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

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

Iodine's impact on tropospheric oxidants : A global model study in GEOS-Chem

We present a global simulation of tropospheric iodine chemistry within the GEOS-Chem chemical transport model. This includes organic and inorganic iodine sources, standard gas-phase iodine chemistry, and simplified higher iodine oxide (I2OX, X=2, 3, 4) chemistry, photolysis, deposition, and parametrized heterogeneous reactions. In comparisons with recent iodine oxide (IO) observations, the simulation shows an average bias of ~+90% with available surface observations in the marine boundary layer (outside of polar regions), and of ~+73¯% within the free troposphere (350 hPa < p < 900 hPa)  over the eastern Pacific. Iodine emissions (3.8 Tg yr-1) are overwhelmingly dominated by the inorganic ocean source, with 76% of this emission from hypoiodous acid (HOI). HOI is also found to be the dominant iodine species in terms of global tropospheric IY burden (contributing up to 70%). The iodine chemistry leads to a significant global tropospheric O3 burden decrease (9.0%) compared to standard GEOS-Chem (v9-2). The iodine-driven OXloss rate1 (748 Tg OX yr-1) is due to photolysis of HOI (78%), photolysis of OIO (21%), and reaction between IO and BrO (1%). Increases in global mean OH concentrations (1.8%) by increased conversion of hydroperoxy radicals exceeds the decrease in OH primary production from the reduced O3 concentration. We perform sensitivity studies on a range of parameters and conclude that the simulation is sensitive to choices in parametrization of heterogeneous uptake, ocean surface iodide, and I2OX (X=2, 3, 4) photolysis. The new iodine chemistry combines with previously implemented bromine chemistry to yield a total bromine- and iodine-driven tropospheric O3 burden decrease of 14.4% compared to a simulation without iodine and bromine chemistry in the model, and a small increase in OH (1.8%). This is a significant impact and so halogen chemistry needs to be considered in both climate and air quality models. Here Ox is defined as O3 + NO2 + 2NO3 + PAN + PMN+PPN + HNO4 + 3N2O5 + HNO3 + BrO + HOBr + BrNO2+2BrNO3 + MPN + IO + HOI + INO2 + 2INO3 + 2OIO+2I2O2 + 3I2O3 + 4I2O4, where PAN=peroxyacetyl nitrate, PPN=peroxypropionyl nitrate, MPN=methyl peroxy nitrate, and MPN=peroxymethacryloyl nitrate

Comparative tracing experiments to investigate epikarst structural and compositional heterogeneity

omparative tracer testing may be used to evaluate the vulnerability of groundwater to specific contaminants by comparing reactive tracer response to that of a simultaneously injected non-reactive “conservative” substance. Conversely, knowledge of tracer reaction with specific materials permits information about subsurface heterogeneity to be inferred. A series of tests completed in the vadose zone overlying a limestone aquifer employed a cocktail of particles along with reactive and non-reactive solute tracers to investigate transport rates between the ground surface and monitoring points approximately 10 m below ground. Short pulse tests revealed both solutes and particulate contaminants could travel at rates of over 10 m/h. Comparison of particle (microorganisms) and non-reactive solute tracer breakthrough revealed that particle tracers experience pore exclusion resulting in higher peak relative concentrations which arrive earlier than those of the solute. Prolonged tracer injection during subsequent experiments confirmed the response observed and illustrated that over 40 % of flow paths between injection and monitoring points were inaccessible to particles, but could allow solutes to pass through them. Similarly, the difference in response between various reactive tracers demonstrated tracers reached monitoring points via multiple flow paths and suggests geochemical heterogeneity plays an important role in influencing tracer behaviour. The results of this investigation highlight the complexity of water flow through the epikarst and the vulnerability of groundwater in karst aquifers to contamination when soil cover is thin to absent

Comparative tracing experiments to investigate epikarst structural and compositional heterogeneity

omparative tracer testing may be used to evaluate the vulnerability of groundwater to specific contaminants by comparing reactive tracer response to that of a simultaneously injected non-reactive “conservative” substance. Conversely, knowledge of tracer reaction with specific materials permits information about subsurface heterogeneity to be inferred. A series of tests completed in the vadose zone overlying a limestone aquifer employed a cocktail of particles along with reactive and non-reactive solute tracers to investigate transport rates between the ground surface and monitoring points approximately 10 m below ground. Short pulse tests revealed both solutes and particulate contaminants could travel at rates of over 10 m/h. Comparison of particle (microorganisms) and non-reactive solute tracer breakthrough revealed that particle tracers experience pore exclusion resulting in higher peak relative concentrations which arrive earlier than those of the solute. Prolonged tracer injection during subsequent experiments confirmed the response observed and illustrated that over 40 % of flow paths between injection and monitoring points were inaccessible to particles, but could allow solutes to pass through them. Similarly, the difference in response between various reactive tracers demonstrated tracers reached monitoring points via multiple flow paths and suggests geochemical heterogeneity plays an important role in influencing tracer behaviour. The results of this investigation highlight the complexity of water flow through the epikarst and the vulnerability of groundwater in karst aquifers to contamination when soil cover is thin to absent

