The impact of traffic emissions on atmospheric ozone and OH: results from QUANTIFY

To estimate the impact of emissions by road, aircraft and ship traffic on ozone and OH in the present-day atmosphere six different atmospheric chemistry models have been used. Based on newly developed global emission inventories for road, ship and aircraft emission data sets each model performed sensitivity simulations reducing the emissions of each transport sector by 5%. The model results indicate that on global annual average lower tropospheric ozone responds most sensitive to ship emissions (50.6%±10.9% of the total traffic induced perturbation), followed by road (36.7%±9.3%) and aircraft exhausts (12.7%±2.9%), respectively. In the northern upper troposphere between 200–300 hPa at 30–60° N the maximum impact from road and ship are 93% and 73% of the maximum effect of aircraft, respectively. The latter is 0.185 ppbv for ozone (for the 5% case) or 3.69 ppbv when scaling to 100%. On the global average the impact of road even dominates in the UTLS-region. The sensitivity of ozone formation per NOx molecule emitted is highest for aircraft exhausts. The local maximum effect of the summed traffic emissions on the ozone column predicted by the models is 0.2 DU and occurs over the northern subtropical Atlantic extending to central Europe. Below 800 hPa both ozone and OH respond most sensitively to ship emissions in the marine lower troposphere over the Atlantic. Based on the 5% perturbation the effect on ozone can exceed 0.6% close to the marine surface (global zonal mean) which is 80% of the total traffic induced ozone perturbation. In the southern hemisphere ship emissions contribute relatively strongly to the total ozone perturbation by 60%–80% throughout the year. Methane lifetime changes against OH are affected strongest by ship emissions up to 0.21 (± 0.05)%, followed by road (0.08 (±0.01)%) and air traffic (0.05 (± 0.02)%). Based on the full scale ozone and methane perturbations positive radiative forcings were calculated for road emissions (7.3±6.2 mWm−2) and for aviation (2.9±2.3 mWm−2). Ship induced methane lifetime changes dominate over the ozone forcing and therefore lead to a net negative forcing (−25.5±13.2 mWm−2).

Long-lived halocarbon trends and budgets from atmospheric chemistry modelling constrained with measurements in polar firn

The budgets of seven halogenated gases (CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, CCl4 and SF6) are studied by comparing measurements in polar firn air from two Arctic and three Antarctic sites, and simulation results of two numerical models: a 2-D atmospheric chemistry model and a 1-D firn diffusion model. The first one is used to calculate atmospheric concentrations from emission trends based on industrial inventories; the calculated concentration trends are used by the second one to produce depth concentration profiles in the firn. The 2-D atmospheric model is validated in the boundary layer by comparison with atmospheric station measurements, and vertically for CFC-12 by comparison with balloon and FTIR measurements. Firn air measurements provide constraints on historical atmospheric concentrations over the last century. Age distributions in the firn are discussed using a Green function approach. Finally, our results are used as input to a radiative model in order to evaluate the radiative forcing of our target gases. Multi-species and multi-site firn air studies allow to better constrain atmospheric trends. The low concentrations of all studied gases at the bottom of the firn, and their consistency with our model results confirm that their natural sources are small. Our results indicate that the emissions, sinks and trends of CFC-11, CFC-12, CFC-113, CFC-115 and SF6 are well constrained, whereas it is not the case for CFC-114 and CCl4. Significant emission-dependent changes in the lifetimes of halocarbons destroyed in the stratosphere were obtained. Those result from the time needed for their transport from the surface where they are emitted to the stratosphere where they are destroyed. Efforts should be made to update and reduce the large uncertainties on CFC lifetimes.

Using Doppler radar with a simple explicit microphysics model to diagnose problems with ice sublimation depth-scales in forecast models

