ALBERT

Description: The North Atlantic Marine Boundary Layer Experiment (NAMBLEX), involving over 50 scientists from 12 institutions, took place at Mace Head, Ireland (53.32° N, 9.90° W), between 23 July and 4 September 2002. A wide range of state-of-the-art instrumentation enabled detailed measurements of the boundary layer structure and atmospheric composition in the gas and aerosol phase to be made, providing one of the most comprehensive in situ studies of the marine boundary layer to date. This overview paper describes the aims of the NAMBLEX project in the context of previous field campaigns in the Marine Boundary Layer (MBL), the overall layout of the site, a summary of the instrumentation deployed, the temporal coverage of the measurement data, and the numerical models used to interpret the field data. Measurements of some trace species were made for the first time during the campaign, which was characterised by predominantly clean air of marine origin, but more polluted air with higher levels of NOx originating from continental regions was also experienced. This paper provides a summary of the meteorological measurements and Planetary Boundary Layer (PBL) structure measurements, presents time series of some of the longer-lived trace species (O3, CO, H2, DMS, CH4, NMHC, NOx, NOy, PAN) and summarises measurements of other species that are described in more detail in other papers within this special issue, namely oxygenated VOCs, HCHO, peroxides, organo-halogenated species, a range of shorter lived halogen species (I2, OIO, IO, BrO), NO3 radicals, photolysis frequencies, the free radicals OH, HO2 and (HO2+Σ RO2), as well as a summary of the aerosol measurements. NAMBLEX was supported by measurements made in the vicinity of Mace Head using the NERC Dornier-228 aircraft. Using ECMWF wind-fields, calculations were made of the air-mass trajectories arriving at Mace Head during NAMBLEX, and were analysed together with both meteorological and trace-gas measurements. In this paper a chemical climatology for the duration of the campaign is presented to interpret the distribution of air-mass origins and emission sources, and to provide a convenient framework of air-mass classification that is used by other papers in this issue for the interpretation of observed variability in levels of trace gases and aerosols.

Description: The North Atlantic Marine Boundary Layer Experiment (NAMBLEX), involving over 50 scientists from 12 institutions, took place at Mace Head, Ireland (53.32° N, 9.90° W), between 23 July and 4 September 2002. A wide range of state-of-the-art instrumentation enabled detailed measurements of the boundary layer structure and atmospheric composition in the gas and aerosol phase to be made, providing one of the most comprehensive in situ studies of the marine boundary layer to date. This overview paper describes the aims of the NAMBLEX project in the context of previous field campaigns in the Marine Boundary Layer (MBL), the overall layout of the site, a summary of the instrumentation deployed, the temporal coverage of the measurement data, and the numerical models used to interpret the field data. Measurements of some trace species were made for the first time during the campaign, which was characterised by predominantly clean air of marine origin, but more polluted air with higher levels of NOx originating from continental regions was also experienced. This paper provides a summary of the meteorological measurements and Planetary Boundary Layer (PBL) structure measurements, presents time series of some of the longer-lived trace species (O3, CO, H2, DMS, CH4, NMHC, NOx, NOy, PAN) and summarises measurements of other species that are described in more detail in other papers within this special issue, namely oxygenated VOCs, HCHO, peroxides, organo-halogenated species, a range of shorter lived halogen species (I2, OIO, IO, BrO), NO3 radicals, photolysis frequencies, the free radicals OH, HO2 and (HO2+ΣRO2), as well as a summary of the aerosol measurements. NAMBLEX was supported by measurements made in the vicinity of Mace Head using the NERC Dornier-228 aircraft. Using ECMWF wind-fields, calculations were made of the air-mass trajectories arriving at Mace Head during NAMBLEX, and were analysed together with both meteorological and trace-gas measurements. In this paper a chemical climatology is presented to interpret the distribution of air-mass origins and emission sources, and to provide a convenient framework of air-mass classification that is used by other papers in this issue for the interpretation of observed variability in levels of trace gases and aerosols.

