Quantification of the depletion of ozone in the plume of Mount Etna

Volcanoes are an important source of inorganic halogen species into the atmosphere. Chemical processing of these species generates oxidised, highly reactive, halogen species which catalyse considerable O₃ destruction within volcanic plumes. A campaign of ground-based in situ O₃, SO₂ and meteorology measurements was undertaken at the summit of Mount Etna volcano in July/August 2012. At the same time, spectroscopic measurements were made of BrO and SO₂ columns in the plume downwind. <br><br> Depletions of ozone were seen at all in-plume measurement locations, with average O₃ depletions ranging from 11–35 nmol mol⁻¹ (15–45%). Atmospheric processing times of the plume were estimated to be between 1 and 4 min. A 1-D numerical model of early plume evolution was also used. It was found that in the early plume O₃ was destroyed at an approximately constant rate relative to an inert plume tracer. This is ascribed to reactive halogen chemistry, and the data suggests the majority of the reactive halogen that destroys O₃ in the early plume is generated within the crater, including a substantial proportion generated in a high-temperature "effective source region" immediately after emission. The model could approximately reproduce the main measured features of the ozone chemistry. Model results show a strong dependence of the near-vent bromine chemistry on the presence or absence of volcanic NO_x emissions and suggest that near-vent ozone measurements can be used as a qualitative indicator of NO_x emission

Chemical munition decision methods for the Vector-in-Commander Combat Simulation

This thesis develops decision logic for the employment of chemical artillery munitions for use in the U .S. Army's Vector-in-Commander (VIC) Combat Simulation. There are three parts to this thesis. The first part uses VIC 's "current state" decision methodology to produce an immediately usable improvement to VIC. This part can be used to write the code necessary for incorporation into VIC . The second part uses the "future state" Generalized Value System (GVS) decision methodology . The third part is a stand alone document which identifies, explains, and contrasts the theoretical "underpinnings" of the VIC decision methodology and the GVS decision methodology.http://archive.org/details/chemicalmunition00glasCaptain, United States ArmyApproved for public release; distribution is unlimited.Approved for public release; distribution is unlimited

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 &mu;g/m³at 0.1 km from Etna&apos;s vents down to ~7 &mu;g/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

Quantification of the depletion of ozone in the plume of Mount Etna

Volcanoes are an important source of inorganic halogen species into the atmosphere. Chemical processing of these species generates oxidised, highly reactive, halogen species which catalyse considerable O3 destruction within volcanic plumes. A campaign of ground-based in situ O3, SO2 and meteorology measurements was undertaken at the summit of Mount Etna volcano in July/August 2012. At the same time, spectroscopic measurements were made of BrO and SO2 columns in the plume downwind. Depletions of ozone were seen at all in-plume measurement locations, with average O3 depletions ranging from 11–35 nmol mol 1 (15–45 %). Atmospheric processing times of the plume were estimated to be between 1 and 4 min. A 1-D numerical model of early plume evolution was also used. It was found that in the early plume O3 was destroyed at an approximately constant rate relative to an inert plume tracer. This is ascribed to reactive halogen chemistry, and the data suggests the majority of the reactive halogen that destroys O3 in the early plume is generated within the crater, including a substantial proportion generated in a high-temperature “effective source region” immediately after emission. The model could approximately reproduce the main measured features of the ozone chemistry. Model results show a strong dependence of the near-vent bromine chemistry on the presence or absence of volcanic NOx emissions and suggest that near-vent ozone measurements can be used as a qualitative indicator of NOx emission

Investigation of chlorine radical chemistry in the Eyjafjallajkull volcanic plume using observed depletions in non-methane hydrocarbons

As part of the effort to understand volcanic plume composition and chemistry during the eruption of the Icelandic volcano Eyjafjallajkull, the CARIBIC atmospheric observatory was deployed for three special science flights aboard a Lufthansa passenger aircraft. Measurements made during these flights included the collection of whole air samples, which were analyzed for non-methane hydrocarbons (NMHCs). Hydrocarbon concentrations in plume samples were found to be reduced to levels below background, with relative depletions characteristic of reaction with chlorine radicals (Cl). Recent observations of halogen oxides in volcanic plumes provide evidence for halogen radical chemistry, but quantitative data for free halogen radical concentrations in volcanic plumes were absent. Here we present the first observation-based calculations of Cl radical concentrations in volcanic plumes, estimated from observed NMHC depletions. Inferred Cl concentrations were between 1.3 × 10 and 6.6 × 10 Cl cm. The relationship between NMHC variability and local lifetimes was used to investigate the ratio between OH and Cl within the plume, with [OH]/[Cl] estimated to be ∼37. Copyright 2011 by the American Geophysical Union

Importance of reactive halogens in the tropical marine atmosphere: A regional modelling study using WRF-Chem

This study investigates the impact of halogens on atmospheric chemistry in the tropical troposphere and explores the sensitivity of this to uncertainties in the fluxes of halogens to the atmosphere and the chemical processing. To do this the regional chemistry transport model WRF-Chem has been extended, for the first time, to include halogen chemistry (bromine, chlorine and iodine chemistry), including heterogeneous recycling reactions involving sea-salt aerosol and other particles, reactions of Br with volatile organic compounds (VOCs), along with oceanic emissions of halocarbons, VOCs and inorganic iodine. The study focuses on the tropical East Pacific using field observations from the TORERO campaign (January-February 2012) to evaluate the model performance. Including all the new processes, the model does a reasonable job reproducing the observed mixing ratios of BrO and IO, albeit with some discrepancies, some of which can be attributed to difficulties in the model’s ability to reproduce the observed halocarbons. This is somewhat expected given the large uncertainties in the air-sea fluxes of the halocarbons in a region where there are few observations of seawater concentrations. We see a considerable impact on the Bry partitioning when heterogeneous chemistry is included, with a greater proportion of the Bry in active forms such as BrO, HOBr and dihalogens. Including debromination of sea-salt increases BrO slightly throughout the free troposphere, but in the tropical marine boundary layer, where the sea-salt particles are plentiful and relatively acidic, debromination leads to overestimation of the observed BrO. However, it should be noted that the modelled BrO was extremely sensitive to the inclusion of reactions between Br and the VOCs, which convert Br to HBr, a far less reactive form of Bry. Excluding these reactions leads to modelled BrO mixing ratios greater than observed. The reactions between Br and aldehydes were found to be particularly important, despite the model underestimating the amount of aldehydes observed in the atmosphere. There are only small changes to Iy partitioning and IO when the heterogeneous reactions, primarly on sea-salt, are included. Our model results show that the tropospheric Ox loss due to halogens is 31%. This loss is mostly due to I (16%) and Br (14%) and it is in good agreement with other estimates from state-of-the-art atmospheric chemistry models

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

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

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