Several previous studies have attempted to assess the sublimation depth-scales of ice particles from clouds into clear air. Upon examining the sublimation depth-scales in the Met Office Unified Model (MetUM), it was found that the MetUM has evaporation depth-scales 2–3 times larger than radar observations. Similar results can be seen in the European Centre for Medium-Range Weather Forecasts (ECMWF), Regional Atmospheric Climate Model (RACMO) and Météo-France models. In this study, we use radar simulation (converting model variables into radar observations) and one-dimensional explicit microphysics numerical modelling to test and diagnose the cause of the deep sublimation depth-scales in the forecast model. The MetUM data and parametrization scheme are used to predict terminal velocity, which can be compared with the observed Doppler velocity. This can then be used to test the hypothesis as to why the sublimation depth-scale is too large within the MetUM. Turbulence could lead to dry air entrainment and higher evaporation rates; particle density may be wrong, particle capacitance may be too high and lead to incorrect evaporation rates or the humidity within the sublimating layer may be incorrectly represented. We show that the most likely cause of deep sublimation zones is an incorrect representation of model humidity in the layer. This is tested further by using a one-dimensional explicit microphysics model, which tests the sensitivity of ice sublimation to key atmospheric variables and is capable of including sonde and radar measurements to simulate real cases. Results suggest that the MetUM grid resolution at ice cloud altitudes is not sufficient enough to maintain the sharp drop in humidity that is observed in the sublimation zone.

Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the air–water interface – A simple proxy for atmospheric aerosol

The reactions between atmospheric oxidants and organic amphiphiles at the air water interface of an aerosol droplet may affect the size and critical supersaturation required for cloud droplet formation. We demonstrate that no reaction occurs between gaseous nitrogen dioxide (1000 ppm in air) and a monolayer of an insoluble amphiphile, oleic acid (cis-9-octadecenoic acid), at the air water interface which removes material from the air water interface. We present evidence that the NO2 isomerises the cis-9-octadecenoic (oleic) acid to trans-9-octadecenoic (elaidic) acid. The study presented here is important for future and previous studies of (1) the reaction between the nitrate radical, NO3, and thin organic films as NO2 is usually present in high concentrations in these experimental systems and (2) the effect of NO2 air pollution on the unsaturated fatty acids and lipids found at the air liquid surface of human lung lining fluid.

Assessing the impact of nano- and micro-scale zerovalent iron particles on soil microbial activities: Particle reactivity interferes with assay conditions and interpretation of genuine microbial effects

The effects of nano-scale and micro-scale zerovalent iron (nZVI and mZVI) particles on general (dehydrogenase and hydrolase) and specific (ammonia oxidation potential, AOP) activities mediated by the microbial community in an uncontaminated soil were examined. nZVI (diameter 12.5 nm; 10 mg gÿ1 soil)apparently inhibited AOP and nZVI and mZVI apparently stimulated dehydrogenase activity but had minimal influence on hydrolase activity. Sterile experiments revealed that the apparent inhibition of AOP could not be interpreted as such due to the confounding action of the particles, whereas, the nZVIenhanced dehydrogenase activity could represent the genuine response of a stimulated microbial population or an artifact of ZVI reactivity. Overall, there was no evidence for negative effects of nZVI or mZVI on the processes studied. When examining the impact of redox active particles such as ZVI on microbial oxidation–reduction reactions, potential confounding effects of the test particles on assay conditions should be considered.

Chemical and aerosol characterisation of the troposphere over West Africa during the monsoon period as part of AMMA

During June, July and August 2006 five aircraft took part in a campaign over West Africa to observe the aerosol content and chemical composition of the troposphere and lower stratosphere as part of the African Monsoon Multidisciplinary Analysis (AMMA) project. These are the first such measurements in this region during the monsoon period. In addition to providing an overview of the tropospheric composition, this paper provides a description of the measurement strategy (flights performed, instrumental payloads, wing-tip to wing-tip comparisons) and points to some of the important findings discussed in more detail in other papers in this special issue. The ozone data exhibits an "S" shaped vertical profile which appears to result from significant losses in the lower troposphere due to rapid deposition to forested areas and photochemical destruction in the moist monsoon air, and convective uplift of ozone-poor air to the upper troposphere. This profile is disturbed, particularly in the south of the region, by the intrusions in the lower and middle troposphere of air from the southern hemisphere impacted by biomass burning. Comparisons with longer term data sets suggest the impact of these intrusions on West Africa in 2006 was greater than in other recent wet seasons. There is evidence for net photochemical production of ozone in these biomass burning plumes as well as in urban plumes, in particular that from Lagos, convective outflow in the upper troposphere and in boundary layer air affected by nitrogen oxide emissions from recently wetted soils. This latter effect, along with enhanced deposition to the forested areas, contributes to a latitudinal gradient of ozone in the lower troposphere. Biogenic volatile organic compounds are also important in defining the composition both for the boundary layer and upper tropospheric convective outflow. Mineral dust was found to be the most abundant and ubiquitous aerosol type in the atmosphere over Western Africa. Data collected within AMMA indicate that injection of dust to altitudes favourable for long-range transport (i.e. in the upper Sahelian planetary boundary layer) can occur behind the leading edge of mesoscale convective system (MCS) cold-pools. Research within AMMA also provides the first estimates of secondary organic aerosols across the West African Sahel and have shown that organic mass loadings vary between 0 and 2 μg m−3 with a median concentration of 1.07 μg m−3. The vertical distribution of nucleation mode particle concentrations reveals that significant and fairly strong particle formation events did occur for a considerable fraction of measurement time above 8 km (and only there). Very low concentrations were observed in general in the fresh outflow of active MCSs, likely as the result of efficient wet removal of aerosol particles due to heavy precipitation inside the convective cells of the MCSs. This wet removal initially affects all particle size ranges as clearly shown by all measurements in the vicinity of MCSs.