Description: This paper presents extensive validation analyses of ozone observations from the Atmospheric Chemistry Experiment (ACE) satellite instruments: the ACE Fourier Transform Spectrometer (ACE-FTS) and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO) instrument. The ACE satellite instruments operate in the mid-infrared and ultraviolet-visible-near-infrared spectral regions using the solar occultation technique. In order to continue the long-standing record of solar occultation measurements from space, a detailed quality assessment is required to evaluate the ACE data and validate their use for scientific purposes. Here we compare the latest ozone data products from ACE-FTS and ACE-MAESTRO with coincident observations from satellite-borne, airborne, balloon-borne and ground-based instruments, by analysing volume mixing ratio profiles and partial column densities. The ACE-FTS version 2.2 Ozone Update product reports more ozone than most correlative measurements from the upper troposphere to the lower mesosphere. At altitude levels from 16 to 44 km, the mean differences range generally between 0 and +10% with a slight but systematic positive bias (typically +5%). At higher altitudes (45–60 km), the ACE-FTS ozone amounts are significantly larger than those of the comparison instruments by up to ~40% (typically +20%). For the ACE-MAESTRO version 1.2 ozone data product, agreement within ±10% (generally better than ±5%) is found between 18 and 40 km for the sunrise and sunset measurements. At higher altitudes (45–55 km), systematic biases of opposite sign are found between the ACE-MAESTRO sunrise and sunset observations. While ozone amounts derived from the ACE-MAESTRO sunrise occultation data are often smaller than the coincident observations (by as much as −10%), the sunset occultation profiles for ACE-MAESTRO show results that are qualitatively similar to ACE-FTS and indicate a large positive bias (+10 to +30%) in this altitude range. In contrast, there is no significant difference in bias found for the ACE-FTS sunrise and sunset measurements. These systematic effects in the ozone profiles retrieved from the measurements of ACE-FTS and ACE-MAESTRO are being investigated. This work shows that the ACE instruments provide reliable, high quality measurements from the tropopause to the upper stratosphere and can be used with confidence in this vertical domain.

Description: This paper presents extensive {bias determination} analyses of ozone observations from the Atmospheric Chemistry Experiment (ACE) satellite instruments: the ACE Fourier Transform Spectrometer (ACE-FTS) and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO) instrument. Here we compare the latest ozone data products from ACE-FTS and ACE-MAESTRO with coincident observations from nearly 20 satellite-borne, airborne, balloon-borne and ground-based instruments, by analysing volume mixing ratio profiles and partial column densities. The ACE-FTS version 2.2 Ozone Update product reports more ozone than most correlative measurements from the upper troposphere to the lower mesosphere. At altitude levels from 16 to 44 km, the average values of the mean relative differences are nearly all within +1 to +8%. At higher altitudes (45–60 km), the ACE-FTS ozone amounts are significantly larger than those of the comparison instruments, with mean relative differences of up to +40% (about +20% on average). For the ACE-MAESTRO version 1.2 ozone data product, mean relative differences are within ±10% (average values within ±6%) between 18 and 40 km for both the sunrise and sunset measurements. At higher altitudes (~35–55 km), systematic biases of opposite sign are found between the ACE-MAESTRO sunrise and sunset observations. While ozone amounts derived from the ACE-MAESTRO sunrise occultation data are often smaller than the coincident observations (with mean relative differences down to −10%), the sunset occultation profiles for ACE-MAESTRO show results that are qualitatively similar to ACE-FTS, indicating a large positive bias (mean relative differences within +10 to +30%) in the 45–55 km altitude range. In contrast, there is no significant systematic difference in bias found for the ACE-FTS sunrise and sunset measurements.

Description: Measurements of organic carbon compounds in both the gas and particle phases made upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) in the atmosphere over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m−3 from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketone and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.

