K. A. Read

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.

A two-column method for long-term monitoring of non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (o-VOCs)

A method has been developed for concurrent analysis of C2-C7 hydrocarbons and C2-C5 oxygenated volatile organic compounds (o-VOCs) including alcohols, aldehydes, ketones and ethers. A multi-bed, Peltier-cooled adsorbent trap, consisting of Carboxen 1000 and Carbopack B, was used to acquire one sample per hour. Upon injection the sample was split in an approximately 50:50 ratio between a 50 m aluminium oxide (Al2O3) porous layer open tubular (PLOT) column and a 10 m LOWOX column. Eluents from each column were then analysed using flame ionisation detection (FID). Regular calibration of the system was performed using a standard cylinder mixture at the parts per billion by volume (ppbV) level for non-methane hydrocarbons (NMHCs) and a permeation tube method for the oxygenated species. The system is fully automated with NMHC detection limits between 1 and 10 parts per trillion by volume (pptV) and o-VOC detection limits between 10 and 40 pptV.

Year-round measurements of nitrogen oxides and ozone in the tropical North Atlantic marine boundary layer

[1] A highly sensitive chemiluminescence instrument has been deployed to measure nitric oxide (NO) and nitrogen dioxide (NO 2 ) at the Cape Verde Atmospheric Observatory in the remote tropical North Atlantic marine boundary layer (MBL). Using two different methods, the instrument was assessed to have a detection limit of around 1.8 parts per trillion by volume (pptv) for NO and 5.5 pptv for NO 2 for hour-long integration periods. The overall accuracy was estimated at ∼18% for NO and 30% for NO 2 . Measurements of NO, NO 2 , and ozone (0 3 ) over a period of 12 months in 2007 show very low levels of NO x (typically <30 pptv) and net daytime ozone destruction on most days of the measurement period. Air originating over Africa exhibited the highest levels of NO x (∼35 pptv) and reduced daily 0 3 destruction, with 0 3 production observed on a few days. Air that had not originated over Africa showed lower NO x levels (∼25 pptv), with greater observed 0 3 destruction. A dependence of the observed 0 3 destruction on NO mixing ratios, averaged over all air masses, was observed and reproduced using a simple box model. The model results imply that the presence of between 17 and 34 pptv of NO (depending on the month) would be required to turn the tropical North Atlantic from an 0 3 destroying to an 0 3 producing regime.

Pollution‐enhanced reactive chlorine chemistry in the eastern tropical Atlantic boundary layer

This study examines atmospheric reactive chlorine chemistry at the Cape Verde Atmospheric Observatory in the eastern tropical Atlantic. During May–June, 2007, Cl2 levels ranged from below detection (∼2 ppt) to 30 ppt. Elevated Cl2 was associated with high HNO3 (40 to 120 ppt) in polluted continental outflow transported in the marine boundary layer (MBL) to the site. Lower Cl2 was observed in recently subsided air masses with multiday free tropospheric oceanic trajectories and in air containing Saharan dust. Model simulations show that the observations of elevated Cl2 in polluted marine air are consistent with initiation of Cl chemistry by OH + HCl and subsequent heterogeneous, autocatalytic Cl cycling involving marine aerosols. Model estimates suggest that Cl atom reactions significantly impact the fates of methane and dimethylsulfide at Cape Verde and are moderately important for ozone cycling.

Uptake of methanol to the North Atlantic Ocean surface

An anticorrelation between atmospheric methanol (CH 3 OH) concentrations and wind speed and a positive correlation between dimethylsulphide (DMS) concentrations and wind speed have been observed at the coastal air monitoring site of Mace Head in Ireland, during a period of cyclonic activity in which the averaged surface wind speed changed substantially as a low-pressure system evolved over the northeast Atlantic. These observations suggest a net air-to-sea flux of CH 3 OH. This conclusion is supported by the good agreement between the wind speed dependencies of the measured gas concentrations and theoretical predictions using wind-induced turbulent gas transfer velocities of DMS and CH 3 OH calculated from a resistance model, embedded in a photochemical box model. For a wind speed of 8 m s -1 , an ocean deposition rate of methanol of between 0.02 and 0.33 cm s -1 is calculated, with a best estimate of 0.09 cm s -1 , in good agreement with deposition rates used in global models and derived from atmospheric budgets. The large uncertainty in the calculated deposition rates is due almost entirely to the uncertainty in the degree of saturation of methanol in the surface ocean, highlighting the critical requirement for measurements of methanol in seawater. Owing to the dependence on wind speed, the deposition rates calculated showed substantial range and the calculated contribution of ocean deposition to total loss of CH 3 OH (ocean uptake and gas phase OH oxidation) varied from approximately 20% to 60%.

Atmospheric mercury concentrations observed at ground-based monitoring sites globally distributed in the framework of the GMOS network

Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010-2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in this paper include a clear gradient of Hg concentrations between the Northern and Southern hemispheres, confirming that the gradient observed is mostly driven by local and regional sources, which can be anthropogenic, natural or a combination of both.

