Volatile organic compound fluxes and mixing ratios in two contrasting atmospheric environments:London and the Amazon rainforest

Volatile organic compounds (VOCs) from biogenic and anthropogenic sources are important constituents of the atmosphere with effects on air quality and climate. Current uncertainties in measurements and models relate to their roles in tropospheric ozone and secondary organic aerosol formation, yet there have been few measurements of their fluxes from contrasting chemical environments. Additional measurements with greater spatial and temporal resolutions are required to constrain uncertainties in atmospheric chemistry and climate models. This thesis presents long-term measurements of VOC fluxes and concentrations in two contrasting environments: central London and the Brazilian Amazon. VOC concentrations were quantified by proton transfer reaction-mass spectrometry and fluxes were calculated using the virtual disjunct eddy covariance method over a period of several months at sites in central London and the Amazon rainforest. In central London, traffic was found to be the main source of aromatic compounds. Oxygenated compounds and isoprene showed strong correlations with light and temperature, suggesting biogenic, evaporative, or secondary atmospheric origins. The seven VOCs measured in central London had a five-month average total emission rate of 1.4 mg m-2 h-1. Comparisons with local and national emission inventories showed that modelled emissions were largely underestimated. Measurements of isoprene and monoterpenes at the remote ZF2 site in the Amazon rainforest showed an 11-month average total emission rate of 2.7 mg m-2 h-1 with considerable seasonal variation, which could not be accurately reproduced using the light and temperature based MEGAN algorithms. This thesis presents the first long-term VOC flux measurements providing information at high temporal resolutions on seasonal variability at an urban site and a pristine tropical forest site. They confirm that the Amazon rainforest is an extremely strong source of reactive carbon to the Earth’s atmosphere exceeding emissions from a developed megacity, such as London, per unit area

Eddy-covariance data with low signal-to-noise ratio:time-lag determination, uncertainties and limit of detection

All eddy-covariance flux measurements are associated with random uncertainties which are a combination of sampling error due to natural variability in turbulence and sensor noise. The former is the principal error for systems where the signal-to-noise ratio of the analyser is high, as is usually the case when measuring fluxes of heat, CO2 or H2O. Where signal is limited, which is often the case for measurements of other trace gases and aerosols, instrument uncertainties dominate. Here, we are applying a consistent approach based on auto- and cross-covariance functions to quantify the total random flux error and the random error due to instrument noise separately. As with previous approaches, the random error quantification assumes that the time lag between wind and concentration measurement is known. However, if combined with commonly used automated methods that identify the individual time lag by looking for the maximum in the cross-covariance function of the two entities, analyser noise additionally leads to a systematic bias in the fluxes. Combining data sets from several analysers and using simulations, we show that the method of time-lag determination becomes increasingly important as the magnitude of the instrument error approaches that of the sampling error. The flux bias can be particularly significant for disjunct data, whereas using a prescribed time lag eliminates these effects (provided the time lag does not fluctuate unduly over time). We also demonstrate that when sampling at higher elevations, where low frequency turbulence dominates and covariance peaks are broader, both the probability and magnitude of bias are magnified. We show that the statistical significance of noisy flux data can be increased (limit of detection can be decreased) by appropriate averaging of individual fluxes, but only if systematic biases are avoided by using a prescribed time lag. Finally, we make recommendations for the analysis and reporting of data with low signal-to-noise and their associated errors

Volatile organic compound fluxes and concentrations in London (ClearfLo)