Description: It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Description: It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Description: The Atmospheric Chemistry Experiment (ACE) mission was launched in August 2003 to sound the atmosphere by solar occultation. Water vapour (H2O), one of the most important molecules for climate and atmospheric chemistry, is one of the key species provided by the two principal instruments, the infrared Fourier Transform Spectrometer (ACE-FTS) and the MAESTRO UV-Visible spectrometer (ACE-MAESTRO). The first instrument performs measurements on several lines in the 1362–2137 cm−1 range, from which vertically resolved H2O concentration profiles are retrieved, from 7 to 90 km altitude. ACE-MAESTRO measures profiles using the water absorption band in the near infrared part of the spectrum at 926.0–969.7 nm. This paper presents a comprehensive validation of the ACE-FTS profiles. We have compared the H2O volume mixing ratio profiles with space-borne (SAGE II, HALOE, POAM III, MIPAS, SMR) observations and measurements from balloon-borne frostpoint hygrometers and a ground based lidar. We show that the ACE-FTS measurements provide H2O profiles with small retrieval uncertainties in the stratosphere (better than 5% from 15 to 70 km, gradually increasing above). The situation is unclear in the upper troposphere, due mainly to the high variability of the water vapour volume mixing ratio in this region. A new water vapour data product from the ACE-MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) is also presented and initial comparisons with ACE-FTS are discussed.

Description: During the 2003 SAGE (Stratospheric Aerosol and Gas Experiment) III Ozone Loss and Validation Experiment (SOLVE) II, the fourteen-channel NASA Ames Airborne Tracking Sunphotometer (AATS-14) was mounted on the NASA DC-8 aircraft and measured spectra of total and aerosol optical depth (TOD and AOD) during the sunlit portions of eight science flights. Values of ozone column content above the aircraft have been derived from the AATS-14 measurements by using a linear least squares method that exploits the differential ozone absorption in the seven AATS-14 channels located within the Chappuis band. We compare AATS-14 columnar ozone retrievals with temporally and spatially near-coincident measurements acquired by the SAGE III and the Polar Ozone and Aerosol Measurement (POAM) III satellite sensors during four solar occultation events observed by each satellite. RMS differences are 19 DU (7% of the AATS value) for AATS-SAGE and 10 DU (3% of the AATS value) for AATS-POAM. In these checks of consistency between AATS-14 and SAGE III or POAM III ozone results, the AATS-14 analyses use airmass factors derived from the relative vertical profiles of ozone and aerosol extinction obtained by SAGE III or POAM III. We also compare AATS-14 ozone retrievals for measurements obtained during three DC-8 flights that included extended horizontal transects with total column ozone data acquired by the Total Ozone Mapping Spectrometer (TOMS) and the Global Ozone Monitoring Experiment (GOME) satellite sensors. To enable these comparisons, the amount of ozone in the column below the aircraft is estimated either by assuming a climatological model or by combining SAGE and/or POAM data with high resolution in-situ ozone measurements acquired by the NASA Langley Research Center chemiluminescent ozone sensor, FASTOZ, during the aircraft vertical profile at the start or end of each flight. Resultant total column ozone values agree with corresponding TOMS and GOME measurements to within 10-15 DU (~3%) for AATS data acquired during two flights - a longitudinal transect from Sweden to Greenland on 21 January, and a latitudinal transect from 47° N to 35° N on 6 February. For the round trip DC-8 latitudinal transect between 34° N and 22° N on 19-20 December 2002, resultant AATS-14 ozone retrievals plus below-aircraft ozone estimates yield a latitudinal gradient that is similar in shape to that observed by TOMS and GOME, but resultant AATS values exceed the corresponding satellite values by up to 30 DU at certain latitudes. These differences are unexplained, but they are attributed to spatial and temporal variability that was associated with the dynamics near the subtropical jet but was unresolved by the satellite sensors. For selected cases, we also compare AATS-14 ozone retrievals with values derived from coincident measurements by the other two DC-8 based solar occultation instruments: the National Center for Atmospheric Research Direct beam Irradiance Airborne Spectrometer (DIAS) and the NASA Langley Research Center Gas and Aerosol Monitoring System (GAMS). AATS and DIAS retrievals agree to within RMS differences of 1% of the AATS values for the 21 January and 19-20 December flights, and 2.3% for the 6 February flight. Corresponding AATS-GAMS RMS differences are ~1.5% for the 21 January flight; GAMS data were not compared for the 6 February flight and were not available for the 19-20 December flight. Line of sight ozone retrievals from coincident measurements obtained by the three DC-8 solar occultation instruments during the SAGE III solar occultation event on 24 January yield RMS differences of 2.1% for AATS-DIAS and 0.5% for AATS-GAMS.

Description: The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv. Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.