Article | Open

Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

  • Scientific Reports 6, Article number: 36821 (2016)
  • doi:10.1038/srep36821
  • Download Citation
Received:
Accepted:
Published online:

Abstract

The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry.

Introduction

During boreal winter, deep convection over the Western Tropical Pacific is the dominant pathway for the transport of surface air to the tropical tropopause layer (TTL, 13–17 km) and into the stratosphere1,2,3. As such, tropospheric composition and chemistry there plays a disproportionately large role in dictating stratospheric composition. Although research activity in the region has increased in recent years airborne observations remain scarce, particularly in the upper part of the free troposphere around the TTL. The CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) dataset is unique in that it covers multiple years and seasons in this particular location and altitude range. Recent campaigns and modeling efforts have concentrated mainly on characterizing regional sources of short-lived halocarbons and quantifying their stratospheric loadings4, with most of the focus being on naturally occurring brominated compounds and, more recently, anthropogenic chlorocarbon emissions5. There is also increased interest in the role of Br and I as oxidants, however, the potential of Cl as an oxidant in the region has so far not been addressed.

Even when present at low levels, Cl radicals can have a profound impact on tropospheric oxidation and radical cycling. Cl chemistry can significantly impact levels of tropospheric ozone, a greenhouse gas that is also a precursor for the OH radical, destroying it in clean environments and enhancing its formation under polluted conditions. Additionally, much faster rates of reaction, in comparison to OH, allow Cl radicals to expedite oxidation of climate-active gases, such as methane (CH4) and dimethyl sulphide. The introduction of reactive chlorine into the troposphere is understood to occur mainly via heterogeneous processes on particulate surfaces, typically sea salt, which release particle bound chlorine into the gas phase6,7. The main mechanisms for chlorine release are (i) displacement of particulate hydrochloric acid by nitric or sulfuric acid, (ii) photochemical production of molecular chlorine on aerosol surfaces, and, in polluted areas with high levels of nitrogen oxides (NOx), (iii) formation of nitryl chloride (ClNO2) by uptake of N2O5 on the surface of chlorine containing aerosols at night8. Once thought to be restricted to the marine and polar boundary layer, recent observations have found that chlorine radicals also play a significant role in coastal urban and even mid-continental areas9,10, believed to be a result of mechanism (iii). While Cl radical concentrations approaching 106 Cl cm−3 have been reported9, the global average marine boundary layer concentration is estimated to be about 103 Cl cm−3, with Cl chemistry generally considered minor on the global scale.

Over two consecutive winter seasons (November 2012 to March 2013 and November 2013 to January 2014) the IAGOS-CARIBIC observatory11 was deployed monthly on round-trip commercial flights between Bangkok, Thailand and Kuala Lumpur, Malaysia (Table 1). Observations were made at cruise altitudes between 9 and 12 km and included the collection of air samples, which were analyzed in the laboratory for over 60 trace gases, including a suite of 20 non-methane hydrocarbons (NMHCs)12. Supporting meteorological analyses13,14 indicate that the air masses encountered had passed over the South China Sea and/or tropical Western Pacific (Fig. 1), except during March 2013, when air masses were from the Indian Ocean. Here we investigate the surprising signals observed in the hydrocarbons during six separate flights with air masses traceable to the South China Sea (November 2012, December 2012, February 2013, November 2013, December 2013 and January 2014; Table 1). These signals were distinctly different from those previously observed at similar altitudes and latitudes elsewhere in the global dataset and indicative of chlorine radical chemistry.

Table 1: Flight dates and fit information for i-butane/n-butane correlations shown in Fig. 2.
Figure 1
Figure 1

(A) Schematic of prevailing meteorological conditions over Southeast Asia and the Maritime Continent during the Northeast (winter) Monsoon (background map from Google Earth Map data: Google, DigitalGlobe). (B,C) 8-day backwards air mass trajectories for air samples collected on flights to Kuala Lumpur during December 2013 (B) and February 2013 (C), overlaid on mean surface (950 hPa) winds for the preceding 10 days. Data visualizations produced using IDL8.5 Excelis Visual Information Solutions, Boulder, Colorado, USA. http://www.harrisgeospatial.com/ProductsandSolutions/GeospatialProducts/IDL.aspx.

