Short-lived Halocarbons Research Articles

Natural short-lived halogens exert an indirect cooling effect on climate

Observational evidence shows the ubiquitous presence of ocean-emitted short-lived halogens in the global atmosphere1–3. Natural emissions of these chemical compounds have been anthropogenically amplified since pre-industrial times4–6, while, in addition, anthropogenic short-lived halocarbons are currently being emitted to the atmosphere7,8. Despite their widespread distribution in the atmosphere, the combined impact of these species on Earth’s radiative balance remains unknown. Here we show that short-lived halogens exert a substantial indirect cooling effect at present (−0.13 ± 0.03 watts per square metre) that arises from halogen-mediated radiative perturbations of ozone (−0.24 ± 0.02 watts per square metre), compensated by those from methane (+0.09 ± 0.01 watts per square metre), aerosols (+0.03 ± 0.01 watts per square metre) and stratospheric water vapour (+0.011 ± 0.001 watts per square metre). Importantly, this substantial cooling effect has increased since 1750 by −0.05 ± 0.03 watts per square metre (61 per cent), driven by the anthropogenic amplification of natural halogen emissions, and is projected to change further (18–31 per cent by 2100) depending on climate warming projections and socioeconomic development. We conclude that the indirect radiative effect due to short-lived halogens should now be incorporated into climate models to provide a more realistic natural baseline of Earth’s climate system.

Spatiotemporal distributions and oceanic emissions of short-lived halocarbons in the East China Sea

Coastal waters are important sources of volatile halocarbons, which are important in atmospheric chemistry. Here, in May (spring) and October (autumn) 2020, we studied the surface, bottom, and sediment-pore seawater concentrations, atmospheric mixing ratios, and sea-to-air fluxes of the three primary short-lived atmospheric halocarbons (CH3I, CH2Br2, and CHBr3) in the East China Sea (ECS). The highest concentrations of the three short-lived halocarbons occurred in coastal waters, such as the Changjiang estuary and Zhejiang coastal waters, reflecting the influence of excessive anthropogenic inputs on the distributions of these gases. Interestingly, the aqueous levels of these gases seemed to be lower compared to previous measurements in this oceanic region, probably due to reduced contributions from local anthropogenic emission sources. The concentrations of CH3I, CH2Br2, and CHBr3 in pore water were significantly higher than those in bottom water, suggesting that sediment could be a source of these short-lived halocarbons. Additionally, the atmospheric mixing ratios of these gases occasionally increased in coastal areas. An air-mass back trajectory analysis showed this was due to continental anthropogenic sources and emissions from enriched waters. The atmospheric mixing ratios of these halocarbons exhibited significant seasonal variability, with significant correlations among atmospheric CH3I, CH2Br2, and CHBr3 in spring, but not in autumn. The sea-to-air fluxes of CH3I, CH2Br2, and CHBr3 indicated that the ECS is a source of these gases. Seasonal differences in CH3I and CH2Br2 fluxes were driven by changes in wind speed and sea surface temperature, while CHBr3 flux changes were associated with changes in its surface seawater concentration.

An indirect-calibration method for non-target quantification of trace gases applied to a time series of fourth-generation synthetic halocarbons at the Taunus Observatory (Germany)

