Steven R. Utembe

Ozone sensors based on WO3: a model for sensor drift and a measurement correction method

The use of a tungstic oxide semiconductor as a sensor for ozone at concentration levels relevant to atmospheric monitoring applications is an important advance in attempts to produce cheap, lightweight and reliable instruments. Problems of stability are a possible obstacle to this application. A model that describes the response of these sensors to ozone is proposed here and using it an explanation for the drift of resistance with time at constant concentrations of ozone is given. Consideration of this drift model enables a measurement routine to be employed that compensates for the drift observed experimentally, thus producing a reliable calibration of the sensor.

Modelling the ambient distribution of organic compounds during the August 2003 ozone episode in the southern UK

A photochemical trajectory model containing speciated emissions of 124 non-methane volatile organic compounds (VOC), and a comprehensive description of the chemistry of VOC degradation, has been used to simulate the chemical evolution of boundary layer air masses arriving at a field campaign site in the southern UK during a widespread and prolonged photochemical pollution event in August 2003. The simulated concentrations and distributions of organic compounds at the arrival location are compared with observations of a series of hydrocarbons and carbonyl compounds, which were measured using GC-FID and multidimensional GC methods. The comparison of the simulated and observed distributions of 34 emitted hydrocarbons provides some support for the magnitude and applied emissions speciation of anthropogenic hydrocarbons, but is indicative of an under representation of the input of biogenic hydrocarbons, particularly at elevated temperatures. Simulations of the detailed distribution of ca. 1250 carbonyl compounds, formed primarily from the degradation of the 124 emitted VOC, focus on 61 aldehydes, ketones, dicarbonyls, hydroxycarbonyls and aromatic aldehydes which collectively account for ca. 90% of the simulated total molar concentration of carbonyls. The simulated distributions indicate that the photolysis of formaldehyde and alpha-dicarbonyls make major contributions to free radical production for the arrival conditions of five case study trajectories. The simulated concentrations of hydroxycarbonyls demonstrate preferential formation of the 1,4-substituted isomers (compared with 1,2- and 1,3-isomers of the same carbon number), which are formed during the initial oxidation sequence of longer chain alkanes.

Secondary organic aerosol formation from a large number of reactive man-made organic compounds.

A photochemical trajectory model has been used to examine the relative propensities of a wide variety of volatile organic compounds (VOCs) emitted by human activities to form secondary organic aerosol (SOA) under one set of highly idealised conditions representing northwest Europe. This study applied a detailed speciated VOC emission inventory and the Master Chemical Mechanism version 3.1 (MCM v3.1) gas phase chemistry, coupled with an optimised representation of gas-aerosol absorptive partitioning of 365 oxygenated chemical reaction product species. In all, SOA formation was estimated from the atmospheric oxidation of 113 emitted VOCs. A number of aromatic compounds, together with some alkanes and terpenes, showed significant propensities to form SOA. When these propensities were folded into a detailed speciated emission inventory, 15 organic compounds together accounted for 97% of the SOA formation potential of UK man made VOC emissions and 30 emission source categories accounted for 87% of this potential. After road transport and the chemical industry, SOA formation was dominated by the solvents sector which accounted for 28% of the SOA formation potential.

On the effect of a global adoption of various fractions of biodiesel on key species in the troposphere

Biodiesel use is being promoted worldwide as a green alternative to conventional diesel. A global three-dimensional chemistry transport model is employed to investigate the impact on air quality and global tropospheric composition of adopting biodiesel as a fractional component of diesel use. Five global simulations are conducted where emission changes of hydrocarbons and nitrogen oxides were applied within the model to investigate changes in tropospheric pollutants. Hydrocarbon emission reductions lead to an overall improvement in air quality with reductions in ozone, organic aerosol, aromatic species and PAN. However when the increase in NOx, caused by increased exhaust temperature, is included there is negligible difference in ozone production between mineral diesel and biodiesel blends. The cause of these effects is discussed. [Received: September 30, 2009; Accepted: December 12, 2009]

Global Budget and Distribution of Peroxyacetyl Nitrate (PAN) for Present and Preindustrial Scenarios

A global 3-D chemistry and transport model, STOCHEM integrated with a detailed VOC oxidation scheme (CRI v2-R5) has been employed to study the important NOx reservoir compound, peroxyacetyl nitrate (PAN). Globally, PAN is produced entirely by the reaction of acetyl peroxy radicals (CH3CO3) with NO2 and up to 2.0 ppb of PAN is found over the polluted regions of North America during June- July-August for the present scenario. The imbalances between model and measurement data are noted, with STOCHEM-CRI overestimating PAN mixing ratios relative to the measurement data by +17 and +80 pptv for the lower and upper troposphere, respectively. The inclusion of additional HOx recycling mechanisms (e.g. related to isoprene oxidation) in STOCHEM-CRI causes a decrease in PAN in a present scenario by as much as 40% over sink regions and reduces the model-measurement disagreement by 90% for the lower troposphere and 40% for the upper troposphere. The lower NOx emissions and CH3CO3 formation upon including HOx recycling in a preindustrial scenario led to a decrease in PAN formation by as much as 40%. The decrease in PAN formation results in less nitrogen being transported to remote regions which in turn leads to the greatest percentage change in O3 concentration (9% decrease) in the equatorial regions.

The Potential of the Geostationary Carbon Cycle Observatory (GeoCarb) to Provide Multi-scale Constraints on the Carbon Cycle in the Americas

The second NASA Earth Venture Mission, Geostationary Carbon Cycle Observatory (GeoCarb), will provide measurements of atmospheric carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), and solar-induced fluorescence (SIF) from Geostationary Orbit (GEO). The GeoCarb mission will deliver daily maps of column concentrations of CO2, CH4, and CO over the observed landmasses in the Americas at a spatial resolution of roughly 10 x 10 km. Persistent measurements of CO2, CH4, CO, and SIF will contribute significantly to resolving carbon emissions and illuminating biotic processes at urban to continental scales, which will allow the improvement of modeled biogeochemical processes in Earth System Models as well as monitor the response of the biosphere to disturbance. This is essential to improve understanding of the Carbon-Climate connection. In this paper, we introduce the instrument and the GeoCarb Mission, and we demonstrate the potential scientific contribution of the mission through a series of CO2 and CH4 simulation experiments. We find that GeoCarb will be able to constrain emissions at urban to continental spatial scales on weekly to annual time scales. The GeoCarb mission particularly builds upon the Orbiting Carbon Obserevatory-2 (OCO-2), which is flying in Low Earth Orbit.