Results

During November and December of both 2012 and 2013 unusually high ratios of i-butane to n-butane were observed, which were not seen on the same route in the following January or February (Fig. 2A). The atmospheric ratio of these compounds typically falls within a range of 0.3 to 0.6 i-butane/n-butane15,16, and observations have largely fallen within this range in a variety of environments, from polluted urban areas to clean background sites. While some point sources are known to have emission ratios falling outside of this range, they are relatively scarce, and the isomeric ratio is largely determined by the ratio in the largest anthropogenic sources (e.g. vehicular emissions, fossil fuels) and in biomass burning emissions. Although observations of NMHCs are few in this region, there is no evidence in the literature that butane emission ratios deviate substantially from ratios observed elsewhere, and furthermore no evidence to support widely varying seasonal emissions. Therefore, it is unlikely that unusual source ratios are at play on such a wide scale.

Figure 2
Figure 2

(A) Correlation plots of i-butane vs. n-butane observed at 9–12 km during flights between Bangkok and Kuala Lumpur (monthly data) and for all CARIBIC flights in the Northern Hemisphere Upper Troposphere (NH UT) between November and March (grey crosses). Dashed lines represent the linear least squares fit to the data and solid lines represent typical minimum and maximum emission ratios (0.3 and 0.6) and the 1:1 line. Fit data can be found in the Table 1. (B) Relationship between the i-butane to n-butane ratio and i-butane to propane ratio during November and December of 2012 and 2013 (blue diamonds), and January 2014 and February 2013 (orange circles).

Near-equal loss rates via reaction with the hydroxyl radical (OH) causes i-butane/n-butane to vary little with transport. However, because the rate of removal of n-butane by the chlorine radical (Cl) is ~50% faster than that of i-butane, Cl oxidation causes the i-butane/n-butane ratio to increase. Ratios in November and December were up to 43% higher than in January and February, and higher still than observed along other CARIBIC routes (Fig. 2A, grey crosses). The higher variability of the highlighted data compared to that taken elsewhere (see grey points in Fig. 2A) is likely due to the colocation of strong convection and higher levels of pollution at the surface. These observed large deviations are well beyond the measurement uncertainty (see Method) and imply significant hydrocarbon losses due to oxidation by Cl in this region.

Direct measurements of chlorine radicals are not currently possible, making indirect methods necessary to estimate Cl abundance and to gauge its importance relative to OH in tropospheric photochemistry. To access this information we have examined variations in the relationships of three NMHCs having suitable rates of reaction with Cl and OH17. Losses of an atmospheric species, A, attributable to a single oxidant, X, can be described by the equation

where [A]t is the concentration at time t, [A]0 is the initial concentrations, kX is the rate of reaction with oxidant X and [X] is the mean concentration of the oxidant during the transport time, Δt. Equation 1 can be rearranged to solve for any of the above parameters, and is often used as the basis for so-called “NMHC photochemical clock” methods17,18,19,20, which are frequently employed to investigate transport times (Δt) or oxidant concentrations. Given the large variability in NMHC concentrations and corresponding uncertainty in their initial levels, these methods more commonly rely on NMHC ratios, comparing observed ratios with typical emission ratios, which tend to lie within narrow ranges and are relatively well-known. In order to reduce the influence of mixing, observed ratios, also referred to as enhancement ratios, are determined from the slopes of the linear least squares fit to the data (Fig. 2, Table 1). Changes in NMHC ratios with processing can be described by combining Equation 1 for two compounds, A and B (expressed here in terms of the natural logarithm):

The further combination of Equation 2 for two different oxidants and NMHC pairs results in a time-independent expression used to derive the relative contributions of OH and Cl:

In Equation 1, A and B represent a NMHC pair having approximately equal rates of reaction with OH but different rates of reaction with Cl (Cl reactive pair), while A and C have approximately equal reaction rates with Cl but different reaction rates with OH (OH reactive pair). By comparing observed ratios (t) to initial ratios (0), it is possible to quantify the mean ratio of Cl to OH encountered by the air mass between emission at the Earth’s surface and sampling at 10–12 km. It should be noted that the ratio derived is an average integrated over the transport path and an influence of in-mixing of other aimasses cannot be ruled out. In this case, in-mixing is most likely to be from the relatively clean and photochemically aged Pacific free troposphere and boundary layer. Since such air will have been predominately oxidized by OH radicals, in-mixing will have the effect of biasing the data towards OH making estimates of the chlorine abundance conservative.