Abstract. Production and use of many synthetic halogenated trace gases are regulated internationally due to their contribution to stratospheric ozone depletion or climate change. In many applications they have been replaced by shorter-lived compounds, which have become measurable in the atmosphere as emissions increased. Non-target monitoring of trace gases rather than targeted measurements of well-known substances is needed to keep up with such changes in the atmospheric composition. We regularly deploy gas chromatography (GC) coupled to time-of-flight mass spectrometry (TOF-MS) for analysis of flask air samples and in situ measurements at the Taunus Observatory, a site in central Germany. TOF-MS acquires data over a continuous mass range that enables a retrospective analysis of the dataset, which can be considered a type of digital air archive. This archive can be used if new substances come into use and their mass spectrometric fingerprint is identified. However, quantifying new replacement halocarbons can be challenging, as mole fractions are generally low, requiring high measurement precision and low detection limits. In addition, calibration can be demanding, as calibration gases may not contain sufficiently high amounts of newly measured substances or the amounts in the calibration gas may have not been quantified. This paper presents an indirect data evaluation approach for TOF-MS data, where the calibration is linked to another compound which could be quantified in the calibration gas. We also present an approach to evaluate the quality of the indirect calibration method, select periods of stable instrument performance and determine well suited reference compounds. The method is applied to three short-lived synthetic halocarbons: HFO-1234yf, HFO-1234ze(E), and HCFO-1233zd(E). They represent replacements for longer-lived hydrofluorocarbons (HFCs) and exhibit increasing mole fractions in the atmosphere. The indirectly calibrated results are compared to directly calibrated measurements using data from TOF-MS canister sample analysis and TOF-MS in situ measurements, which are available for some periods of our dataset. The application of the indirect calibration method on several test cases can result in uncertainties of around 6 % to 11 %. For hydro(chloro-)fluoroolefines (denoted H(C)FOs), uncertainties up to 23 % are achieved. The indirectly calculated mole fractions of the investigated H(C)FOs at Taunus Observatory range between measured mole fractions at urban Dübendorf and Jungfraujoch stations in Switzerland.

The emission of volatile halocarbons by seaweeds and their response towards environmental changes

Volatile halocarbons can deplete the protective stratospheric ozone layer contributing to global climate change and may even affect local climate through aerosol production. These compounds are produced through anthropogenic and biogenic processes. Biogenic halocarbons may be produced as defence compounds, anti-oxidants or by-products of metabolic processes. These compounds include very short-lived halocarbons (VSLH), e.g. bromoform (CHBr3), dibromomethane (CH2Br2), methyl iodide (CH3I), diiodomethane (CH2I2). Efforts to quantify the biogenic sources of these compounds, especially those of marine origin, e.g. seaweeds, phytoplankton and seagrass meadows, are often complicated by inherent biological variability as well as spatial and temporal changes in emissions. The contribution of the coastal region and the oceans to the stratospheric load of halocarbons has been widely debated. This highlights the need to understand the factors affecting the release of these compounds from marine sources for which data for modelling purposes are generally lacking. Seaweeds are important sources of biogenic halocarbons subjected to changing environmental conditions. Huge uncertainties in the prediction of current and future global halocarbon pool exist due to the lack of spatial and temporal data input from coastal and oceanic sources. Therefore, investigating the effect of changing environmental conditions on the emission of VSLH by the seaweeds could help towards better estimations of halocarbon emissions. This is especially important in light of global changes in both climate and the environment, the expansion of seaweed cultivation industry and the interactions between halocarbon emission and their environment. In this paper, we review current knowledge of seaweed halocarbon emissions, how environmental factors affect these emissions and identify gaps in understanding. Our aim is to direct much needed research to improve understanding of the contribution of marine biogenic sources of halocarbons and their impact on the environment.

Transport of short-lived halocarbons to the stratosphere over the Pacific Ocean

Abstract. The effectiveness of transport of short-lived halocarbons to the upper troposphere and lower stratosphere remains an important uncertainty in quantifying the supply of ozone-depleting substances to the stratosphere. In early 2014, a major field campaign in Guam in the western Pacific, involving UK and US research aircraft, sampled the tropical troposphere and lower stratosphere. The resulting measurements of CH3I, CHBr3 and CH2Br2 are compared here with calculations from a Lagrangian model. This methodology benefits from an updated convection scheme that improves simulation of the effect of deep convective motions on particle distribution within the tropical troposphere. We find that the observed CH3I, CHBr3 and CH2Br2 mixing ratios in the tropical tropopause layer (TTL) are consistent with those in the boundary layer when the new convection scheme is used to account for convective transport. More specifically, comparisons between modelled estimates and observations of short-lived CH3I indicate that the updated convection scheme is realistic up to the lower TTL but is less good at reproducing the small number of extreme convective events in the upper TTL. This study consolidates our understanding of the transport of short-lived halocarbons to the upper troposphere and lower stratosphere by using improved model calculations to confirm consistency between observations in the boundary layer, observations in the TTL and atmospheric transport processes. Our results support recent estimates of the contribution of short-lived bromocarbons to the stratospheric bromine budget.

