Estimation of the total VOC reactivity with OH by pump-and-probe OH lidar to determine a new indicator for ozone production

Many of our most severe problems of environmental pollution involve the Earth's atmosphere. The adverse effects of atmospheric pollution are particularly evident in the low troposphere, especially in urban/suburban areas where many sources contribute to the atmospheric burden. Ozone (O3) is one of the major constituents of the air pollution over cities commonly called photochemical smog. It is a secondary pollutant, produced by the reaction of primary pollutants, nitrogen oxides (NOx) and hydrocarbons (VOC), in the presence of sunlight. Although hydrocarbons and NOx have long been identified as the two key precursors to photochemical O3, the development of an effective strategy for reducing ozone production in photochemical smog by controlling the anthropogenic emissions of these precursors has proved to be problematic. The objective of the present study is to present and demonstrate the robustness of a new observable "indicator" for determining the sensitivity of ozone formation to VOC and NOx (VOC- and NOx-limited regime). This indicator is based on the reactivity of VOC and NOx with respect to OH. Simulation tests of the ability of this new indicator Θ = τOHVOC/τOHNOx to distinguish between a NOx and a VOC-limited regime were performed with a box model and a 3D model applied to a specific episode of photochemical smog (Athens) and of a less polluted area (the Swiss plateau). Whereas the NOx reactivity 1/τOHNOx can easily be measured by standard methods, the total VOC reactivity 1/τOHVOC will be estimated by measuring the inverse lifetime of OH with a new Pump-and-Probe Lidar instrument. The method consists of producing high OH concentrations by the flash photolysis of ozone and the subsequent O(1D) reaction with H2O and by following the OH relaxation by laser-induced fluorescence (LIF). Numerical simulation of the experiment will show that the total VOC reactivity with OH can be obtained by measuring the inverse lifetime of the OH and its absolute initial concentration with the Pump-and-Probe experiment as well as the NOx, CO and O3 concentrations with standard trace-gas detectors. This total in-situ VOC reactivity will be used to determine the new indicator Θ but will also help to test the accuracy of the VOC-lumped chemical mechanism in the numerical atmospheric simulation. In order to demonstrate the feasibility of the Pump-and-Probe experiment, laboratory investigations have been performed in controlled atmosphere: OH absorption and fluorescence emission spectra allowed the OH transition bands and the non-resonant fluorescence wavelength to be identified. High-resolution OH absorption spectra allowed the OH effective absorption cross section to be determined for assessing the experimental sensitivity and retrieving the OH concentration. The experimental retrieval of the rate constant for the OH+CH4 and OH+NO2 reactions reveals the ability of the pump-and-probe experiment to monitor the chemical kinetics of OH at atmospheric pressure and room temperature. OH relaxation measured in different VOC/NOx/O3 gas mixtures confirm the relevance of the model predictions of the OH relaxation approximated by a first-order chemical decay and the validity of the total VOC reactivity with respect to OH estimated by such an approximation. A first in-situ OH relaxation measurement realized directly in the air of the laboratory showed that the pump-and-probe method could be performed under typical PBL conditions. Preliminary range-resolved measurements yielding vertical profiles of the OH concentrations produced by flash photolysis of ambient ozone suggest a promising future for the Lidar pump-and-probe technique. The perspectives for the Pump-and-Probe Lidar experiment are expressed in the concluding section.

Ozone and water vapor measurements by Raman lidar in the planetary boundary layer

The temporal and spatial retrieve of ozone (O3) concentration and water vapor (H2O) mixing ratio in the troposphere is of essential interest. Contrary to the stratospheric case, the tropospheric ozone can have a harmful impact, with its toxic effect, on humans and vegetation, accelerating the degradation of the minerals and participating in the green-house problem. Concerning the water vapor, knowledge of its highly variable concentration is essential to both the chemistry of the troposphere (O(1D) + H2O —> 2 OH) where it participates, among others, in the generation of the hydroxyl radical (OH) and to the meteorology. Water vapor is the dominant green-house gas, it plays an important role in the atmospheric chemistry. The conversion and transport of water in the atmosphere is the essential point in the earth's radiation budget. Due to the complexity and the non-linearity of the air pollution system including emissions, chemistry, thermal radiation, transport and deposition, pollution abatement strategies can only be designed rightly by the use of a three-dimensional mesoscale Eulerian photochemical transport model. To check such models, measurement campaigns are undertaken, in which many physical (wind, temperature, H2O, etc.) and chemical parameters (emissions and imissions) are measured at different parts of the atmosphere. LIDAR (LIght Detection And Ranging), which is a real-time method for measuring air pollutants in situ, is one of the best tools to make 3-D measurements of gases concentrations like O3, H2O and others. Contrary to the ground based measurements that are highly sensitive to the very local conditions, lidar sensitivity and resolution in space and time is optimal to obtain measurements and to compare or give some input data for the models. During the last thirty years, (elastic backscatter) Differential Absorption Lidar (DIAL) has been established as a convenient tool for the monitoring of the three dimensional real time concentrations of air pollutants [Measures, 1992], [Schoulepnikoff et al., 1998]. But the DIAL apparatus has shown limitations: — the operation in layers with high aerosol loading like in the Planetary Boundary Layer (PBL) where they are highly variable — the simultaneous detection of several atmospheric components or pollutants is impossible [Bösenberg, 1996] — the detection at short range is difficult due to the high dynamics. Furthermore, due to its spectrum and the strong influence from other elements, the water vapor can not be easily measured in the UV with classical DIAL systems. The goal of this work was to develop a method to simultaneously measure the ozone absolute concentration and the water vapor mixing ratio in the PBL. Experiments with Nd : YAG and KrF lasers were made and utilization of both analog and photon counting techniques, increasing the dynamic range, were investigated. To retrieve the ozone concentration profile, we take advantage of the simultaneous spontaneous Raman backscattering on the molecules of nitrogen (N2) and oxygen (O2) that have different ozone absorption cross-sections. Thus with a modified DIAL technique, the ozone concentration can be measured without most of the interference from poorly known backscatter by particles. Water vapor mixing ratio profile can also be obtained with a set of three Raman backscattered signals, simultaneously detected, from the molecules of H2O, N2 and O2. The main advantage of this Raman system is its essential independence to the wavelength dependent backscatter problems as induced by aerosols, and the fact that the N2 and O2 concentrations are well known as well as the Raman cross-sections of interest. Although the Raman cross-sections are two or three orders of magnitude lower than the elastic backscattering cross-sections, they are compensated by the proportionally much higher concentrations of O2, N2 and H2O compared to trace gases like O3. The development of the Raman — DIAL method for atmospheric measurements in the PBL presents several challenges. One is the development of highly-sensitive lidar systems, in particular the optical receiver, the spectrometer and the signal acquisition for the Raman part of the Raman-DIAL system. Also the data processing procedure for simultaneous evaluation of the ozone and the water vapor profiles. Both of these challenges present a number of issues, theoretical and practical, that are investigated in the frame of this work.

