J. B. McQuaid

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.

Modeling OH, HO2, and RO2 radicals in the marine boundary layer: 1. Model construction and comparison with field measurements

An observationally constrained box model has been constructed in order to investigate the chemistry of the marine boundary layer at Mace Head, a remote location on the west coast of Ireland. The primary aim of the model is to reproduce concentrations of the hydroxyl (OH) and hydroperoxy (HO2) radicals measured by an in situ fluorescence assay by gas expansion (PAGE) instrument, and the sum of peroxy radicals ∑([HO2]+[RO2]) determined by a peroxy radical chemical amplification (PERCA) instrument. The model has been constructed based on observed concentrations of a suite of non-methane hydrocarbons, measured in situ by gas chromatography. The chemical mechanism for the model is a subset of a comprehensive master chemical mechanism (MCM). This paper describes in detail the construction of the model, as well as the underlying approach. Comparisons of modeled and measured concentrations of radical species, from a recent field campaign held at the Mace Head Atmospheric Observatory during July and August 1996 (EASE 96), are also presented. For the limited OH data available from this campaign, the model tends to overestimate the observations by about 40%, although this discrepancy is within the uncertainties of the model (±31%, 2σ) and the PAGE measurements (±75% on average, 2σ). For HO2 the model reproduces the concentrations well on one day but less well on another. Low HOx concentrations compared to model results have been observed previously, with greater than expected heterogeneous losses invoked to explain the differences. Comparisons between measurements of peroxy radicals made by chemical amplification and model predictions show good agreement over a wide range of conditions.

Nitrogen management is essential to prevent tropical oil palm plantations from causing ground-level ozone pollution

More than half the worlds rainforest has been lost to agriculture since the Industrial Revolution. Among the most widespread tropical crops is oil palm (Elaeis guineensis): global production now exceeds 35 million tonnes per year. In Malaysia, for example, 13% of land area is now oil palm plantation, compared with 1% in 1974. There are enormous pressures to increase palm oil production for food, domestic products, and, especially, biofuels. Greater use of palm oil for biofuel production is predicated on the assumption that palm oil is an “environmentally friendly” fuel feedstock. Here we show, using measurements and models, that oil palm plantations in Malaysia directly emit more oxides of nitrogen and volatile organic compounds than rainforest. These compounds lead to the production of ground-level ozone (O3), an air pollutant that damages human health, plants, and materials, reduces crop productivity, and has effects on the Earths climate. Our measurements show that, at present, O3 concentrations do not differ significantly over rainforest and adjacent oil palm plantation landscapes. However, our model calculations predict that if concentrations of oxides of nitrogen in Borneo are allowed to reach those currently seen over rural North America and Europe, ground-level O3 concentrations will reach 100 parts per billion (109) volume (ppbv) and exceed levels known to be harmful to human health. Our study provides an early warning of the urgent need to develop policies that manage nitrogen emissions if the detrimental effects of palm oil production on air quality and climate are to be avoided.

Meteorology, air quality, and health in London: The ClearfLo project

AbstractAir quality and heat are strong health drivers, and their accurate assessment and forecast are important in densely populated urban areas. However, the sources and processes leading to high concentrations of main pollutants, such as ozone, nitrogen dioxide, and fine and coarse particulate matter, in complex urban areas are not fully understood, limiting our ability to forecast air quality accurately. This paper introduces the Clean Air for London (ClearfLo; www.clearflo.ac.uk) project’s interdisciplinary approach to investigate the processes leading to poor air quality and elevated temperatures.Within ClearfLo, a large multi-institutional project funded by the U.K. Natural Environment Research Council (NERC), integrated measurements of meteorology and gaseous, and particulate composition/loading within the atmosphere of London, United Kingdom, were undertaken to understand the processes underlying poor air quality. Long-term measurement infrastructure installed at multiple levels (street and eleva...

Chemical composition observed over the mid-atlantic and the detection of pollution signatures far from source regions

The atmospheric composition of the central North Atlantic region has been sampled using the FAAM BAe146 instrumented aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) campaign, part of the wider International Consortium for Atmospheric Research on Transport and Transformation (ICARTT). This paper presents an overview of the ITOP campaign. Between late July and early August 2004, twelve flights comprising 72 hours of measurement were made in a region from approximately 20 to 40°W and 33 to 47°N centered on Faial Island, Azores, ranging in altitude from 50 to 9000 m. The vertical profiles of O3 and CO are consistent with previous observations made in this region during 1997 and our knowledge of the seasonal cycles within the region. A cluster analysis technique is used to partition the data set into air mass types with distinct chemical signatures. Six clusters provide a suitable balance between cluster generality and specificity. The clusters are labeled as biomass burning, low level outflow, upper level outflow, moist lower troposphere, marine and upper troposphere. During this summer, boreal forest fire emissions from Alaska and northern Canada were found to provide a major perturbation of tropospheric composition in CO, PAN, organic compounds and aerosol. Anthropogenic influenced air from the continental boundary layer of the USA was clearly observed running above the marine boundary layer right across the mid-Atlantic, retaining high pollution levels in VOCs and sulfate aerosol. Upper level outflow events were found to have far lower sulfate aerosol, resulting from washout on ascent, but much higher PAN associated with the colder temperatures. Lagrangian links with flights of other aircraft over the USA and Europe show that such signatures are maintained many days downwind of emission regions. Some other features of the data set are highlighted, including the strong perturbations to many VOCs and OVOCs in this remote region.