Novel approaches to improve estimates of short-lived halocarbon emissions during summer from the Southern Ocean using airborne observations

Abstract. Fluxes of halogenated volatile organic compounds (VOCs) over the Southern Ocean remain poorly understood, and few atmospheric measurements exist to constrain modeled emissions of these compounds. We present observations of CHBr3, CH2Br2, CH3I, CHClBr2, CHBrCl2, and CH3Br during the O2∕N2 Ratio and CO2 Airborne Southern Ocean (ORCAS) study and the second Atmospheric Tomography mission (ATom-2) in January and February of 2016 and 2017. Good model–measurement correlations were obtained between these observations and simulations from the Community Earth System Model (CESM) atmospheric component with chemistry (CAM-Chem) for CHBr3, CH2Br2, CH3I, and CHClBr2 but all showed significant differences in model : measurement ratios. The model : measurement comparison for CH3Br was satisfactory and for CHBrCl2 the low levels present precluded us from making a complete assessment. Thereafter, we demonstrate two novel approaches to estimate halogenated VOC fluxes; the first approach takes advantage of the robust relationships that were found between airborne observations of O2 and CHBr3, CH2Br2, and CHClBr2. We use these linear regressions with O2 and modeled O2 distributions to infer a biological flux of halogenated VOCs. The second approach uses the Stochastic Time-Inverted Lagrangian Transport (STILT) particle dispersion model to explore the relationships between observed mixing ratios and the product of the upstream surface influence of sea ice, chl a, absorption due to detritus, and downward shortwave radiation at the surface, which in turn relate to various regional hypothesized sources of halogenated VOCs such as marine phytoplankton, phytoplankton in sea-ice brines, and decomposing organic matter in surface seawater. These relationships can help evaluate the likelihood of particular halogenated VOC sources and in the case of statistically significant correlations, such as was found for CH3I, may be used to derive an estimated flux field. Our results are consistent with a biogenic regional source of CHBr3 and both nonbiological and biological sources of CH3I over these regions.

How marine emissions of bromoform impact the remote atmosphere

Abstract. It is an open question how localized elevated emissions of bromoform (CHBr3) and other very short-lived halocarbons (VSLHs), found in coastal and upwelling regions, and low background emissions, typically found over the open ocean, impact the atmospheric VSLH distribution. In this study, we use the Lagrangian dispersion model FLEXPART to simulate atmospheric CHBr3 resulting from assumed uniform background emissions, and from elevated emissions consistent with those derived during three tropical cruise campaigns. The simulations demonstrate that the atmospheric CHBr3 distributions in the uniform background emissions scenario are highly variable with high mixing ratios appearing in regions of convergence or low wind speed. This relation holds on regional and global scales. The impact of localized elevated emissions on the atmospheric CHBr3 distribution varies significantly from campaign to campaign. The estimated impact depends on the strength of the emissions and the meteorological conditions. In the open waters of the western Pacific and Indian oceans, localized elevated emissions only slightly increase the background concentrations of atmospheric CHBr3, even when 1∘ wide source regions along the cruise tracks are assumed. Near the coast, elevated emissions, including hot spots up to 100 times larger than the uniform background emissions, can be strong enough to be distinguished from the atmospheric background. However, it is not necessarily the highest hot spot emission that produces the largest enhancement, since the tug-of-war between fast advective transport and local accumulation at the time of emission is also important. Our results demonstrate that transport variations in the atmosphere itself are sufficient to produce highly variable VSLH distributions, and elevated VSLHs in the atmosphere do not always reflect a strong localized source. Localized elevated emissions can be obliterated by the highly variable atmospheric background, even if they are orders of magnitude larger than the average open ocean emissions.