Here we use i-butane and n-butane as the Cl reactive pair, and propane and i-butane as the OH reactive pair (Table 2), and comparison of these ratios already shows qualitatively the influence of Cl (Fig. 2B). If OH alone acts on an air parcel, i-butane/propane would decrease with processing, while i-butane/n-butane remains constant; conversely, Cl chemistry alone would cause i-butane/n-butane to increase with i-butane/propane staying the same. As OH is omnipresent in the sunlit troposphere, changes in both ratios are expected when Cl is also present, and this behavior is indeed observed in November and December of both years. In contrast, the January and February variability in i-butane/n-butane is small (vertical axis in Fig. 2B), indicating that Cl chemistry was negligible at this time, see discussion. Analogous assessments with combinations of higher hydrocarbons were not possible as these more reactive species were mostly below the 1 pptv detection limit in this altitude range.

Table 2: Rates of reaction with OH and Cl and classification for Fig. 3 for various hydrocarbons32,36 at 298 K and 1 atm.

Using Equation 3 we have estimated the radical ratio, [Cl]:[OH], during each month in order to constrain the relative importance of Cl as an oxidant (Fig. 3A). The role of Cl radicals generally becomes significant at [Cl]:[OH] of about 10−3, when Cl radical concentrations (usually lower than OH) and rate coefficients (usually faster than with OH) combine so that Cl-initiated oxidation competes with that of OH7,21. We therefore express the ratio as Cl:103 OH, such that values >1 indicate relative levels of Cl significant in oxidative processes. In the absence of corresponding surface measurements, we have applied literature values of 0.6 and 0.3 for i-butane/n-butane and i-butane/propane, respectively, derived from observations made in the Pearl River Delta region of China22, and note that these values are nearly identical to observations made in other urban areas throughout Asia23,24. Our observations in November and December of both years correspond to [Cl]:[OH] between 9.1 ± 2.3 and 16.0 ± 2.3 Cl:103 OH (errors denote 95% confidence interval based on the error of the slopes of the correlations) (Fig. 3A). Therefore assuming a value for OH of 1 × 106 molecules cm−3, then Cl radicals were present at levels between 0.9–1.6 × 104 molecules cm−3. It should be noted, however, that this is the transit average and if the chlorine signature is created when the emissions are fresh (see discussion) then very much higher chlorine radical concentrations (approaching 106 molecules cm−3) are present. The largest uncertainty in these estimates lies in the choice of initial ratios, however, applying values that span the range of typical reported ratios for these species we find that even the most conservative estimates correspond to [Cl]:[OH] >1 Cl:103 OH. It should be noted that this method provides an estimate of [Cl]:[OH] integrated over the history of the air mass and does not fully account for the mixing in of air masses having different photochemical histories, although this influence is reduced through the use of enhancement ratios. As mixing most likely results in the introduction of air masses having been acted on exclusively by OH, the result would be an underestimation of [Cl]:[OH] in the initial air mass. Thus our measurements indicate the presence of significant quantities of Cl radicals in November and December.

Figure 3
Figure 3

(A) Mean (black squares) and range (grey bars) of [Cl]:[OH] calculated for each month (see text). Error bars denote 95% confidence interval for the mean. (B) Mean relative removal rates by Cl and OH for methane, alkanes, alkenes and short-lived halocarbons (see Table 2), estimated for each month, with error bars indicating the spread. The dashed lines represent where removal by Cl and OH are equal (upper line) and where removal by Cl is 10% that of OH (lower line).

To explore the significance of Cl as a tropospheric oxidant we have used the results derived above to calculate the rate of removal by Cl relative to removal by OH during each month for four classes of hydrocarbons important in this region: methane, alkanes, alkenes, and short-lived halocarbons (Fig. 3B, Table 2). The rate of reaction between an NMHC and either OH or Cl is determined for 298 K and 1 atm as it is assumed that the chlorine chemistry occurs near the ground (see discussion). Oxidant-specific removal rates are determined as the product of the rate coefficient, kX, and oxidant concentration, [X]; therefore, the relative rate of removal by Cl to removal by OH can be determined as

Relative removal rates were calculated for methane and, in the case of alkanes, alkenes and short-lived halocarbons, as the average value for a set of representative species (Table 2).

In November and December, when we found [Cl]:[OH] is an order of magnitude greater than in January and February, Cl is the dominant sink for alkanes, with removal rates up to twice as fast as by reaction with OH (Fig. 3B). Removal of methane and alkenes by Cl is also large, accounting for up to 20% and 13% of methane and alkene removal, respectively. Conversely, Cl is only a minor sink (<5%) for directly emitted short-lived halocarbons, the abundances and fates of which have been given much recent attention in this region owing to their uncertain role in stratospheric ozone loss25. Therefore we find that regional Cl chemistry has a strong potential for formation of long-lived chlorinated products via alkene oxidation, while doing little to decrease the abundances of primary halocarbons.

Discussion

Knowledge of the transport pathways of the sampled air masses is critical to identifying the source of these Cl radicals. During boreal winter, regional circulation patterns are controlled by the Northeast Monsoon (November – March), which, at the surface, transports air masses over the South China Sea to equatorial Southeast Asia. Here they can be lofted to higher altitudes via the frequent strong convection present there26 with overall transport times between 3 and 7 days. Transport from East Asia is strongest at the onset of the monsoon and weakens in later months, as surface winds change to bring more air from the Western Pacific (Fig. 1A). Prevailing wind patterns are punctuated by incidences of rapid meridional transport, or cold surges, which expedite the movement of pollution to the south27. As the height of peak convective outflow (~12–13 km) is close to our CARIBIC sampler flight altitudes the probability of encountering convective outflow is very high2. Measurements were taken at 10–12 km, well below the local tropopause (16–18 km) and there was no indication in the ozone or RH data of stratospheric influence. Thus, our data will to a large extent reflect the composition and chemistry of convected air from the surface. These transport patterns are evident for the observation period (Fig. 1B,C), and vertical wind speeds combined with relative humidity and equivalent potential temperature support the presence of convection, with maximum intensity over Borneo (Fig. 4). Pollution export was evident in our observations during November and December, with typical urban/industrial tracers, such as dichloromethane, being well above background28. This strongly suggests that the effect is associated with pollution outflow.

Figure 4
Figure 4

Monthly mean plots of vertical winds speeds at 500 hPa (a,b), equivalent potential temperature at 700 hPa (c,d), and relative humidity at 500 hPa (e,f), from the ECMWF archive. Figures on the left (a,c,e) are for February 2013 and figures on the right (b,d,f) are for December 2013. These parameters are used to identify the most active convective spots, and therefore the most likely regions of uplift, for the region during these months. More negative vertical wind speeds (upward movement) and higher potential temperatures (warmer/more moist air) are indicative of a greater potential for convective activity, while relative humidity at 500 hPa is an indication of which air masses have most recently been influenced by (more humid) air, presumably from the boundary layer. Data visualizations produced using IDL8.5 Excelis Visual Information Solutions, Boulder, Colorado, USA. http://www.harrisgeospatial.com/ProductsandSolutions/GeospatialProducts/IDL.aspx.

Given the association with polluted air masses, ClNO2 seems a likely agent for producing the observed chlorine radical signatures. Previous observations have shown ClNO2 formation to be an important process in coastal urban areas, where anthropogenic emissions interact with sea salt aerosols21,29. Moreover, there is growing observational support for mid-continental ClNO2 sources30, and modelling studies predict strong ClNO2 formation over Southeast Asia during winter31. Recently, extremely high levels of Cl-NO2 have been reported in the plumes of Chinese megacities32,33,34. Estimated levels in the residual layer based on their measurement data ranged from 1.7 to over 4 ppb leading to chlorine radical production rates in excess of 1 ppb hr−1. In the light of this finding it seems likely that mechanism iii is the most likely source of the chlorine radical chemistry in our study. It should be noted that while Cl chemistry is most significant in November and December, the source regions of the air masses were different in January – March. High Cl-NO2 concentrations have been measured at the ground in the Pearl river delta region in both winter34 and summer32,33 suggesting that the apparent seasonality in the signal observed at altitude stems from the meteorology rather than a variation of source strength.

In comparison to previous measurements made in the United States (Texas35 and California21) the recently reported levels of Cl-NO2 and NOx are significantly higher32. Rather than providing only a transient surge of Cl radicals at sunrise, levels of Cl-NO2 were sustained for much longer and even grew for four hours after dawn. The high levels of NO2 present can serve to suppress OH (through HNO3 formation) and in doing so prevent the masking of Cl radical chemistry by secondary OH production shown by Young et al.21. Therefore the combination of high sustained ClNO2 and NO2 levels over the mainland China source region may explain why the chlorine chemistry is so profound that it can be observed by our aircraft at 10 km altitude.

We note that a ClNO2 source of Cl radicals would also serve as a source of nitrate (NO3) radicals, which also react with the NMHCs discussed here. NO3 would also be expected to play a role in nighttime oxidation in regions having high levels of NOx and O3 (regardless of the presence of ClNO2), as would be expected for polluted air masses originating in continental Asia. However, reactions of alkanes with NO3 proceed over one thousand times more slowly than with Cl (or OH) and are on the order of 10−17–10−16 cm3 molec−1 s−1 and would not be expected to be a dominant loss mechanism. More significantly, the reaction of NO3 with i-butane is faster than with n-butane, so reaction with NO3 would cause the ratio of i-butane/n-butane to decrease over time. This again suggests that the significant Cl radical abundances we have derived from our data are likely underestimates.

In addition to the influence on tropospheric oxidative cycles, Cl radical chemistry occurring in these polluted air masses would be expected to result in the formation of secondary chlorinated species via reaction with the alkenes that are abundant in anthropogenic pollution. While oxidation of alkanes by Cl occurs via the same (hydrogen abstraction) process as by OH, resulting in more rapid formation of oxygenated products (e.g. formaldehyde, acetone)36, oxidation of alkenes proceeds via addition of Cl and results in the formation of chlorinated products (e.g. formyl chloride and chloroacetone)37,38, creating a relatively long-lived (>1 month) Cl reservoir. These chlorinated secondary products of hydrocarbon oxidation by OH are not included in current inventories, which so far only consider the products of halocarbon oxidation by OH5. Nonetheless, these in-situ chlorinated products can enter the stratosphere and contribute to the total stratospheric reactive chlorine budget, which is key to stratospheric ozone depletion but not yet closed39.

In the Western Tropical Pacific region, where transport patterns facilitate global redistribution of pollutants and persistent deep convection creates a fast-track to the stratosphere, the regional chlorine chemistry described here can lead to global scale impacts. Chlorine chemistry on the scale suggested by our observations would perturb significantly both the composition and radical abundances of the free troposphere, thereby affecting concentrations of greenhouse gases such as methane. Additionally, oxygenated and chlorinated species produced via Cl chemistry, can be transported to and across the TTL. These findings also point to a potential mechanism for chlorine, possibly extracted from sea salt by anthropogenic NOx pollution via ClNO2 formation, to enhance atmospheric oxidation capacity and enter the stratosphere as chlorinated products of hydrocarbon oxidation, exacerbating ozone depletion.

Methods

Air sample collection and NMHC analysis

The CARIBIC scientific payload consists of 15 measurement systems, is fully automated, and carries out in-situ trace gas and aerosol measurements, as well as remote sensing by DOAS and the collection of aerosol and whole air samples11. Supporting meteorological analyses are based on the TRAJKS model13,14 and included 8-day backward trajectories for the air samples. During flights between Bangkok and Kuala Lumpur air samples were collected in glass sampling flasks, with 7 samples collected on the way to Kuala Lumpur and 7 on the return to Bangkok. The flasks are 2.7 L in volume and are filled to ~4.5 bar at pre-determined, 8 minute (~125 km) intervals with collection times of about 30 s (~7 km). Upon return of the container to the institute in Mainz the air samples are removed and analyzed in the laboratory for NMHCs. This analysis uses an HP-6890 gas chromatograph (GC) coupled with a flame ionization detector (FID), where, prior to analysis, a 1l (STP) aliquot of sample is pretreated by drying followed by cryogenic pre-concentration and cryo-focusing12. A suite of 20 compounds is measured, consisting of the C2-C8 alkanes, ethyne and the BTEX aromatics (benzene, toluene, ethylbenzene and the xylenes). Calibration of NMHCs is based on individual compound response factors determined from analysis of a synthetic mixture of NMHCs (accuracy of ±2%) purchased from the National Physical Laboratory (NPL, United Kingdom). The compounds discussed herein (n-butane, i-butane and propane) have analytical precisions and accuracies of less than 1%, limits of detection of 1 ppt, and overall uncertainties of less than 5%. As of this writing over 6000 CARIBIC whole air samples have been measured on this system.

Additional Information

How to cite this article: Baker, A. K. et al. Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia. Sci. Rep. 6, 36821; doi: 10.1038/srep36821 (2016).

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

References

  1. 1.

    & A Stratospheric Fountain? Journal of the Atmospheric Sciences 38, 2789–2796, doi: 10.1175/1520-0469 (1981).

  2. 2.

    , , & Seasonal differences of vertical-transport efficiency in the tropical tropopause layer: On the interplay between tropical deep convection, large-scale vertical ascent, and horizontal circulations. Journal of Geophysical Research: Atmospheres 117, D05302, doi: 10.1029/2011JD016992 (2012).

  3. 3.

    , & Air-Mass Origin in the Tropical Lower Stratosphere: The Influence of Asian Boundary Layer Air. Geophysical Research Letters, doi: 10.1002/2015GL063937 (2015).

  4. 4.

    et al. Deriving an atmospheric budget of total organic bromine using airborne in situ measurements from the western Pacific area during SHIVA. Atmos. Chem. Phys. 14, 6903–6923, doi: 10.5194/acp-14-6903-2014 (2014).

  5. 5.

    et al. Growth in stratospheric chlorine from short-lived chemicals not controlled by the Montreal Protocol. Geophysical Research Letters 42, 4573–4580, doi: 10.1002/2015GL063783 (2015).

  6. 6.

    & The role of halogen species in the troposphere. Chemosphere 52, 325–338, doi: 10.1016/s0045-6535(03)00216-9 (2003).

  7. 7.

    & Reactive halogen chemistry in the troposphere. Chemical Society Reviews 41, 6448–6472 (2012).

  8. 8.

    et al. Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride. Proceedings of the National Academy of Sciences 106, 13647–13654, doi: 10.1073/pnas.0904195106 (2009).

  9. 9.

    et al. Nat. Geosci. 1, 324 (2008).

  10. 10.

    et al. Nature 464, 271 (2010).

  11. 11.

    et al. Civil Aircraft for the regular investigation of the atmosphere based on an instrumented container: The new CARIBIC system. Atmospheric Chemistry and Physics 7, 4953–4976 (2007).

  12. 12.

    , & Analysis of non-methane hydrocarbons in air samples collected aboard the CARIBIC passenger aircraft. Atmospheric Measurement Techniques 3, 311–321, doi: 10.5194/amt-3-311-2010 (2010).

  13. 13.

    , & Sensitivity of trajectories to data resolution and its dependence on the starting point: In or outside a tropopause fold. Meteorological Applications 3, 267–273, doi: 10.1002/met.5060030308 (1996).

  14. 14.

    Meteorological analysis of CARIBIC by KNMI, (2014).

  15. 15.

    et al. Internal consistency tests for evaluation of measurements of anthropogenic hydrocarbons in the troposphere. Journal of Geophysical Research - Atmospheres 103, 22339–22359, doi: 10.1029/98jd01364 (1998).

  16. 16.

    et al. Reconstruction of Northern Hemisphere 1950–2010 atmospheric non-methane hydrocarbons. Atmospheric Chemistry and Physics 14, 1463–1483, doi: 10.5194/acp-14-1463-2014 (2014).

  17. 17.

    et al. Measurements of C2-C6 hydrocarbons during the Polar Sunrise1992 Experiment: Evidence for Cl atom and Br atom chemistry. Journal of Geophysical Research - Atmospheres 99, 25355–25368, doi: 10.1029/94jd01243 (1994).

  18. 18.

    , , , & The indirect determination of chlorine atom concentration in the troposphere from changes in the patterns of non-methane hydrocarbons. Tellus B 49, 592–601, doi: 10.1034/j.1600-0889.49.issue5.13.x (1997).

  19. 19.

    et al. Spatial and temporal variability of nonmethane hydrocarbon mixing ratios and their relation to photochemical lifetime. J. Geophys. Res. 103, 13557–13567, doi: 10.1029/97jd01715 (1998).

  20. 20.

    et al. Indications of photochemical histories of Pacific air masses from measurements of atmospheric trace species at Point Arena, California. Journal of Geophysical Research: Atmospheres 97, 15883–15901, doi: 10.1029/92JD01242 (1992).

  21. 21.

    et al. Chlorine as a primary radical: evaluation of methods to understand its role in initiation of oxidative cycles. Atmos. Chem. Phys. 14, 3427–3440, doi: 10.5194/acp-14-3427-2014 (2014).

  22. 22.

    et al. Ambient mixing ratios of nonmethane hydrocarbons (NMHCs) in two major urban centers of the Pearl River Delta (PRD) region: Guangzhou and Dongguan. Atmospheric Environment 42, 4393–4408, doi: 10.1016/j.atmosenv.2008.01.028 (2008).

  23. 23.

    et al. Volatile organic compounds in 43 Chinese cities. Atmospheric Environment 39, 5979–5990, doi: 10.1016/j.atmosenv.2005.06.029 (2005).

  24. 24.

    et al. Characteristics and diurnal variations of NMHCs at urban, suburban, and rural sites in the Pearl River Delta and a remote site in South China. Atmospheric Environment 41, 8620–8632, doi: 10.1016/j.atmosenv.2007.07.029 (2007).

  25. 25.

    et al. Efficiency of short-lived halogens at influencing climate through depletion of stratospheric ozone. Nature Geoscience 8, 186–190, doi: 10.1038/ngeo2363 (2015).

  26. 26.

    & Tropical Climatology: an introduction to the Climates of the Low Latitudes, 2nd edition. edn, (Wiley, 1998).

  27. 27.

    et al. Rapid transport of East Asian pollution to the deep tropics. Atmospheric Chemistry and Physics 15, 3565–3573, doi: 10.5194/acp-15-3565-2015 (2015).

  28. 28.

    et al. Increasing concentrations of dichloromethane, CH2Cl2, inferred from CARIBIC air samples collected 1998–2012. Atmospheric Chemistry and Physics 15, 1939–1958, doi: 10.5194/acp-15-1939-2015 (2015).

  29. 29.

    et al. High levels of nitryl chloride in the polluted subtropical marine boundary layer. Nature Geoscience 1, 324–328, doi: 10.1038/ngeo177 (2008).

  30. 30.

    et al. A large atomic chlorine source inferred from mid-continental reactive nitrogen chemistry. Nature 464, 271–274, doi: 10.1038/nature08905 (2010).

  31. 31.

    , , & Importance of tropospheric ClNO2 chemistry across the Northern Hemisphere. Geophysical Research Letters 41, 4050–4058, doi: 10.1002/2014GL059962 (2014).

  32. 32.

    et al. Significant concentrations of nitryl chloride sustained in the morning: Investigations of the causes and impacts on ozone production in a polluted region of northern China. Atmospheric Chemistry and Physics Discussions, doi: 10.5194/acp-2016-439, (2016).

  33. 33.

    et al. impacts of heterogeneous uptake of dinitrogen pentoxide and chlorine activation on ozone and reactive nitrogen partitioning: Improvement and application of WRF-Chem model in southern China. Atmospheric Chemistry and Physics Discussions doi: 10.5194/acp-2016-412 (2016).

  34. 34.

    et al. Observations of nitryl chloride and modeling its source and effect on ozone in the planetary boundary layer of southern China. Journal of Geophysical Research: atmospheres, 121, 2476–2489, doi: 10.1002/2015JD024556 (2016).

  35. 35.

    , & In land concentrations of Cl2 and ClNO2 in southeast Texas suggest chlorine chemistry significantly contributes to atmospheric reactivity. Atmosphere, 6, 1487–1506, doi: 10.3390/atmos6101487 (2015).

  36. 36.

    et al. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II - gas phase reactions of organic species. Atmospheric Chemistry and Physics 6, 3625–4055, doi: 10.5194/acp-6-3625-2006 (2006).

  37. 37.

    et al. Cl atom initiated oxidation of 1-alkenes under atmospheric conditions. Atmospheric Environment 67, 93–100, doi: 10.1016/j.atmosenv.2012.10.039 (2013).

  38. 38.

    et al. Laboratory and Theoretical Study of the Oxy Radicals in the OH- and Cl-Initiated Oxidation of Ethene. The Journal of Physical Chemistry A 102, 8116–8123, doi: 10.1021/jp981937d (1998).

  39. 39.

    et al. Ozone-Depleting Substances (ODSs) and Other Gases of Interest to the Montreal Protocol, Chapter 1 in Scientific Assessment of Ozone Depletion: 2014, Global Ozone Research and Monitoring Project-Report No. 55. 1–101 (2014).

Download references

Acknowledgements

The authors would like to thank the entire CARIBIC team for their hard work and dedication, in particular Claus Koeppel for construction, installation and maintenance of the whole air sampler. Figure 1A was created with the assistance of Martin Riekert of markenfaktur. CARIBIC is part of the European Research Infrastructure, IAGOS (In-service Aircraft for a Global Observing System). Operation of the CARIBIC observatory is possible through the support and cooperation of Lufthansa and Lufthansa Technik, and our home airports in Frankfurt and Munich. Financial support is provided by the Max Planck Society, Karlsruhe Institute of Technology, the German Research Foundation (DFG) and Frankfurt Airport.

Author information

Affiliations

  1. Max Planck Institute for Chemistry, Mainz, Germany

    • Angela K. Baker
    • , Carina Sauvage
    • , Ute R. Thorenz
    • , Carl A. M. Brenninkmeijer
    •  & Jonathan Williams
  2. Royal Netherlands Meteorological Institute (KNMI), De Bilt, the Netherlands

    • Peter van Velthoven
  3. National Centre for Atmospheric Science, University of East Anglia, Norwich, United Kingdom

    • David E. Oram
  4. Karlsruhe Institute of Technology, Karlsruhe, Germany

    • Andreas Zahn

Authors

  1. Search for Angela K. Baker in:

  2. Search for Carina Sauvage in:

  3. Search for Ute R. Thorenz in:

  4. Search for Peter van Velthoven in:

  5. Search for David E. Oram in:

  6. Search for Andreas Zahn in:

  7. Search for Carl A. M. Brenninkmeijer in:

  8. Search for Jonathan Williams in:

Contributions

A.B. and J.W. wrote the manuscript. A.B., J.W., C.S. and U.T. conducted NMHC analyses. C.B. and A.Z. are the CARIBIC lead scientists and oversaw planning and execution of measurement flights and the provision of aircraft data. P.v.V. provided meteorological and backwards trajectory data for the flights. D.O. conducted halocarbon analyses. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Jonathan Williams.

Supplementary information

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Creative Commons BYThis work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/