Characterisation of virus transport and attenuation in epikarst using short pulse and prolonged injection multi-tracer testing

Attenuation processes controlling virus fate and transport in the vadose zone of karstified systems can strongly influence groundwater quality. This research compares the breakthrough of two bacteriophage tracers (H40/1 and T7), with contrasting properties, at subsurface monitoring points following application onto an overlying composite sequence of thin organic soil and weathered limestone (epikarst). Short pulse multi-tracer test results revealed that T7 (Source concentration, Co = 1.8 × 106 pfu/mL) and H40/1 (Co = 5.9 × 106 pfu/mL) could reach sampling points 10 m below ground less than 30 min after tracer application. Contrasting deposition rates, determined from simulated tracer responses, reflected the potential of the ground to differentially attenuate viruses. Prolonged application of both T7 (Co = 2.3 × 104 pfu/mL) and H40/1 (Co = 1.3 × 105 pfu/mL) over a five hour period during a subsequent test, in which ionic strength levels observed at monitoring points rose consistently, corresponded to a rapid rise in T7 levels, followed by a gradual decline before the end of tracer injection; this reflected reaction-limited deposition in the system. T7\u27s response contrasted with that of H40/1, whose concentration remained constant over a three hour period before declining dramatically prior to the end of tracer injection. Subsequent application of lower ionic strength tracer-free flush water generated a rapid rise in H40/1 levels and a more gradual release of T7. Results highlight the benefits of employing prolonged injection multi-tracer tests for identifying processes not apparent from conventional short pulse tests. Study findings demonstrate that despite rapid transport rates, the epikarst is capable of physicochemical filtration of viruses and their remobilization, depending on virus type and hydrochemical conditions

BrO measurements over the Eastern North-Atlantic

The aim of the work presented here was to detect BrO in the marine boundary layer over the Eastern North-Atlantic by Multi AXis-Differential Optical Absorption Spectroscopy (MAX-DOAS) of scattered sunlight. With this technique, information about the concentration and the vertical profile of trace gases in the atmosphere can be gained. BrO can be formed in the marine atmosphere by degradation of biogenic organohalogens or by oxidation of bromide in sea salt aerosol. BrO influences the chemistry in marine air in many ways, e.g. since it catalytically destroys ozone, changes the NO&lt;sub&gt;2&lt;/sub&gt;/NO-ratio as well as the OH/HO&lt;sub&gt;2&lt;/sub&gt;-ratio and oxidises DMS. However, the abundance and the significance of BrO in the marine atmosphere is not yet fully understood. &lt;br&gt;&lt;br&gt; We report on data collected during a ship cruise, which took place along the West African Coast in February 2007, within the framework of the Surface Ocean PRocesses in the ANthropocene project (SOPRAN). Tropospheric BrO could be detected during this cruise at peak mixing ratios of (10.2&amp;plusmn;3.7) ppt at an assumed layer height of 1 km on 18 February 2007. Furthermore, it was found that the mean BrO concentrations increased when cruising close to the African Coast suggesting that at least part of the BrO might have originated from there

KARSYS: a pragmatic approach to karst hydrogeological system conceptualisation. Assessment of groundwater reserves and resources in Switzerland

An approach is presented for the hydrogeological conceptualisation of karst systems. The KARSYS approach helps hydrogeologists working in karst regions to address in a pragmatic and efficient way the three following questions. (1) Where does the water of a karst spring come from? (2) Through which underground routes does it flow? (3) What are the groundwater reserves and where are they? It is based on a three dimensional model of the carbonate aquifer geometry (3D geological model) coupled to a series of simple fundamental principles of karst hydraulics. This provides, within a limited effort, a consistent hydrogeological conceptual model of karst flow systems within any investigation area. The level of detail can be adjusted according to the targeted degree of confidence. Two examples of its application are presented; the approach was first applied with a low level of detail on a national scale in order to assess the groundwater reserves in karst aquifers in Switzerland, suggesting a groundwater volume of 120 km3. On a regional scale, it was applied with a higher level of detail to some selected karst systems in order to assess their hydropower potential. The KARSYS approach may provide very useful information for water management improvement in karst regions (vulnerability assessment, impact assessment, water supply, flood hazards, landslides, etc.). It leads, in a very cost-effective manner, to a new and highly didactic representation of karst systems as well as to new concepts concerning the delineation of catchment areas in karst regions