Volatile halocarbon measurements in the marine boundary layer at Cape Point, South Africa

Volatile organic halocarbons play a significant role in the biogeochemical cycling of halogens in the atmosphere. High frequency, in situ measurements of methyl iodide (CH3I), bromoform (CHBr3), dibromomethane (CH2Br2) and methyl bromide (CH3Br) were measured in the marine boundary layer at Cape Point, South Africa by an automated Absorption Desorption System-Gas Chromatography-Mass Spectrometer (ADS-GC-MS) between January and November 2017. These are the first multi-halocarbon measurements recorded at Cape Point and represent the longest time series to date. Baseline wind conditions were established using both wind direction and radon (222Rn) concentration as markers of clean air. The baseline mixing ratios observed were 0.61 ± 0.29, 2.02 ± 0.89, 1.08 ± 0.17 and 6.09 ± 0.50 ppt, for CH3I, CHBr3, CH2Br2, and CH3Br, respectively. A statistically significant difference in short-lived halocarbon occurrence was established between anthropogenically affected and clean marine air masses for CH3Br at the Cape Point site. The CHBr3 and CH2Br2 mixing ratios were not statistically different (p > 0.05) when comparing the anthropogenically affected and clean marine air masses. The mixing ratios of CH3I suggested a strong seasonal variation with higher production in austral Summer-Autumn months than in the austral Winter-Spring months. A general chemical decay line was calculated for baseline CH2Br2 and CHBr3 measurements at Cape Point. An analysis of the ln([CH2Br2]/[CHBr3]):ln([CHBr3]) ratio for the Cape Point dataset exhibited a slight deflection to the right of the general chemical decay line, suggesting the influence of greater [CHBr3]:[CH2Br2] source ratios rather than their dilution.

Effect of irradiance on the emission of short-lived halocarbons from three common tropical marine microalgae.

Marine algae have been reported as important sources of biogenic volatile halocarbons that are emitted into the atmosphere. These compounds are linked to destruction of the ozone layer, thus contributing to climate change. There may be mutual interactions between the halocarbon emission and the environment. In this study, the effect of irradiance on the emission of halocarbons from selected microalgae was investigated. Using controlled laboratory experiments, three tropical marine microalgae cultures, Synechococcus sp. UMACC 371 (cyanophyte), Parachlorella sp. UMACC 245 (chlorophyte) and Amphora sp. UMACC 370 (diatom) were exposed to irradiance of 0, 40 and 120 µmol photons m−2s−1. Stress in the microalgal cultures was indicated by the photosynthetic performance (Fv/Fm, maximum quantum yield). An increase in halocarbon emissions was observed at 120 µmol photons m−2s−1, together with a decrease in Fv/Fm. This was most evident in the release of CH3I by Amphora sp. Synechococcus sp. was observed to be the most affected by irradiance as shown by the increase in emissions of most halocarbons except for CHBr3 and CHBr2Cl. High positive correlation between Fv/Fm and halocarbon emission rates was observed in Synechococcus sp. for CH2Br2. No clear trends in correlation could be observed for the other halocarbons in the other two microalgal species. This suggests that other mechanisms like mitochondria respiration may contribute to halocarbon production, in addition to photosynthetic performance.

A quantitative assessment of distributions and sources of tropospheric halocarbons measured in Singapore

