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.
Key Points
Stratospheric Cl from short‐lived chemicals has increased significantly
Increasing Cl due to rapid growth in surface emissions of CH2Cl2
COCl2 and HCl from VSLS make a nonzero contribution to stratospheric Cl
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Volcanoes are very strong sources of sulphur, acids and other gases, as well as particles, that are of atmospheric relevance. Some gases only behave as passive tracers, others affect the formation, ...growth or chemical characteristics of aerosol particles and many lead to adverse effects on vegetation and human health when deposited in the vicinity of volcanoes. In this article the main effects of volcanic emissions on atmospheric chemistry are discussed, with a focus on sulphur and halogen compounds, and to a smaller extent on climate. We primarily focus on quiescent degassing but the main effects of explosive eruptions on the troposphere and stratosphere are covered as well. The key distinction between chemistry in magmatic and hydrothermal settings and the atmosphere is that the atmosphere is oxidising whereas the chemistry is typically reducing in the former cases due to very low oxygen concentrations. Rapid catalytic cycles involving radicals are a further characteristic of atmospheric chemistry. Most reaction cycles involve the photolysis of molecules as a key part of the reaction chains. Recent measurements of halogen radicals in volcanic plumes showed that volcanic plumes are chemically very active. We explain the formation mechanism of halogen oxides in plumes as well as their relevance for the atmosphere.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
The role of ice in the formation of chemically active halogens in the environment requires a full understanding because of its role in atmospheric chemistry, including controlling the regional ...atmospheric oxidizing capacity in specific situations. In particular, ice and snow are important for facilitating multiphase oxidative chemistry and as media upon which marine algae live. This paper reviews the nature of environmental ice substrates that participate in halogen chemistry, describes the reactions that occur on such substrates, presents the field evidence for ice-mediated halogen activation, summarizes our best understanding of ice-halogen activation mechanisms, and describes the current state of modeling these processes at different scales. Given the rapid pace of developments in the field, this paper largely addresses advances made in the past five years, with emphasis given to the polar boundary layer. The integrative nature of this field is highlighted in the presentation of work from the molecular to the regional scale, with a focus on understanding fundamental processes. This is essential for developing realistic parameterizations and descriptions of these processes for inclusion in larger scale models that are used to determine their regional and global impacts.
We present a comprehensive chemical mechanism for gas-phase iodine, to be used for modelling tropospheric chemistry. The mechanism has been compiled from evaluated data and individual literature ...studies, where available; a number of key processes have not been studied experimentally or theoretically and in these cases estimations have been made. The uncertainty associated with these assumptions is evaluated. We analyze the mechanism using a box-model under a variety of boundary layer scenarios – representative of environments where iodine species have been observed – to study the response of the chemical system to changes in the kinetic parameters of selected reactions. We focus in particular on key species such as IO, OIO, INO3 and I2Oy and the impact of iodine chemistry on ozone formation and HOx levels. The results indicate that the chemical system is most sensitive to reactions leading to comparatively stable iodine compounds, which should be a focus of future laboratory studies.
► Assembled gas-phase inorganic iodine chemical mechanism. ► Analyzed mechanism using box-model under different scenarios. ► Response of mechanism to changes in kinetic parameters of selected reactions. ► Mechanism most sensitive to reactions forming stable iodine species. ► Laboratory studies of some key reactions are urgently needed.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
We present model studies with the one-dimensional model MISTRA to investigate the potential role of frost flowers, recycling on snow, and open leads in the depletion of tropospheric ozone in the ...Arctic spring. In our model, we assumed frost flower aerosols to be the major source of bromine. We show that a major ozone depletion event can be satisfactorily reproduced only if the recycling on snow of deposited bromine into gas phase bromine is assumed. In the model, this cycling is more efficient than the bromine explosion process and maintains sufficiently high levels of bromine to deplete ozone down to few nmol mol−1 within four days. We assessed the influence of different surface combinations (open lead/frost flowers) on the chemistry in the model. Results showed noticeable modifications affecting the composition of aerosols and the deposition velocities. A model run with a series of coupled frost flower fields and open leads, separated by large areas of snow, showed results comparable with field observations. In addition, we studied the effects of modified temperature of either the frost flower field or the ambient airmass. A warmer frost flower field increases the relative humidity and the aerosol deposition rate. The deposition/re-emission process gains in importance, inducing more reactive bromine in the gas phase, and a stronger ozone depletion. A decrease of 1K in airmass temperature shows in our model that the aerosol uptake capacities of all gas phase species substantially increases, leading to enhanced uptake of acids from the gas phase. Consequently, the so-called bromine explosion accelerated and O3 mixing ratios decreased. In our model representation, variations in wind speed affected the aerosol source function and influenced the amount of bromine in the atmosphere and thus the ozone depletion strength. Recent studies have suggested the important role of the precipitation of calcium carbonate (CaCO3) out of the brine layer for the possible acidification of the liquid phase by acid uptake. Our investigation showed that this precipitation is a crucial process for the timing of the bromine explosion in aerosols. Nevertheless, model runs with either 50% precipitation or complete precipitation displayed a relatively weak difference in ozone mixing ratios after four simulated days. By considering conditions typical for "Arctic Haze" pollution events at the start of the run we obtained a low pH in frost flower aerosols due to a greater mixing ratio of SO2, and a strong recycling efficiency via large aerosol number concentration. The aerosol acidification during a haze event most likely intensifies the ozone depletion strength and occurrence. The comparison between our modeled deposition on snow and sampled snow at Barrow (Alaska) shows that approximately 75% of deposited bromine may be re-emitted into the gas phase as Br2/BrCl. Among several non-halogen fluxes from the snow, model simulations showed that only HONO affects the chemistry. Finally, we investigated the release of Br2 potentially produced by heterogeneous reactions directly on frost flowers. In this case, we obtained unrealistic results of aerosol compositions and deposition rates on snow compared to observations in the Arctic.