EPFL2001

Improvement of an urban turbulence parametrization for meteorological operational forecast and air quality modeling

Clive Muller

During the last century, urban pollution has increased with the growth of cities. Urban air quality has become a high priority as it is directly linked to concerns such as human exposure and health. The present work is dedicated to urban air quality modeling with focus on urban meteorology. The main goal is to improve meteorological and air quality simulations in urban areas. Based on measurements and numerical air quality simulations, Chapter 3 describes the meteorological situation and tests an emission inventory for an ozone pollution episode in Mexico City (2 March 1997), in order to determine the principal factors to be accounted in an air quality study. The Mexico City case shows the great influence of meteorological conditions and pollutant emissions on air quality. A thorough understanding of the phenomena governing the meteorological conditions, like small scale convergence, and an accurate emission inventory validated by VOC measurements in the city, are sensitive elements in an air quality study. In Chapter 4, the presence of an Urban Heat Island (UHI) is underlined over the city of Basel (Switzerland) with the BUBBLE measurements. Further on, the ability of aLMo (the operational weather prediction model of MeteoSwiss) to reproduce the effect of a city on the boundary layer atmospheric flow fields is investigated. Results show that aLMo is not able to reproduce the UHI and hence that its surface scheme based on the Monin-Obukhov Similarity Theory (MOST) is not adapted for the urban areas. Therefore, the Buildings Effects Parametrization (BEP) which has been developed by Martilli et al.(2002) especially for urban areas, is implemented in aLMo. Results show that alMo is now able to reproduce the main behavior of the urban boundary layer as the UHI and BEP has hence a real enhancement potential for aLMo. Chapter 5 shows the sensitivity of aLMo with respect to its vertical resolution. In order to limit the sensitivity of aLMo to the grid resolution, BEP is modified. The mesoscale model furnishes the upper boundary conditions for the inner calculation of BEP. That is, BEP recalculates independently the vertical profiles of wind, temperature and energy based on the surface fluxes of momentum, heat and turbulent kinetic energy. The results obtained show a decrease in the sensitivity to the resolution and a better agreement with the measurements. Furthermore, the modified version of BEP gives additional meteorological fields (temperature, wind and TKE) in the urban canopy. The computed temperature in the urban canopy shows a good agreement with measurements in a Basel street canyon. This work shows that it is not necessary to have a high resolution for taking into account modification of the atmospheric flow fields induced by a city.

EPFL2007

Une première mesure lidar combinée d'ozone et de vent, à partir d'une instrumentation et d'une méthodologie coup par coup

During these last decades, air pollution has drawn the attention of scientists because of the deterioration of the human environment that it has caused. Unfortunately, the study of this dynamic phenomenon is very complex and requires the use of models that compute the evolution of the physico-chemical parameters of the atmosphere. Moreover, the predictions of the numerical simulations have to be validated by range- and time-resolved measurements, carried out continuously up to the top of the planetary boundary layer. Only the optical radar or lidar satisfies these specifications: for this reason the Laboratory for Air and Soil Pollution (LPAS) of the Swiss Federal Institute of Technology (EPFL) has developed such a system in order to provide the modellers with information complementary to that given by the ground measurements. This instrument, after mounting on a mobile platform, has determined the concentration of the key molecule ozone during several field campaigns, demonstrating its reliability and precision. Moreover, the EPFL system is a shot per shot lidar, able to record each detected signal and not only its average in a time interval. This feature is innovative to lidar determinations of tropospheric ozone and allows one to measure accurately the statistical error, to correct for the effect of systematic biases and to observe the dynamic behaviour of the atmosphere: the measurement of the statistical error has been used to build a model of the signal and of its noise, useful in the design of future lidar systems and for the comparison of the various data processing algorithms. the correction of the bias caused by the artificial deformation of the statistical distribution of the signal at long distance has led to a considerable increase of the range of the retrieved ozone profiles, the observation of the dynamic behaviour of the atmosphere has resulted in the first simultaneous measurement of a pollutant concentration and of the wind velocity with the same data set recorded by a lidar.

EPFL1996