Alfonso Saiz-Lopez

Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean

Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is ∼50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

Atmospheric Chemistry of Iodine

Atmospheric Chemistry of Iodine Alfonso Saiz-Lopez,* John M. C. Plane,* Alex R. Baker, Lucy J. Carpenter, Roland von Glasow, Juan C. G omez Martín, Gordon McFiggans, and Russell W. Saunders Laboratory for Atmospheric and Climate Science (CIAC), CSIC, Toledo, Spain School of Chemistry, University of Leeds, Leeds, LS2 9JT, United Kingdom School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, United Kingdom Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom School of Earth, Atmospheric & Environmental Sciences, University of Manchester, Manchester, M13 9PL, United Kingdom

Tropospheric Halogen Chemistry:Sources, Cycling, and Impacts

In the past 40 years, atmospheric chemists have come to realize that halogens exert a powerful influence on the chemical composition of the troposphere and through that influence affect the fate of pollutants and may affect climate. Of particular note for climate is that halogen cycles affect methane, ozone, and particles, all of which are powerful climate forcing agents through direct and indirect radiative effects. This influencecomes from the high reactivity of atomic halogen radicals (e.g.,Cl, Br, I) and halogen oxides (e.g., ClO, BrO, IO, and higher oxides), known as reactive halogen species in this review. These reactive halogens are potent oxidizers for organic and inorganic compounds throughout the troposphere.

Atmospheric ammonia and its impacts on regional air quality over the megacity of Shanghai, China.

Atmospheric ammonia (NH3) has great environmental implications due to its important role in ecosystem and global nitrogen cycle, as well as contribution to secondary particle formation. Here, we report long-term continuous measurements of NH3 at different locations (i.e. urban, industrial and rural) in Shanghai, China, which provide an unprecedented portrait of temporal and spatial characteristics of atmospheric NH3 in and around this megacity. In addition to point emission sources, air masses originated from or that have passed over ammonia rich areas, e.g. rural and industrial sites, increase the observed NH3 concentrations inside the urban area of Shanghai. Remarkable high-frequency NH3 variations were measured at the industrial site, indicating instantaneous nearby industrial emission peaks. Additionally, we observed strong positive exponential correlations between NH4+/(NH4++NH3) and sulfate-nitrate-ammonium (SNA) aerosols, PM2.5 mass concentrations, implying a considerable contribution of gas-to-particle conversion of ammonia to SNA aerosol formation. Lower temperature and higher humidity conditions were found to favor the conversion of gaseous ammonia to particle ammonium, particularly in autumn. Although NH3 is currently not included in China’s emission control policies of air pollution precursors, our results highlight the urgency and importance of monitoring gaseous ammonia and improving its emission inventory in and around Shanghai.

Modelling future changes to the stratospheric source gas injection of biogenic bromocarbons

Simulations with a chemistry-climate model (CCM) show a future increase in the stratospheric source gas injection (SGI) of biogenic very short-lived substances (VSLS). For 2000, the modelled SGI of bromine from VSLS is similar to 1.7 parts per trillion (pptv) and largest over the tropical West Pacific. For 2100, this increases to similar to 2.0 and similar to 2.7 pptv when the model is forced with Intergovernmental Panel on Climate Change (IPCC) representative concentration pathways (RCPs) 4.5 and 8.5. The increase is largely due to stronger tropical deep convection transporting more CHBr3 to the lower stratosphere. For CH2Br2, CHBr2Cl, CH2BrCl and CHBrCl2, changes to primary oxidant OH determines their SGI contribution. Under RCP 4.5 (moderate warming), OH increases in a warmer, more humid troposphere. Under RCP 8.5 (extreme warming) OH decreases significantly due to a large methane increase, allowing greater SGI of bromine from these VSLS. Potentially enhanced VSLS emissions in the future would further increase these estimates. Citation: Hossaini, R., et al. (2012), Modelling future changes to the stratospheric source gas injection of biogenic bromocarbons, Geophys. Res. Lett., 39, L20813, doi:10.1029/2012GL053401.

The convective transport of active species in the tropics (Contrast) experiment

The Convective Transport of Active Species in the Tropics (CONTRAST) experiment was conducted from Guam (13.5° N, 144.8° E) during January-February 2014. Using the NSF/NCAR Gulfstream V research aircraft, the experiment investigated the photochemical environment over the tropical western Pacific (TWP) warm pool, a region of massive deep convection and the major pathway for air to enter the stratosphere during Northern Hemisphere (NH) winter. The new observations provide a wealth of information for quantifying the influence of convection on the vertical distributions of active species. The airborne in situ measurements up to 15 km altitude fill a significant gap by characterizing the abundance and altitude variation of a wide suite of trace gases. These measurements, together with observations of dynamical and microphysical parameters, provide significant new data for constraining and evaluating global chemistry climate models. Measurements include precursor and product gas species of reactive halogen compounds that impact ozone in the upper troposphere/lower stratosphere. High accuracy, in-situ measurements of ozone obtained during CONTRAST quantify ozone concentration profiles in the UT, where previous observations from balloon-borne ozonesondes were often near or below the limit of detection. CONTRAST was one of the three coordinated experiments to observe the TWP during January-February 2014. Together, CONTRAST, ATTREX and CAST, using complementary capabilities of the three aircraft platforms as well as ground-based instrumentation, provide a comprehensive quantification of the regional distribution and vertical structure of natural and pollutant trace gases in the TWP during NH winter, from the oceanic boundary to the lower stratosphere.

