release was that of Chernobyl accident, in April 1986. To our knowledge this is the first data about 137Cs reference level determination in cloud water. The comparison between cloud water and rain water concentrations showed a ratio cloud/rain ranging between 3.4 and 8.1, in agreement with previous studies performed on inorganic compounds. Scavenging efficiencies of aerosols by cloud droplets were also calculated with the additional aerosol concentrations routinely measured at the station and were quite low (0.13-0.40) compared to what has previously been observed for inorganic soluble ions.