The fate of NOx emissions due to nocturnal oxidation at high latitudes: 1-D simulations and sensitivity experiments

The fate of nitrogen oxide pollution during high-latitude winter is controlled by reactions of dinitrogen pentoxide (N2O5) and is highly affected by the competition between heterogeneous atmospheric reactions and deposition to the snowpack. MISTRA (MIcrophysical STRAtus), a 1-D photochemical model, simulated an urban pollution plume from Fairbanks, Alaska to investigate this competition of N2O5 reactions and explore sensitivity to model parameters. It was found that dry deposition of N2O5 made up a significant fraction of N2O5 loss near the snowpack, but reactions on aerosol particles dominated loss of N2O5 over the integrated atmospheric column. Sensitivity experiments found the fate of NOx emissions were most sensitive to NO emission flux, photolysis rates, and ambient temperature. The results indicate a strong sensitivity to urban area density, season and clouds, and temperature, implying a strong sensitivity of the results to urban planning and climate change. Results suggest that secondary formation of particulate (PM2.5) nitrate in the Fairbanks downtown area does not contribute significant mass to the total PM2.5 concentration, but appreciable amounts are formed downwind of downtown due to nocturnal NOx oxidation and subsequent reaction with ammonia on aerosol particles

Accommodation coefficient of HOBr on deliquescent sodium bromide aerosol particles

Uptake of HOBr on sea salt aerosol, sea salt brine or ice is believed to be a key process providing a source of photolabile bromine (Br₂) and sustaining ozone depletion cycles in the Arctic troposphere. In the present study, uptake of HOBr on sodium bromide (NaBr) aerosol particles was investigated at an extremely low HOBr concentration of 300 cm^-3 using the short-lived radioactive isotopes ^83-86Br. Under these conditions, at maximum one HOBr molecule was taken up per particle. The rate of uptake was clearly limited by the mass accommodation coefficient, which was calculated to be 0.6 ± 0.2. This value is a factor of 10 larger than estimates used in earlier models. The atmospheric implications are discussed using the box model "MOCCA'', showing that the increase of the accommodation coefficient of HOBr by a factor of 10 only slightly affects net ozone loss, but significantly increases chlorine release

Tracer Measurements in Growing Sea Ice Support Convective Gravity Drainage Parameterizations

Gravity drainage is the dominant process redistributing solutes in growing sea ice. Modeling gravity drainage is therefore necessary to predict physical and biogeochemical variables in sea ice. We evaluate seven gravity drainage parameterizations, spanning the range of approaches in the literature, using tracer measurements in a sea ice growth experiment. Artificial sea ice is grown to around 17 cm thickness in a new experimental facility, the Roland von Glasow air‐sea‐ice chamber. We use NaCl (present in the water initially) and rhodamine (injected into the water after 10 cm of sea ice growth) as independent tracers of brine dynamics. We measure vertical profiles of bulk salinity in situ, as well as bulk salinity and rhodamine in discrete samples taken at the end of the experiment. Convective parameterizations that diagnose gravity drainage using Rayleigh numbers outperform a simpler convective parameterization and diffusive parameterizations when compared to observations. This study is the first to numerically model solutes decoupled from salinity using convective gravity drainage parameterizations. Our results show that (1) convective, Rayleigh number‐based parameterizations are our most accurate and precise tool for predicting sea ice bulk salinity; and (2) these parameterizations can be generalized to brine dynamics parameterizations, and hence can predict the dynamics of any solute in growing sea ic

The tropospheric processing of acidic gases and hydrogen sulphide in volcanic gas plumes as inferred from field and model investigations