In situ , gas chromatographicmeasurements of non-methane hydrocarbons and dimethylsulfide at a remote coastal location (Mace Head, Eire)July–August 1996

Atmospheric non-methane hydrocarbons (NMHC) and dimethyl sulfide (DMS) have been monitored at a remote coastal location (Mace Head, Eire) using adsorption sampling techniques with analysis by in situ gas chromatography as part of the ACSOE OXICOA 1996 campaign. Concentrations varied considerably during the campaign but can be consistently interpreted by consideration of the relevant back-trajectory of the monitored air mass. Isoprene is confirmed as the most important NMHC in determining OH removal, contributing to up to 20%. Isoprene shows strong diurnal variations, although the structure of the diurnal pattern depends on the origin of the air mass. In contrast to previous studies, DMS concentrations during the campaign appeared to show no consistent diurnal variation.

Two high-speed, portable GC systems designed for the measurement of non-methane hydrocarbons and PAN: results from the Jungfraujoch High Altitude Observatory.

Near real-time measurements of light non-methane hydrocarbons (NMHCs) and peroxyacetyl nitrate (PAN) have been performed in the free troposphere using two fast gas chromatography (GC) instruments designed for use on aircraft. A GC-helium ionisation detector (HID) system measured 15 C(2)-C(5) hydrocarbons with 5 min time resolution and a dual channel GC-Electron Capture Detector (ECD) measured PAN with 90 s resolution. Both instruments had low parts per trillion by volume (pptV) detection limits and ran continuously at the remote Jungfraujoch (JFJ) research station in the Swiss Alps (46.55[degree]N, 7.98[degree]E), 3580 m above mean sea level (AMSL), during February/March 2003. Carbon monoxide, ozone, nitrogen oxide and nitrogen dioxide and all odd nitrogen species (NO(y)) were also measured continuously. Hydrocarbons and CO were strongly correlated in all air-masses whilst PAN exhibited both positive and negative correlations with respect to O(3), dependent on age and origin of the air-mass sampled. PAN was found to contribute [similar]20% to the NO(y) sampled on average. The experiment, as well as providing interesting datasets from this remote location, also demonstrated that when optimised, GC techniques have the potential to measure at a time resolution significantly greater than is traditionally considered, with high sensitivity and low uncertainty.

The Fennec Automatic Weather Station (AWS) Network: Monitoring the Saharan Climate System

TheFennecautomaticweatherstation(AWS)networkconsistsofeightstationsinstalledacrosstheSahara, with four in remote locations in the central desert, where no previous meteorological observations have existed. The AWS measures temperature, humidity, pressure, wind speed, wind direction, shortwave and longwave radiation (upwelling and downwelling), ground heat flux, and ground temperature. Data are recorded every 3 min 20 s, that is, at 3 times the temporal resolution of the World Meteorological Organization’s standard 10-min reporting for winds and wind gusts. Variations in wind speeds on shorter time scales are recorded through the use of second- and third-order moments of 1-Hz data. Using the Iridium RouterBased Unrestricted Digital Internetworking Connectivity Solutions (RUDICS) service, data are transmitted in near‐real time (1-h lag) to the United Kingdom, where calibrations are applied and data are uploaded to the Global Telecommunications System (GTS), for assimilation into forecast models. This paper describes the instrumentation used and the data available from the network. Particular focus is given to the engineering applied to the task of making measurements in this remote region and challenging climate. The communications protocol developed to operate over the Iridium RUDICS satellite service is described. Transmitting the second moment of the wind speed distribution is shown to improve estimates of the dust-generating potential of observed winds, especially for winds close to the threshold speed for dust emission of the wind speed distribution. Sources of error are discussed and some preliminary results are presented, demonstrating the system’s potential to record key features of this region.

PHYSICAL EXCHANGES AT THE AIR-SEA INTERFACE UK-SOLAS Field Measurements

As part of the U.K. contribution to the international Surface Ocean–Lower Atmosphere Study, a series of three related projects—DOGEE, SEASAW, and HiWASE—undertook experimental studies of the processes controlling the physical exchange of gases and sea spray aerosol at the sea surface. The studies share a common goal: to reduce the high degree of uncertainty in current parameterization schemes. The wide variety of measurements made during the studies, which incorporated tracer and surfactant release experiments, included direct eddy correlation fluxes, detailed wave spectra, wind history, photographic retrievals of whitecap fraction, aerosol-size spectra and composition, surfactant concentration, and bubble populations in the ocean mixed layer. Measurements were made during three cruises in the northeast Atlantic on the RRS Discovery during 2006 and 2007; a fourth campaign has been making continuous measurements on the Norwegian weather ship Polarfront since September 2006. This paper provides an overview of the three projects and some of the highlights of the measurement campaigns.

Diurnal cycles of short-lived tropospheric alkenes at a north Atlantic coastal site

Abstract Observation of diurnal cycles in atmospheric concentrations of reactive alkenes are reported from measurements performed at a North Atlantic coastal site (Mace Head, Eire 53°19′34″N; 9°54′14″W). Species seen to exhibit distinct cycles included isoprene, ethene, propene, 1-butene, iso-butene and a substituted C6 alkene. Five hundred and thirty air mass classified measurements were performed over a 4 week period at approximately hourly frequency and demonstrate that during periods when air flow resulted from unpolluted oceanic regions a clear daily cycle in concentrations existed, peaking at around solar noon for all species. These observations support the proposed mechanism of production via photochemical degradation of organic carbon in sea water. The observed concentrations showed strong correlation (propene R2>0.75) with solar flux, with little relationship to other meteorological or chemical parameters. The species’ short atmospheric lifetimes indicate that the source of emission was from local coastal waters within close proximity of the sampling site. At solar noon concentrations of reactive alkenes from oceanic sources were responsible for up to 88% of non-methane hydrocarbon reaction with the hydroxyl radical at this coastal marine site.