This work reports the first ground-based atmospheric measurements of 26 halocarbons in Singapore, an urban-industrial city-state in Southeast (SE) Asia. A total of 166 whole air canister samples collected during two intensive 7 Southeast Asian Studies (7SEAS) campaigns (August–October 2011 and 2012) were analyzed for C1-C2 halocarbons using gas chromatography-electron capture/mass spectrometric detection. The halocarbon dataset was supplemented with measurements of selected non-methane hydrocarbons (NMHCs), C1-C5 alkyl nitrates, sulfur gases and carbon monoxide to better understand sources and atmospheric processes. The median observed atmospheric mixing ratios of CFCs, halons, CCl4 and CH3CCl3 were close to global tropospheric background levels, with enhancements in the 1–17% range. This provided the first measurement evidence from SE Asia of the effectiveness of Montreal Protocol and related national-scale regulations instituted in the 1990s to phase-out ozone depleting substances (ODS). First- and second-generation CFC replacements (HCFCs and HFCs) dominated the atmospheric halocarbon burden with HFC-134a, HCFC-22 and HCFC-141b exhibiting enhancements of 39–67%. By combining near-source measurements in Indonesia with receptor data in Singapore, regionally transported peat-forest burning smoke was found to impact levels of several NMHCs (ethane, ethyne, benzene, and propane) and short-lived halocarbons (CH3I, CH3Cl, and CH3Br) in a subset of the receptor samples. The strong signatures of these species near peat-forest fires were potentially affected by atmospheric dilution/mixing during transport and by mixing with substantial urban/regional backgrounds at the receptor. Quantitative source apportionment was carried out using positive matrix factorization (PMF), which identified industrial emissions related to refrigeration, foam blowing, and solvent use in chemical, pharmaceutical and electronics industries as the major source of halocarbons (34%) in Singapore. This was followed by marine and terrestrial biogenic activity (28%), residual levels of ODS from pre-Montreal Protocol operations (16%), seasonal incidences of peat-forest smoke (13%), and fumigation related to quarantine and pre-shipment (QPS) applications (7%).

The possible roles of algae in restricting the increase in atmospheric CO2 and global temperature

ABSTRACTAnthropogenic inputs are increasing the CO2 content of the atmosphere, and the CO2 and total inorganic C in the surface ocean and, to a lesser degree, the deep ocean. The greenhouse effect of the increased CO2 (and, to a lesser extent, other greenhouse gases) is very probably the major cause of present global warming. The warming increases temperature of the atmosphere and the surface ocean to a greater extent than the deep ocean, with shoaling of the thermocline, decreasing nutrient flux to the surface ocean where there is greater mean photosynthetic photon flux density. These global changes influence algae in nature. However, it is clear that algae are important, via the biological pump, in decreasing the steady state atmospheric and ocean surface CO2, and thus decreasing radiative forcing, a reduction enhanced by algal increases in albedo. As well as these natural processes there are possibilities that algae can, with human intervention, partly offset the increase in atmospheric CO2. One possibility is to grow algae as sources of fuel for transport, in principle providing an energy source that is close to CO2-neutral. The other possibility is to increase the role of algae in sequestering CO2 as organic C over periods of hundreds or more years in the deep ocean and marine sediments and/or increasing albedo and decreasing radiative forcing of temperature. There are problems, currently unresolved, in the economically viable production of algal biofuels without carbon trading subsidies. Enhanced algal CO2 sequestration also has costs, both in resource input (phosphorus (P) from high P content rocks, a limited resource with a competing use as an agricultural fertilizer) and adverse environmental effects. For example, ocean anoxic zones producing N2O and increased algal production of short-lived halocarbons by algae that both, through breakdown, destroy O3 and increase UV flux to the Earth’s surface.

Emission of short-lived halocarbons by three common tropical marine microalgae during batch culture

Very short-lived halocarbons of marine biogenic origin play an important role in affecting tropospheric and stratospheric chemistry. In recent years, more attention has been paid to tropical regions where the influence of strong convective forces is responsible for rapid uplifting of the volatile organohalogens from the open surface waters into the atmosphere. This laboratory-based study reports on three common tropical marine microalgae capable of emitting a range of short-lived halocarbons, namely, CH3I, CHBr3, CH2Br2, CHBr2Cl, and CHCl3. Chlorophyll a and cell density were highly correlated to the quantity of all five compounds emitted (p < 0.01). The diatom Amphora sp. UMACC 370 had a higher range of CH3I emission rate (10.55–64.18 pmol mg−1 chl a day−1, p < 0.01) than the cyanobacterium Synechococcus sp. UMACC 371 and chlorophyte Parachlorella sp. UMACC 245 (1.04–3.86 pmol mg−1 chl a day−1 and 0–2.16 pmol mg−1 chl a day−1, p < 0.01, respectively). Furthermore, iodine was the dominant halogen emitted in terms of total combined halide mass of all three species. Overall, the emissions of short-lived halocarbons were both species- and growth phase-dependent, highlighting the importance of considering cell physiological conditions when determining gas emission rates.