A pervasive role for biomass burning in tropical high ozone/low water structures

Air parcels with mixing ratios of high O3 and low H2O (HOLW) are common features in the tropical western Pacific (TWP) mid-troposphere (300–700 hPa). Here, using data collected during aircraft sampling of the TWP in winter 2014, we find strong, positive correlations of O3 with multiple biomass burning tracers in these HOLW structures. Ozone levels in these structures are about a factor of three larger than background. Models, satellite data and aircraft observations are used to show fires in tropical Africa and Southeast Asia are the dominant source of high O3 and that low H2O results from large-scale descent within the tropical troposphere. Previous explanations that attribute HOLW structures to transport from the stratosphere or mid-latitude troposphere are inconsistent with our observations. This study suggest a larger role for biomass burning in the radiative forcing of climate in the remote TWP than is commonly appreciated.

Airborne measurements of organic bromine compounds in the Pacific tropical tropopause layer

Significance This study reports an extensive set of in situ measurements of natural organic bromine species at the tropical tropopause. Compared with prior estimates, this study reduces the uncertainty of the contribution of reactive bromine to stratospheric ozone depletion. We compare measurements over the Eastern and Western Pacific, two regions characterized by different transport dynamics, to show the influence of convective events on the chemistry of the tropopause region. Using measurements and modeling, we describe the budget and partitioning of bromine at the tropical tropopause and evaluate the contribution of bromine to ozone destruction in the lower stratosphere. Very short-lived brominated substances (VSLBr) are an important source of stratospheric bromine, an effective ozone destruction catalyst. However, the accurate estimation of the organic and inorganic partitioning of bromine and the input to the stratosphere remains uncertain. Here, we report near-tropopause measurements of organic brominated substances found over the tropical Pacific during the NASA Airborne Tropical Tropopause Experiment campaigns. We combine aircraft observations and a chemistry−climate model to quantify the total bromine loading injected to the stratosphere. Surprisingly, despite differences in vertical transport between the Eastern and Western Pacific, VSLBr (organic + inorganic) contribute approximately similar amounts of bromine [∼6 (4−9) parts per thousand] to the stratospheric input at the tropical tropopause. These levels of bromine cause substantial ozone depletion in the lower stratosphere, and any increases in future abundances (e.g., as a result of aquaculture) will lead to larger depletions.

Glyoxal observations in the global marine boundary layer

Glyoxal is an important intermediate species formed by the oxidation of common biogenic and anthropogenic volatile organic compounds such as isoprene, toluene, and acetylene. Although glyoxal has been shown to play an important role in urban and forested environments, its role in the open ocean environment is still not well understood, with only a few observations showing evidence for its presence in the open ocean marine boundary layer (MBL). In this study, we report observations of glyoxal from 10 field campaigns in different parts of the worlds oceans. These observations together represent the largest database of glyoxal in the MBL. The measurements are made with similar instruments that have been used in the past, although the open ocean values reported here, average of about 25 parts per trillion by volume (pptv) with an upper limit of 40 pptv, are much lower than previously reported observations that were consistently higher than 40 pptv and had an upper limit of 140 pptv, highlighting the uncertainties in the differential optical absorption spectroscopy method for the retrieval of glyoxal. Despite retrieval uncertainties, the results reported in this work support previous suggestions that the currently known sources of glyoxal are insufficient to explain the average MBL concentrations. This suggests that there is an additional missing source, more than a magnitude larger than currently known sources, which is necessary to account for the observed atmospheric levels of glyoxal. Therefore, it could play a more important role in the MBL than previously considered.

Bimodal distribution of free tropospheric ozone over the tropical western Pacific revealed by airborne observations

A recent airborne field campaign over the remote western Pacific obtained the first intensive in situ ozone sampling over the warm pool region from oceanic surface to 15 km altitude (near 360 K potential temperature level). The new data set quantifies ozone in the tropical tropopause layer under significant influence of convective outflow. The analysis further reveals a bimodal distribution of free tropospheric ozone mixing ratio. A primary mode, narrowly distributed around 20 ppbv, dominates the troposphere from the surface to 15 km. A secondary mode, broadly distributed with a 60 ppbv modal value, is prominent between 3 and 8 km (320 K to 340 K potential temperature levels). The latter mode occurs as persistent layers of ozone-rich drier air and is characterized by relative humidity under 45%. Possible controlling mechanisms are discussed. These findings provide new insight into the physical interpretation of the “S”-shaped mean ozone profiles in the tropics.