It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in ...snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.
HOCl and Cl2 observations in marine air Lawler, M J; Sander, R; Carpenter, L J ...
Atmospheric chemistry and physics,
08/2011, Volume:
11, Issue:
15
Journal Article
Peer reviewed
Open access
Cl atoms in the marine atmosphere may significantly impact the lifetimes of methane and other hydrocarbons. However, the existing estimates of Cl atom levels in marine air are based on indirect ...evidence. Here we present measurements of the Cl precursors HOCl and Cl2 in the marine boundary layer during June of 2009 at the Cape Verde Atmospheric Observatory in the eastern tropical Atlantic. These are the first measurements of tropospheric HOCl. HOCl and Cl2 levels were low in air with open ocean back trajectories, with maximum levels always below 60 and 10 ppt (pmol/mol), respectively. In air with trajectories originating over Europe, HOCl and Cl2 levels were higher, with HOCl maxima exceeding 100 ppt each day and Cl2 reaching up to 35 ppt. The increased Cl cycling associated with long distance pollutant transport over the oceans likely impacts a wide geographic area and represents a mechanism by which human activities have increased the reactivity of the marine atmosphere. Data-constrained model simulations indicate that Cl atoms account for approximately 15 % of methane destruction on days when aged polluted air arrives at the site. A photochemical model does not adequately simulate the observed abundances of HOCl and Cl2 , raising the possibility of an unknown HOCl source.
Current understanding of the behaviour of sea breezes in the offshore environment is limited but rapidly requires improvement due, not least, to the expansion of the offshore wind energy industry. ...Here we report on contrasting characteristics of three sea‐breeze types on five coastlines around the southern North Sea from an 11 year model‐simulated climatology. We present and test an identification method which distinguishes sea‐breeze types which can, in principle, be adapted for other coastlines around the world. The coherence of the composite results for each type demonstrates that the method is very effective in resolving and distinguishing characteristics and features. Some features, such as jets and calm zones, are shown to influence offshore wind farm development areas, including the sites of the proposed wind farms up to 200 km offshore. A large variability in sea‐breeze frequency between neighbouring coastlines of up to a factor of 3 is revealed. Additionally, there is a strong association between sea‐breeze type on one coastline and that which may form coincidentally on another nearby. This association can be as high as 86% between, for example, the North Norfolk and East Norfolk coasts. We show, through associations between sea‐breeze events on coastlines with contrasting orientations, that each coastline can be important for influencing the wind climate of another. Furthermore, we highlight that each sea‐breeze type needs separate consideration in wind power resource assessment and that future larger turbines will be more sensitive to sea‐breeze impacts.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The behaviour and characteristics of the marine component of sea breeze cells have received little attention relative to their onshore counterparts. Yet there is a growing interest and dependence on ...the offshore wind climate from, for example, a wind energy perspective. Using idealized model experiments, we investigate the sea breeze circulation at scales which approximate to those of the southern North Sea, a region of major ongoing offshore wind farm development. We also contrast the scales and characteristics of the pure and the little known corkscrew and backdoor sea breeze types, where the type is pre-defined by the orientation of the synoptic scale flow relative to the shoreline. We find, crucially, that pure sea breezes, in contrast to corkscrew and backdoor types, can lead to substantial wind speed reductions offshore and that the addition of a second eastern coastline emphasises this effect through generation of offshore "calm zones". The offshore extent of all sea breeze types is found to be sensitive to both the influence of Coriolis acceleration and to the boundary layer scheme selected. These extents range, for example for a pure sea breeze produced in a 2 m s super(-1) offshore gradient wind, from 0 km to 21 km between the Mellor-Yamada-Nakanishi-Niino and the Yonsei State University schemes respectively. The corkscrew type restricts the development of a backdoor sea breeze on the opposite coast and is also capable of traversing a 100 km offshore domain even under high along-shore gradient wind speed (>15 m s super(-1)) conditions. Realistic variations in sea surface skin temperature and initializing vertical thermodynamic profile do not significantly alter the resulting circulation, though the strengths of the simulated sea breezes are modulated if the effective land-sea thermal contrast is altered. We highlight how sea breeze impacts on circulation need to be considered in order to improve the accuracy of both assessments of the offshore wind energy climate and forecasts of wind energy output.
We studied the oxidation of dimethylsulfide (DMS) in the marine boundary layer (MBL) with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is ...still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA) with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV)* (=SO2,aq+HSO3-+SO32-) with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA) to non-sea salt sulfate (nss-SO42-) production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.
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