Halocarbon emissions by selected tropical seaweeds: species-specific and compound-specific responses under changing pH.

Five tropical seaweeds, Kappaphycus alvarezii (Doty) Doty ex P.C. Silva, Padina australis Hauck, Sargassum binderi Sonder ex J. Agardh (syn. S. aquifolium (Turner) C. Agardh), Sargassum siliquosum J. Agardh and Turbinaria conoides (J. Agardh) Kützing, were incubated in seawater of pH 8.0, 7.8 (ambient), 7.6, 7.4 and 7.2, to study the effects of changing seawater pH on halocarbon emissions. Eight halocarbon species known to be emitted by seaweeds were investigated: bromoform (CHBr3), dibro­momethane (CH2Br2), iodomethane (CH3I), diiodomethane (CH2I2), bromoiodomethane (CH2BrI), bromochlorometh­ane (CH2BrCl), bromodichloromethane (CHBrCl2), and dibro­mochloromethane (CHBr2Cl). These very short-lived halocarbon gases are believed to contribute to stratospheric halogen concentrations if released in the tropics. It was observed that the seaweeds emit all eight halocarbons assayed, with the exception of K. alvarezii and S. binderi for CH2I2 and CH3I respectively, which were not measurable at the achievable limit of detection. The effect of pH on halocarbon emission by the seaweeds was shown to be species-specific and compound specific. The highest percentage changes in emissions for the halocarbons of interest were observed at the lower pH levels of 7.2 and 7.4 especially in Padina australis and Sargassum spp., showing that lower seawater pH causes elevated emissions of some halocarbon compounds. In general the seaweed least affected by pH change in terms of types of halocarbon emission, was P. australis. The commercially farmed seaweed K. alvarezii was very sensitive to pH change as shown by the high increases in most of the compounds in all pH levels relative to ambient. In terms of percentage decrease in maximum quantum yield of photosynthesis (Fv∕Fm) prior to and after incubation, there were no significant correlations with the various pH levels tested for all seaweeds. The correlation between percentage decrease in the maximum quantum yield of photosynthesis (Fv∕Fm) and halocarbon emission rates, was significant only for CH2BrCl emission by P. australis (r = 0.47; p ≤ 0.04), implying that photosynthesis may not be closely linked to halocarbon emissions by the seaweeds studied. Bromine was the largest contributor to the total mass of halogen emitted for all the seaweeds at all pH. The highest total amount of bromine emitted by K. alvarezii (an average of 98% of total mass of halogens) and the increase in the total amount of chlorine with decreasing seawater pH fuels concern for the expanding seaweed farming activities in the ASEAN region.

Halocarbon emissions from marine phytoplankton and climate change

Long-lived and short-lived halocarbons have long been known for their adverse effects on atmospheric chemistry, especially ozone depletion that may be directly or indirectly influenced by global climate change. Marine organisms including phytoplankton contribute shorter-lived halocarbon compounds to the atmosphere. Oceans cover more than 70% of the Earth’s surface making the marine phytoplankton a significant presence. Changes in the environment will inevitably affect this widely distributed group of organisms. Various predictions have been made about how phytoplankton will respond to climate change, but as yet little is known about the interactions between phytoplankton, climate change and halocarbon emissions. We provide a summary of studies on halocarbon emissions by marine phytoplankton isolated from different climatic zones that includes data from our recent studies on tropical marine phytoplankton. It is important to determine and characterize the contribution of the phytoplankton to the halocarbon load in the atmosphere to allow their interaction with the changing global climate to be understood. Using these data, we compare the range of halocarbons emitted by phytoplankton with halocarbon emission data for seaweeds, a well-known biogenic contributor of short-lived halocarbons. Sorensen’s coefficient of similarity of 0.50 was calculated, which suggests that half of the detected halocarbon species present in seaweeds are also present in phytoplankton.