Improving the constraints on the atmospheric fate and depletion rates of acidic compounds persistently emitted by non-erupting (quiescent) volcanoes is important for quantitatively predicting the environmental impact of volcanic gas plumes. Here, we present new experimental data coupled with modelling studies to investigate the chemical processing of acidic volcanogenic species during tropospheric dispersion. Diffusive tube samplers were deployed at Mount Etna, a very active open-conduit basaltic volcano in eastern Sicily, and Vulcano Island, a closed-conduit quiescent volcano in the Aeolian Islands (northern Sicily). Sulphur dioxide (SO₂), hydrogen sulphide (H₂S), hydrogen chloride (HCl) and hydrogen fluoride (HF) concentrations in the volcanic plumes (typically several minutes to a few hours old) were repeatedly determined at distances from the summit vents ranging from 0.1 to ~10 km, and under different environmental conditions. At both volcanoes, acidic gas concentrations were found to decrease exponentially with distance from the summit vents (e.g., SO₂ decreases from ~10 000 μg/m³at 0.1 km from Etna's vents down to ~7 μg/m³ at ~10 km distance), reflecting the atmospheric dilution of the plume within the acid gas-free background troposphere. Conversely, SO₂/HCl, SO₂/HF, and SO₂/H₂S ratios in the plume showed no systematic changes with plume aging, and fit source compositions within analytical error. Assuming that SO₂ losses by reaction are small during short-range atmospheric transport within quiescent (ash-free) volcanic plumes, our observations suggest that, for these short transport distances, atmospheric reactions for H₂S and halogens are also negligible. The one-dimensional model MISTRA was used to simulate quantitatively the evolution of halogen and sulphur compounds in the plume of Mt. Etna. Model predictions support the hypothesis of minor HCl chemical processing during plume transport, at least in cloud-free conditions. Larger variations in the modelled SO₂/HCl ratios were predicted under cloudy conditions, due to heterogeneous chlorine cycling in the aerosol phase. The modelled evolution of the SO₂/H₂S ratios is found to be substantially dependent on whether or not the interactions of H₂S with halogens are included in the model. In the former case, H₂S is assumed to be oxidized in the atmosphere mainly by OH, which results in minor chemical loss for H₂S during plume aging and produces a fair match between modelled and measured SO₂/H₂S ratios. In the latter case, fast oxidation of H₂S by Cl leads to H₂S chemical lifetimes in the early plume of a few seconds, and thus SO₂ to H₂S ratios that increase sharply during plume transport. This disagreement between modelled and observed plume compositions suggests that more in-detail kinetic investigations are required for a proper evaluation of H₂S chemical processing in volcanic plumes

Reactive halogen chemistry in volcanic plumes

Bromine monoxide (BrO) and sulphur dioxide (SO2) abundances as a function of the distance from the source were measured by ground-based scattered-light Multi AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) in the volcanic plumes of Mt. Etna on Sicily, Italy in August-October 2004 and May 2005 and Villarica in Chile in November 2004. BrO and SO2 spatial distributions in a cross section of Mt. Etna’s plume were also determined by Imaging DOAS. We observed an increase in the BrO/SO2 ratio in the plume from below the detection limit near the vent to about 4.5 x 10-4 at 19 km (Mt. Etna) and to about 1.3 x 10-4 at 3 km (Villarica) distance, respectively. Additional attempts were undertaken to evaluate the compositions of individual vents on Mt. Etna. Furthermore, we detected the halogen species ClO and OClO. This is the first time that OClO could be detected in a volcanic plume. Using calculated thermodynamic equilibrium compositions as input data for a one–dimensional photochemical model, we could reproduce the observed BrO and SO2 vertical columns in the plume and their ratio as function of distance from the volcano as well as vertical BrO and SO2 profiles across the plume with current knowledge of multiphase halogen chemistry, but only when we assumed the existence of an ”effective source region”, where volcanic volatiles and ambient air are mixed at about 600°C (in the proportions of 60% and 40%, respectively

The tropospheric processing of acidic gases and hydrogen sulphide in volcanic gas plumes as inferred from field and model investigations

Improving the constraints on the atmospheric fate and depletion rates of acidic compounds persistently emitted by non-erupting (quiescent) volcanoes is important for quantitatively predicting the environmental impact of volcanic gas plumes. Here, we present new experimental data coupled with modelling studies to investigate the chemical processing of acidic volcanogenic species during tropospheric dispersion. Diffusive tube samplers were deployed at Mount Etna, a very active open-conduit basaltic volcano in eastern Sicily, and Vulcano Island, a closed-conduit quiescent volcano in the Aeolian Islands (northern Sicily). Sulphur dioxide (SO2), hydrogen sulphide (H2S), hydrogen chloride (HCl) and hydrogen fluoride (HF) concentrations in the volcanic plumes (typically several minutes to a few hours old) were repeatedly determined at distances from the summit vents ranging from 0.1 to ~10 km, and under different environmental conditions. At both volcanoes, acidic gas concentrations were found to decrease exponentially with distance from the summit vents (e.g., SO2 decreases from ~10,000 μg/m3 at 0.1 km from Etna’s vents down to ~7 _μg/m3 at ~10km distance), reflecting the atmospheric dilution of the plume within the acid gas-free background troposphere. Conversely, SO2/HCl, SO2/HF, and SO2/H2S ratios in the plume showed no systematic changes with plume aging, and fit source compositions within analytical error. Assuming that SO2 losses by reaction are small during short-range atmospheric transport within quiescent (ash-free) volcanic plumes, our observations suggest that, for these short transport distances, atmospheric reactions for H2S and halogens are also negligible. The one-dimensional model MISTRA was used to simulate quantitatively the evolution of halogen and sulphur compounds in the plume of Mt. Etna. Model predictions support the hypothesis of minor HCl chemical processing during plume transport, at least in cloud-free conditions. Larger variations in the modelled SO2/HCl ratios were predicted under cloudy conditions, due to heterogeneous chlorine cycling in the aerosol phase. The modelled evolution of the SO2/H2S ratios is found to be substantially dependent on whether or not the interactions of H2S with halogens are included in the model. In the former case, H2S is assumed to be oxidized in the atmosphere mainly by OH, which results in minor chemical loss for H2S during plume aging and produces a fair match between modelled and measured SO2/H2S ratios. In the latter case, fast oxidation of H2S by Cl leads to H2S chemical lifetimes in the early plume of a few seconds, and thus SO2 to H2S ratios that increase sharply during plume transport. This disagreement between modelled and observed plume compositions suggests that more in-detail kinetic investigations are required for a proper evaluation of H2S chemical processing in volcanic plumes