Transport in the low-latitude tropopause zone diagnosed using particle trajectories

Recent literature has described a “transition zone” between the average top of deep convection in the Tropics and the stratosphere. Here transport across this zone is investigated using an offline trajectory model. Particles were advected by the resolved winds from the European Centre for Medium-Range Weather Forecasts reanalyses. For each boreal winter clusters of particles were released in the upper troposphere over the four main regions of tropical deep convection (Indonesia, central Pacific, South America, and Africa). Most particles remain in the troposphere, descending on average for every cluster. The horizontal components of 5-day trajectories are strongly influenced by the El Niño–Southern Oscillation (ENSO), but the Lagrangian average descent does not have a clear ENSO signature. Tropopause crossing locations are first identified by recording events when trajectories from the same release regions cross the World Meteorological Organization lapse rate tropopause. Most crossing events occur 5–15 days after release, and 30-day trajectories are sufficiently long to estimate crossing number densities. In a further two experiments slight excursions across the lapse rate tropopause are differentiated from the drift deeper into the stratosphere by defining the “tropopause zone” as a layer bounded by the average potential temperature of the lapse rate tropopause and the profile temperature minimum. Transport upward across this zone is studied using forward trajectories released from the lower bound and back trajectories arriving at the upper bound. Histograms of particle potential temperature (θ) show marked differences between the transition zone, where there is a slow spread in θ values about a peak that shifts slowly upward, and the troposphere below 350 K. There forward trajectories experience slow radiative cooling interspersed with bursts of convective heating resulting in a well-mixed distribution. In contrast θ histograms for back trajectories arriving in the stratosphere have two distinct peaks just above 300 and 350 K, indicating the sharp change from rapid convective heating in the well-mixed troposphere to slow ascent in the transition zone. Although trajectories slowly cross the tropopause zone throughout the Tropics, all three experiments show that most trajectories reaching the stratosphere from the lower troposphere within 30 days do so over the west Pacific warm pool. This preferred location moves about 30°–50° farther east in an El Niño year (1982/83) and about 30° farther west in a La Niña year (1988/89). These results could have important implications for upper-troposphere–lower-stratosphere pollution and chemistry studies.

Compact cosmic ray detector for unattended atmospheric ionisation monitoring

Two vertical cosmic ray telescopes for atmospheric cosmic ray ionization event detection are compared. Counter A, designed for low power remote use, was deployed in the Welsh mountains; its event rate increased with altitude as expected from atmospheric cosmic ray absorption. Independently, Counter B’s event rate was found to vary with incoming particle acceptance angle. Simultaneous colocated comparison of both telescopes exposed to atmospheric ionization showed a linear relationship between their event rates.

System performance in IR atmospheric radiometry

System aspects of filter radiometer optics used to sense planetary atmospheres are described. Thus the lenses, dichroic beamsplitters and filters in longwave channels of the Mars Observer PMIRR Pressure Modulator Infrared radiometer instrument are assessed individually, and as systems at 20.7µm, 31.9µm, 47.2µm wavelength. A window filter and a longwave calibration filter of the SCARAB earth observer instrument are assessed similarly.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Free atmospheric CO2 enrichment increased above ground biomass but did not affect symbiotic N2-fixation and soil carbon dynamics in a mixed deciduous stand in Wales

Through increases in net primary production (NPP), elevated CO2 is hypothesizes to increase the amount of plant litter entering the soil. The fate of this extra carbon on the forest floor or in mineral soil is currently not clear. Moreover, increased rates of NPP can be maintained only if forests can escape nitrogen limitation. In a Free atmospheric CO2 Enrichment (FACE) experiment near Bangor, Wales, 4 ambient CO2 and 4 FACE plots were planted with patches of Betula pendula, Alnus glutinosa and Fagus sylvatica on a former arable field. Four years after establishment, only a shallow L forest floor litter layer had formed due to intensive bioturbation. Total soil C and N contents increased irrespective of treatment and species as a result of afforestation. We could not detect an additional C sink in the soil, nor were soil C stabilization processes affected by FACE. We observed a decrease of leaf N content in Betula and Alnus under FACE, while the soil C/N ratio decreased regardless of CO2 treatment. The ratio of N taken up from the soil and by N2-fixation in Alnus was not affected by FACE. We infer that increased nitrogen use efficiency is the mechanism by which increased NPP is sustained under elevated CO2 at this site.

Non-intrusive monitoring of atmospheric CO2 in analogue models of terrestrial carbon cycle

1. Closed Ecological Systems (CES) are small manmade ecosystems which do not have any material exchange with the surrounding environment. Recent ecological and technological advances enable successful establishment and maintenance of CES, making them a suitable tool for detecting and measuring subtle feedbacks and mechanisms. 2. As a part of an analogue (physical) C cycle modelling experiment, we developed a non-intrusive methodology to control the internal environment and to monitor atmospheric CO2 concentration inside 16 replicated CES. Whilst maintaining an air-tight seal of all CES, this approach allowed for access to the CO2 measuring equipment for periodic re-calibration and repairs. 3. To ensure reliable cross-comparison of CO2 observations between individual CES units and to minimise the cost of the system, only one CO2 sampling unit was used. An ADC BioScientific OP-2 (open-path) analyser mounted on a swinging arm was passing over a set of 16 measuring cells. Each cell was connected to an individual CES with air continuously circulating between them. 4. Using this setup, we were able to continuously measure several environmental variables and CO2 concentration within each closed system, allowing us to study minute effects of changing temperature on C fluxes within each CES. The CES and the measuring cells showed minimal air leakage during an experimental run lasting, on average, 3 months. The CO2 analyser assembly performed reliably for over 2 years, however an early iteration of the present design proved to be sensitive to positioning errors. 5. We indicate how the methodology can be further improved and suggest possible avenues where future CES based research could be applied.

Observations of Saharan dust layer electrification

Electrification of atmospheric dust influences the coagulation, wet removal and fall speeds of dust particles. Alignment of dust particles can also occur in fair weather atmospheric electrical conditions if the particles are charged. However, very few electrical measurements made in elevated dust layers exist. Balloon-borne charge and particle instrumentation have been used to investigate the electrical properties of elevated Saharan dust layers. Soundings from the Cape Verde Islands, which experience frequent Saharan dust outbreaks, intercepted several dust layers. Two balloon soundings during summer 2009 detected dust particles in layers up to 4 km altitude. Simultaneous electrical measurements showed charge inside the dust layers, with a maximum measured charge density of 25 pC m − 3, sufficient to influence wet removal processes.

Olive oil increases the number of triacylglycerol-rich chylomicron particles compared with other oils: an effect retained when a second standard meal is fed

Background: Compared with the postprandial events after a single meal, different events occur when a second meal is ingested 4–6 h after a first meal. There is a rapid appearance of chylomicrons in the circulation carrying fat ingested with the first meal, with a peak 1 h after the second meal. Objective: Our goal was to examine whether different dietary oils have effects on the storage of triacylglycerol as a result of differences in their digestion, absorption, and incorporation into chylomicrons. Design: A single-blind, randomized, within-subject crossover design was used to study the effects of palm oil, safflower oil, a mixture of fish and safflower oil, and olive oil on postprandial apolipoprotein (apo) B-48, retinyl ester, and triacylglycerol in the Sf > 400 fraction with the use of a sequential meal protocol. Results: For triacylglycerol, retinyl ester, and apo B-48, the time to reach peak concentration was significantly earlier after the second meal than after the first meal (P < 0.005). This was apparent with each of the dietary oils. The pattern of the apo B-48 response differed significantly among the dietary oils, with olive oil resulting in higher concentrations after both meals (P = 0.003). The ratio of triacylglycerol to apo B-48 was significantly lower after olive oil feeding than after feeding with the other oils (P = 0.02). Conclusions: The rapid entry of chylomicrons after the ingestion of a second meal 5 h after a first meal was seen with all of the oils investigated. The short-term ingestion of olive oil produced more chylomicrons than did the other dietary oils, which may have been due to differences in the metabolic handling of olive oil within the gut.