A comparison of very short lived halocarbon (VSLS) and DMS aircraft measurements in the tropical west Pacific from CAST, ATTREX and CONTRAST

Abstract. We present a comparison of aircraft measurements of halogenated very short lived substances (VSLSs) and dimethyl sulphide (DMS, C2H6S) from a co-ordinated campaign in January–February 2014 in the tropical west Pacific. Measurements were made on the NASA Global Hawk, NCAR Gulfstream-V High-performance Instrumented Airborne Platform for Environmental Research (GV HIAPER) and UK Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 (see Sect. 2.2) using four separate gas chromatography–mass spectrometry (GC-MS) instruments: one operated by the University of Miami (UoM), one from the National Center for Atmospheric Research (NCAR) and two from the University of York (UoY). DMS was measured on the BAe-146 and GV. The instruments were inter-calibrated for halocarbons during the campaign period using two gas standards on separate scales: a National Oceanic and Atmospheric Administration (NOAA) SX-3581 standard representative of clean low-hydrocarbon air, and an Essex canister prepared by UoM, representative of coastal air, which was higher in VSLS and hydrocarbon content. UoY and NCAR use the NOAA scale/standard for VSLS calibration, and UoM uses a scale based on dilutions of primary standards calibrated by GC with FID (flame ionisation detector) and AED (atomic emission detector). Analysis of the NOAA SX-3581 standard resulted in good agreement for CH2Cl2, CHCl3, CHBr3, CH2Br2, CH2BrCl, CHBrCl2, CHBr2Cl, CH3I, CH2ICl and CH2I2 (average relative standard deviation (RSD) &lt; 10 %). Agreement was in general slightly poorer for the UoM Essex canister with an RSD of &lt; 13 %. Analyses of CHBrCl2 and CHBr3 in this standard however showed significant variability, most likely due to co-eluting contaminant peaks, and a high concentration of CHBr3, respectively. These issues highlight the importance of calibration at atmospherically relevant concentrations ( ∼ 0.5–5 ppt for VSLSs; see Fig. 5 for individual ranges). The UoY in situ GC-MS measurements on board the BAe-146 compare favourably with ambient data from NCAR and UoM; however the UoY whole-air samples showed a negative bias for some lower-volatility compounds. This systematic bias could be attributed to sample line losses. Considering their large spatial variability, DMS and CH3I displayed good cross-platform agreement without any sampling bias, likely due to their higher volatility. After a correction was performed based upon the UoY in situ vs. whole-air data, all four instrument datasets show good agreement across a range of VSLSs, with combined mean absolute percentage errors (MAPEs) of the four platforms throughout the vertical profiles ranging between 2.2 (CH2Br2) and 15 (CH3I) % across a large geographic area of the tropical west Pacific. This study shows that the international VSLS calibration scales and instrumental techniques discussed here are in generally good agreement (within ∼ 10 % across a range of VSLSs), but that losses in aircraft sampling lines can add a major source of uncertainty. Overall, the measurement uncertainty of bromocarbons during these campaigns is much less than the uncertainty in the quantity of VSLS bromine estimated to reach the stratosphere of between 2 and 8 pptv.

Observation of the Variations of Very Short-Lived Halocarbon Emissions in Tropical Coastal Marine Boundary Layer

Halocarbons (methyl iodide, bromoform and dibromomethane) are produced naturally and the source has been found to be largely from the ocean. In recent years, the role of very short-lived halocarbons in the atmospheric chemistry has attracted many researchers in this field. Dissolved halocarbons in sea water and atmospheric halocarbons were taken at 73 different positions across South China Sea and Sulu Sea during the SHIVA measurement campaign on RV SONNE cruise from Singapore to Manila on the 15 to 29 November 2011. Both water and canister samples of air were analyzed on two different purge-and-trap (PT) gas chromatographic systems. Significant levels of halocarbons were observed during day-time and night-time in the tropical marine boundary layer. All of the halocarbons show higher concentrations at the coastal area compare to the location in the open sea.