The tropospheric processing of acidic gases and hydrogen sulphide in volcanic gas plumes as inferred from field and model investigations

Improving the constraints on the atmospheric fate and depletion rates of acidic compounds persistently emitted by non-erupting (quiescent) volcanoes is important for quantitatively predicting the environmental impact of volcanic gas plumes. Here, we present new experimental data coupled with modelling studies to investigate the chemical processing of acidic volcanogenic species during tropospheric dispersion. Diffusive tube samplers were deployed at Mount Etna, a very active open-conduit basaltic volcano in eastern Sicily, and Vulcano Island, a closed-conduit quiescent volcano in the Aeolian Islands (northern Sicily). Sulphur dioxide (SO2), hydrogen sulphide (H2S), hydrogen chloride (HCl) and hydrogen fluoride (HF) concentrations in the volcanic plumes (typically several minutes to a few hours old) were repeatedly determined at distances from the summit vents ranging from 0.1 to 10 km, and under different environmental conditions. At both volcanoes, acidic gas concentrations were found to decrease exponentially with distance from the summit vents (e.g., SO2 decreases from 10 000 μg/m3 at 0.1 km from Etna’s vents down to 7 μg/m3 at 10 km distance), reflecting the atmospheric dilution of the plume within the acid gas-free background troposphere. Conversely, SO2/HCl, SO2/HF, and SO2/H2S ratios in the plume showed no systematic changes with plume aging, and fit source compositions within analytical error. Assuming that SO2 losses by reaction are small during short-range atmospheric transport within quiescent (ash-free) volcanic plumes, our observations suggest that, for these short transport distances, atmospheric reactions for H2S and halogens are also negligible. The one-dimensional model MISTRA was used to simulate quantitatively the evolution of halogen and sulphur compounds in the plume of Mt. Etna. Model predictions support the hypothesis of minor HCl chemical processing during plume transport, at least in cloud-free conditions. Larger variations in the modelled SO2/HCl ratios were predicted under cloudy conditions, due to heterogeneous chlorine cycling in the aerosol phase. The modelled evolution of the SO2/H2S ratios is found to be substantially dependent on whether or not the interactions of H2S with halogens are included in the model. In the former case, H2S is assumed to be oxidized in the atmosphere mainly by OH, which results in minor chemical loss for H2S during plume aging and produces a fair match between modelled and measured SO2/H2S ratios. In the latter case, fast oxidation of H2S by Cl leads to H2S chemical lifetimes in the early plume of a few seconds, and thus SO2 to H2S ratios that increase sharply during plume transport. This disagreement between modelled and observed plume compositions suggests that more in-detail kinetic investigations are required for a proper evaluation of H2S chemical processing in volcanic plumes

Kinetics of isothermal and non-isothermal precipitation in an Al-6at%Si alloy

A novel theory which describes the progress of a thermally activated reaction under isothermal and linear heating conditions is presented. It incorporates nucleation, growth and impingement and takes account of temperaturedependent solubility. The model generally fits very well to isothermal calorimetry and differential scanning calorimetry data on precipitation in an Al-6 at.% Si alloy. Analysis of the data shows that two processes occur in this precipitation reaction: growth of large Si particles and growth of pre-existing small nuclei. Determination of the sizes of Si precipitates by transmission electron microscopy indicates that interfacial energy contributions are small and have a negligible influence on solubilit

Growth in Stratospheric Chlorine from Short-Lived Chemicals not Controlled by the Montreal Protocol

We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS (ClyVSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl3), dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), trichloroethene (C2HCl3), and 1,2-dichloroethane (CH2ClCH2Cl), we infer a 2013 ClyVSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection of source gases dominates this supply, accounting for ∼83% of the total. The remainder comes from VSLS-derived organic products, phosgene (COCl2, 7%) and formyl chloride (CHClO, 2%), and also hydrogen chloride (HCl, 8%). Stratospheric ClyVSLS increased by ∼52% between 2005 and 2013, with a mean growth rate of 3.7 ppt Cl/yr. This increase is due to recent and ongoing growth in anthropogenic CH2Cl2 - the most abundant chlorinated VSLS not controlled by the Montreal Protocol. ©2015