OH and halogen atom influence on the variability of non-methane hydrocarbons in the Antarctic Boundary Layer

Ozone measurements from Measurements of OZone and wAter vapour by aIrbus in-service airCraft (MOZAIC) have been assimilated into the global chemical transport model ofMétéo France known as Mod`ele de Chimie Atmosphérique `a Grande Echelle (MOCAGE). The assimilation makes improvements to the free model simulations of ozone in the upper troposphere and lower stratosphere, which are generally overestimated in the tropical region and underestimated in mid-latitudes. The tropical–subtropical gradient of ozone is also improved following assimilation and comparison with vertical profiles from ozonesondes suggests that the assimilation leads to a better representation of the vertical gradient around the tropopause.We use the assimilated fields to calculate a value for the flux of ozone across the tropopause. The net flux of ozone from stratosphere to troposphere is found to be 451 Tg yr-1 before assimilation and 383 Tg yr-1 after assimilation. The downward flux of ozone in the mid-latitudes exhibits an annual cycle with maximum flux occurring in early spring and minimum flux in autumn.

Multiannual observations of acetone, methanol, and acetaldehyde in remote tropical atlantic air: implications for atmospheric OVOC budgets and oxidative capacity.

Oxygenated volatile organic compounds (OVOCs) in the atmosphere are precursors to peroxy acetyl nitrate (PAN), affect the tropospheric ozone budget, and in the remote marine environment represent a significant sink of the hydroxyl radical (OH). The sparse observational database for these compounds, particularly in the tropics, contributes to a high uncertainty in their emissions and atmospheric significance. Here, we show measurements of acetone, methanol, and acetaldehyde in the tropical remote marine boundary layer made between October 2006 and September 2011 at the Cape Verde Atmospheric Observatory (CVAO) (16.85° N, 24.87° W). Mean mixing ratios of acetone, methanol, and acetaldehyde were 546 ± 295 pptv, 742 ± 419 pptv, and 428 ± 190 pptv, respectively, averaged from approximately hourly values over this five-year period. The CAM-Chem global chemical transport model reproduced annual average acetone concentrations well (21% overestimation) but underestimated levels by a factor of 2 in autumn and overestimated concentrations in winter. Annual average concentrations of acetaldehyde were underestimated by a factor of 10, rising to a factor of 40 in summer, and methanol was underestimated on average by a factor of 2, peaking to over a factor of 4 in spring. The model predicted summer minima in acetaldehyde and acetone, which were not apparent in the observations. CAM-Chem was adapted to include a two-way sea-air flux parametrization based on seawater measurements made in the Atlantic Ocean, and the resultant fluxes suggest that the tropical Atlantic region is a net sink for acetone but a net source for methanol and acetaldehyde. Inclusion of the ocean fluxes resulted in good model simulations of monthly averaged methanol levels although still with a 3-fold underestimation in acetaldehyde. Wintertime acetone levels were better simulated, but the observed autumn levels were more severely underestimated than in the standard model. We suggest that the latter may be caused by underestimated terrestrial biogenic African primary and/or secondary OVOC sources by the model. The model underestimation of acetaldehyde concentrations all year round implies a consistent significant missing source, potentially from secondary chemistry of higher alkanes produced biogenically from plants or from the ocean. We estimate that low model bias in OVOC abundances in the remote tropical marine atmosphere may result in up to 8% underestimation of the global methane lifetime due to missing model OH reactivity. Underestimation of acetaldehyde concentrations is responsible for the bulk (∼70%) of this missing reactivity.

Discrepancy between simulated and observed ethane and propane levels explained by underestimated fossil emissions

Ethane and propane are the most abundant non-methane hydrocarbons in the atmosphere. However, their emissions, atmospheric distribution, and trends in their atmospheric concentrations are insufficiently understood. Atmospheric model simulations using standard community emission inventories do not reproduce available measurements in the Northern Hemisphere. Here, we show that observations of pre-industrial and present-day ethane and propane can be reproduced in simulations with a detailed atmospheric chemistry transport model, provided that natural geologic emissions are taken into account and anthropogenic fossil fuel emissions are assumed to be two to three times higher than is indicated in current inventories. Accounting for these enhanced ethane and propane emissions results in simulated surface ozone concentrations that are 5–13% higher than previously assumed in some polluted regions in Asia. The improved correspondence with observed ethane and propane in model simulations with greater emissions suggests that the level of fossil (geologic + fossil fuel) methane emissions in current inventories may need re-evaluation.Observations of ethane and propane distributions in the atmosphere are reproduced in simulations with an atmospheric chemistry transport model, if fossil emissions are a factor of two to three higher than previously assumed.

Perspectives and Integration in SOLAS Science

Why a chapter on Perspectives and Integration in SOLAS Science in this book? SOLAS science by its nature deals with interactions that occur: across a wide spectrum of time and space scales, involve gases and particles, between the ocean and the atmosphere, across many disciplines including chemistry, biology, optics, physics, mathematics, computing, socio-economics and consequently interactions between many different scientists and across scientific generations. This chapter provides a guide through the remarkable diversity of cross-cutting approaches and tools in the gigantic puzzle of the SOLAS realm.