Long-term halocarbon observations from a coastal and an inland site in Sabah, Malaysian Borneo

Abstract. Short-lived halocarbons are believed to have important sources in the tropics, where rapid vertical transport could provide a significant source to the stratosphere. In this study, quasi-continuous measurements of short-lived halocarbons are reported for two tropical sites in Sabah (Malaysian Borneo), one coastal and one inland (rainforest). We present the observations for C2Cl4, CHBr3, CH2Br2* (actually ~80% CH2Br2 and ~20% CHBrCl2) and CH3I from November 2008 to January 2010 made using our μDirac gas chromatographs with electron capture detection (GC-ECD). We focus on the first 15 months of observations, showing over one annual cycle for each compound and therefore adding significantly to the few limited-duration observational studies that have been conducted thus far in southeast Asia. The main feature in the C2Cl4 behaviour at both sites is its annual cycle, with the winter months being influenced by northerly flow with higher concentrations, typical of the Northern Hemisphere, and with the summer months influenced by southerly flow and lower concentrations representative of the Southern Hemisphere. No such clear annual cycle is seen for CHBr3, CH2Br2* or CH3I. The baseline values for CHBr3 and CH2Br2* are similar at the coastal (overall median: CHBr3 1.7 ppt, CH2Br2* 1.4 ppt) and inland sites (CHBr3 1.6 ppt, CH2Br2* 1.1 ppt), but periods with elevated values are seen at the coast (overall 95th percentile: CHBr3 4.4 ppt, CH2Br2ast 1.9 ppt), presumably resulting from the stronger influence of coastal emissions. Overall median bromine values from [CHBr3 × 3] + [CH2Br2* × 2] are 8.0 ppt at the coast and 6.8 ppt inland. The median values reported here are largely consistent with other limited tropical data and imply that southeast Asia generally is not, as has been suggested, a hot spot for emissions of these compounds. These baseline values are consistent with the most recent emissions found for southeast Asia using the p-TOMCAT (Toulouse Off-line Model of Chemistry And Transport) model. CH3I, which is only observed at the coastal site, is the shortest-lived compound measured in this study, and the observed atmospheric variations reflect this, with high variability throughout the study period.

Halocarbons associated with Arctic sea ice

Short-lived halocarbons were measured in Arctic sea–ice brine, seawater and air above the Greenland and Norwegian seas (~81°N, 2–5°E) in mid-summer, from a melting ice floe at the edge of the ice pack. In the ice floe, concentrations of C2H5I, 2-C3H7I and CH2Br2 showed significant enhancement in the sea ice brine, of average factors of 1.7, 1.4 and 2.5 times respectively, compared to the water underneath and after normalising to brine volume. Concentrations of mono-iodocarbons in air are the highest ever reported, and our calculations suggest increased fluxes of halocarbons to the atmosphere may result from their sea–ice enhancement. Some halocarbons were also measured in ice of the sub-Arctic in Hudson Bay (~55°N, 77°W) in early spring, ice that was thicker, colder and less porous than the Arctic ice in summer, and in which the halocarbons were concentrated to values over 10 times larger than in the Arctic ice when normalised to brine volume. Concentrations in the Arctic ice were similar to those in Antarctic sea ice that was similarly warm and porous. As climate warms and Arctic sea ice becomes more like that of the Antarctic, our results lead us to expect the production of iodocarbons and so of reactive iodine gases to increase.

Very short‐lived halocarbons over the tropical Atlantic

Very short lived halocarbons (VSLH), including CHBr3, CH2Br2, CHCl3, C2H5I, and CH2ClI, can be transported upward through the atmosphere from the marine boundary layer and contribute to ozone depletion—as far up as the lower stratosphere in the case of brominated and chlorinated compounds. VSLH are released from algae, marine bacteria, and photochemical breakdown of organic material in the ocean, but there are uncertainties in the contributions from these sources, and global distributions are not well known because there are wide spatial variations in fluxes of VSLH from sea to air.

Estimating the climate significance of halogen-driven ozone loss in the tropical marine troposphere

Abstract. We have integrated observations of tropospheric ozone, very short-lived (VSL) halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units) of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately −0.10 W m−2 to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m−2 contribution of tropospheric ozone to present-day radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone.