Very short-lived bromomethanes measured by the CARIBIC observatory over the North Atlantic, Africa and Southeast Asia during 2009-2013

Short-lived organic brominated compounds make up a significant part of the organic bromine budget in the atmosphere. Emissions of these compounds are highly variable and there are limited measurements, particularly in the extra-tropical upper troposphere/lower stratosphere and tropical troposphere. Measurements of five very short-lived bromomethanes (VSLB) were made in air samples collected on the CARIBIC project aircraft over three flight routes; Germany to Venezuela/Columbia during 2009-2011, Germany to South Africa during 2010 and 2011 and Germany to Thailand/Kuala Lumpur, Malaysia during 2012 and 2013. In the tropical troposphere, as the most important entrance region to the stratosphere, we observe a total mean organic bromine derived from these compounds across all flights at 10-12 km altitude of 3.4 ± 1.5 ppt. Individual mean tropical tropospheric mixing ratios across all flights were 0.43, 0.74, 0.14, 0.23 and 0.11 ppt for CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CH2BrCl respectively. The highest levels of VSLB-derived bromine (4.20 ± 0.56 ppt) were observed in flights between Bangkok and Kuala Lumpur indicating that the South China Sea is an important source region for these compounds. Across all routes, CHBr and CHBr2 accounted for 34% (4.7-71) and 48% (14-73) respectively of total bromine derived from the analysed VSLB in the tropical mid-upper troposphere totalling 82% (54-89). In samples collected between Germany and Venezuela/Columbia, we find decreasing mean mixing ratios with increasing potential temperature in the extra-tropics. Tropical mean mixing ratios are higher than extra-tropical values between 340-350 K indicating that rapid uplift is important in determining mixing ratios in the lower tropical tropopause layer in the West Atlantic tropics. O3 was used as a tracer for stratospherically influenced air and we detect rapidly decreasing mixing ratios for all VSLB above ∼100 ppb O3 corresponding to the extra-tropical tropopause layer

On the use of mass-conserving wind fields in chemistry-transport models

A new method has been developed that provides mass-conserving wind fields for global chemistry-transport models. In previous global Eulerian modeling studies a mass-imbalance was found between the model mass transport and the surface pressure tendencies. Several methods have been suggested to correct for this imbalance, but so far no satisfactory solution has been found. Our new method solves these problems by using the wind fields in a spherical harmonical form (divergence and vorticity) by mimicing the physics of the weather forecast model as closely as possible. A 3-D chemistry-transport model was used to show that the calculated ozone fields with the new processing method agree remarkably better with ozone observations in the upper troposphere and lower stratosphere. In addition, the calculated age of air in the lower stratosphere show better agreement with observations, although the air remains still too young in the extra-tropical stratosphere

Of tortoise necks and dialects: a new edition of the Grammaticus Leidensis

In this article we provide a new edition of the Byzantine treatise on Greek dialects known under the name Grammaticus Leidensis, in its earliest recoverable form, together with a discussion of the most unusual and intriguing features of this concise treatise.Descriptive and Comparative Linguistic

Tropospheric O3 distribution over the Indian Ocean during spring 1995 evaluated with a chemistry-climate model

An analysis of tropospheric O 3 over the Indian Ocean during spring 1995 is presented based on O 3 soundings and results from the chemistry-general circulation model ECHAM (European Centre Hamburg Model). The ECHAM model is nudged towards actual meteorology using ECMWF analyses, to enable a direct comparison between model results and in situ observations. The model reproduces observed CO levels in different air mass categories. The model also reproduces the general tendencies and the diurnal variation in the observed surface pressure, although the amplitude of the diurnal variation in the amplitude is underestimated. The model simulates the general O 3 tendencies as seen in the sonde observations. Tropospheric O 3 profiles were characterized by low surface concentrations (< 10 ppbv), mid-tropospheric maxima (60-100 ppbv, between 700-250 hPa) and upper-tropospheric minima (< 20 ppbv, between 250-100 hPa). Large-scale upper tropospheric O 3 minima were caused by convective transport of O 3 -depleted boundary layer air in the Inter Tropical Convergence Zone (ITCZ). Similarly, an upper tropospheric O 3 minimum was caused by cyclone Marlene south of the ITCZ. The mid-tropospheric O 3 maxima were caused by transport of polluted African air. The ECHAM model appears to overestimate surface O 3 levels, and does not reproduce the diurnal variations very well This could be related to unaccounted multiphase O 3 destruction mechanisms involving low level clouds and aerosols, and missing halogen chemistr