Volatile organic compounds (VOCs) from anthropogenic sources such as fuel combustion or evaporative emissions can directly and indirectly affect human health. Some VOCs, such as benzene and 1,3- butadiene are carcinogens. These and other VOCs contribute to the formation of ozone (O3) and aerosol particles, which have effects on human health and the radiative balance of the atmosphere. Although in the UK VOC emissions are subject to control under European Commission Directive 2008/50/EC and emission reducing echnologies have been implemented, urban air pollution remains a concern. Urban air quality is likely to remain a priority since currently >50% of the global population live in urban areas with trends in urbanization and population migration predicted to increase. The ClearfLo project is a large multi-institutional consortium funded by the UK Natural Environment Research Council (NERC) and provides integrated measurements of meteorology, gas phase and particulate composition of the atmosphere over London. Both long term and IOP measurements were made at street and elevated locations at a range of sites across London and its surroundings during 2011 and 2012. Mixing ratios of a selection of nine VOCs were measured using a high sensitivity proton transfer reaction-mass spectrometer (PTR-MS) at a ground level urban background (North Kensington) and kerbside (Marylebone Road) site during the winter IOP. VOC fluxes were measured by virtually disjunct eddy covariance (vDEC) at an elevated urban site (King’s College Strand) in Aug-Dec 2012. Our results for the first IOP showed that most of the selected compound concentrations depended on traffic emissions, although there was a marked difference between the urban ackground and kerbside sites. We identified some temperature effects on VOC concentrations. We also present the first analyses of VOC flux measurements over London. Preliminary analyses indicate most compounds associated with vehicle emissions closely followed diurnal traffic counts. Fluxes of isoprene and methanol appear to be controlled by light intensity and temperature, consistent with a redominantly biogenic source of these compounds

Seasonal and diurnal trends in concentrations and fluxes of volatile organic compounds in central London

Concentrations and fluxes of seven volatile organic compounds (VOCs) were measured between August and December 2012 at a rooftop site in central London as part of the ClearfLo project (Clean Air for London). VOC concentrations were quantified using a proton transfer reaction mass spectrometer (PTR-MS) and fluxes were calculated using a virtual disjunct eddy covariance technique. The median VOC fluxes, including aromatics, oxygenated compounds and isoprene, ranged from 0.07 to 0.33 mgm&#x100000;^-2 h^-&#x100000;1. Median mixing ratios were 7.3 ppb for methanol and < 1 ppb for the other compounds. Strong relationships were observed between the fluxes and concentrations of some VOCs with traffic density and between the fluxes and concentrations ofisoprene and oxygenated compounds with photosynthetically active radiation (PAR) and temperature. An estimated 50–90% of the fluxes of aromatic VOCs were attributable to traffic activity, which showed little seasonal variation, suggesting that boundary layer effects or possibly advected pollutionmay be the primary causes of increased concentrations of aromatics in winter. Isoprene, methanol and acetaldehyde fluxes and concentrations in August and September showed high correlations with PAR and temperature, when fluxes andconcentrations were largest suggesting that biogenic sources contributed to their fluxes. Modelled biogenic isoprene fluxes from urban vegetation using the Guenther et al. (1995) algorithm agreed well with measured fluxes in August andSeptember. Comparisons of estimated annual benzene emissions from both the London and the National Atmospheric Emissions Inventories agreed well with measured benzene fluxes. Flux footprint analysis indicated emission sourceswere localised and that boundary layer dynamics and source strengths were responsible for temporal and spatial VOC flux and concentration variability during the measurement period

Assessing the carbon and climate benefit of restoring degraded agricultural peat soils to managed wetlands

Restoring degraded peat soils presents an attractive, but largely untested, climate change mitigation approach. Drained peat soils used for agriculture can be large greenhouse gas sources. By restoring subsided peat soils to managed, impounded wetlands, significant agricultural emissions are avoided, and soil carbon can be sequestered and protected. Here, we synthesize 36 site-years of continuous carbon dioxide and methane flux data from a mesonetwork of eddy covariance towers in the Sacramento-San Joaquin Delta in California, USA to compute carbon and greenhouse gas budgets for drained agricultural land uses and compare these to restored deltaic wetlands. We found that restored wetlands effectively sequestered carbon and halted soil carbon loss associated with drained agricultural land uses. Depending on the age and disturbance regime of the restored wetland, many land use conversions from agriculture to restored wetland resulted in emission reductions over a 100-year timescale. With a simple model of radiative forcing and atmospheric lifetimes, we showed that restored wetlands do not begin to accrue greenhouse gas benefits until nearly a half century, and become net sinks from the atmosphere after a century. Due to substantial interannual variability and uncertainty about the multi-decadal successional trajectory of managed, restored wetlands, ongoing ecosystem flux measurements are critical for understanding the long-term impacts of wetland restoration for climate change mitigation

Isoprene emission potentials from European oak forests derived from canopy flux measurements: an assessment of uncertainties and inter-algorithm variability

International audienc

The ÉCLAIRE Bosco Fontana integrated experiment in the context of the PEGASOS Po Valley study

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