Methyl chloride as a tracer of tropical tropospheric air in the lowermost stratosphere inferred from IAGOS-CARIBIC passenger aircraft measurements

We present variations of methyl chloride (CH3Cl) and nitrous oxide (N2O) in the lowermost stratosphere (LMS) obtained from air samples collected by the In-service Aircraft for a Global Observing System-Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container (IAGOS-CARIBIC) passenger aircraft observatory for the period 2008-2012. To correct for the temporal increase of atmospheric N2O, the CARIBIC N2O data are expressed as deviations from the long-term trend at the northern hemispheric baseline station Mauna Loa, Hawaii (Delta N2O).Delta N2O undergoes a pronounced seasonal variation in the LMS with a minimum in spring. The amplitude increases going deeper in the LMS (up to potential temperature of 40 K above the thermal tropopause), as a result of the seasonally varying subsidence of air from the stratospheric overworld. Seasonal variation of CH3Cl above the tropopause is similar in phase to that of Delta N2O. Significant correlations are found between CH3Cl and Delta N2O in the LMS from winter to early summer, both being affected by mixing between stratospheric air and upper tropospheric air. This correlation, however, disappears in late summer to autumn. The slope of the CH3Cl-Delta N2O correlation observed in the LMS allows us to determine the stratospheric lifetime of CH3Cl to be 35 +/- 7 years. Finally, we examine the partitioning of stratospheric air and tropical/extratropical tropospheric air in the LMS based on a mass balance approach using Delta N2O and CH3Cl. This analysis clearly indicates efficient inflow of tropical tropospheric air into the LMS in summer and demonstrates the usefulness of CH3Cl as a tracer of tropical tropospheric air

The influence of biogenic emissions from Africa on tropical tropospheric ozone during 2006: a global modeling study

We have performed simulations using a 3-D global chemistry-transport model to investigate the influence that biogenic emissions from the African continent exert on the composition of the troposphere in the tropical region. For this purpose we have applied two recently developed biogenic emission inventories provided for use in large-scale global models (Granier et al., 2005; LathiSre et al., 2006) whose seasonality and temporal distribution for biogenic emissions of isoprene, other volatile organic compounds and NO is markedly different. The use of the 12 year average values for biogenic emissions provided by LathiSre et al. (2006) results in an increase in the amount of nitrogen sequestrated into longer lived reservoir compounds which contributes to the reduction in the tropospheric ozone burden in the tropics. The associated re-partitioning of nitrogen between PAN, HNO3 and organic nitrates also results in a similar to 5% increase in the loss of nitrogen by wet deposition. At a global scale there is a reduction in the oxidizing capacity of the model atmosphere which increases the atmospheric lifetimes of CH4 and CO by similar to 1.5% and similar to 4%, respectively. Comparisons against a range of different measurements indicate that applying the 12 year average of LathiSre et al. (2006) improves the performance of TM4_AMMA for 2006 in the tropics. By the use of sensitivity studies we show that the release of NO from soils in Africa accounts for between similar to 2-45% of tropospheric ozone in the African troposphere, similar to 10% in the upper troposphere and between similar to 5-20% of the tropical tropospheric ozone column over the tropical Atlantic Ocean. The subsequent reduction in OH over the source regions allows enhanced transport of CO out of the region. For biogenic volatile organic C1 to C3 species released from Africa, the effects on tropical tropospheric ozone are rather limited, although this source contributes to the global burden of VOC by between similar to 2-4% and has a large influence on the organic composition of the troposphere over the tropical Atlantic Ocean