Statistical methods for accounting and understanding ozone trends derived from observations

Emissions of ozone precursors have been regulated in Europe since around 1990 with air quality control measures, which resulted in reductions of nitrogen oxides and volatile organic compounds concentrations. In order to understand how these measures have affected tropospheric ozone, it is important to investigate its long-term temporal evolution in different types of environments and various geographic regions. Uncertainties in ozone long-term trends are associated to variations originating from meteorological influence on ozone. Also, ozone temporal evolution can vary significantly among different regions and types of environment. In this PhD thesis we used sophisticated statistical tools, and developed robust statistical approaches to study long-term trends of tropospheric ozone that reflect emissions reductions. First, we focus on a meteorological adjustment of ozone observations in order to derive long-term trends with lower uncertainties compared to common practices. In addition, a classification scheme for stations in Europe is needed to interpret response of ozone in site groups with similar spatio-temporal characteristics. A detailed long-term trend analysis was performed based on decomposition of the mean ozone observations in the time domain. The different time-dependent variations of ozone were extracted, namely the long-term trend, seasonal and short-term variability. This allows subtraction of the meteorologically driven seasonal variation from the observations and estimation of long-term trends on de-seasonalized concentrations. In addition, ozone peak concentrations were investigated using a localized regression approach, which corrects for meteorological influence. The meteorological adjustment of the mean and peak ozone allows estimation of long-term trends with lower uncertainty. A site grouping in Europe was developed using the long-term and seasonal variations of ozone. The implemented clustering approach based on the long-term variation resulted in a site type classification while a geographical classification was achieved on the seasonal variation. We observed that, despite the implementation of regulations, mean ozone has been increasing in most of the sites until mid-2000s, although, afterwards, a decline or a leveling off was observed. The point when the trend changes from increasing to decreasing depends on the site type; the closer a site locates to emission sources the later the change occurred. Also, it was concluded that with time urban and rural environments become more similar in terms of ozone concentrations. On the other hand, peak ozone has been reducing in most stations, while in sites close to emissions it increased until mid-2000s when it started to level off. The influence of air pollutants hemispheric transport is depicted in remote sites, where ozone increased until beginning of 2000s and decreased afterwards. A two-dimensional classification scheme, reflecting site type and region, has showed that mainly the site type influences ozone long-term trends, while the location is more important for temporal changes in ozone inter-annual cycle and relationship to temperature.

Reactions of nitrogen-containing compounds with ozone: kinetics and mechanisms

Sung Eun Lim

Nitrogen-containing moieties are widespread in natural waters in dissolved organic nitrogen and micropollu-tants. They are often susceptible to an electrophilic attack of ozone because of the electron-rich nature of the neutral form of nitrogen in organic compounds. This indicates that reactions of nitrogen-containing compounds with ozone inevitably occur in water and wastewater treatment where ozonation is applied for disinfection or oxidation. Despite the relevance to ozone chemistry, the knowledge on reactions of ozone with some principal nitrogen-containing functional groups is limited. The aim of this thesis was to elucidate reaction mechanisms of nitrogen-containing compounds with ozone for common nitrogen-containing functional groups: aliphatic amines and azoles. The primary objectives were (1) to determine the second-order rate constants for the reactions of nitrogen-containing compounds with ozone (kO3), (2) to identify/quantify transformation products and reactive oxygen species, (3) to perform kinetic simulations and quantum chemical computations to supplement or corroborate empirical evidences. Reaction mechanisms were proposed by compiling the results from all aspects, providing a better understanding of nitrogen-ozone chemistry. The investigation of triethylamine, diethylamine, and ethylamine yielded kO3 of the neutral form of amines ranging from 9.310^4 M-1 s-1 to 2.210^6 M-1 s-1. The apparent kO3 at pH 7 for potential or identified transformation products were 6.810^5 M-1 s-1 for N,N-diethylhydroxylamine, ~10^5 M-1 s-1 for N-ethylhydroxylamine, 1.910^3 M-1 s-1 for N-ethylethanimine oxide, and 3.4 M-1 s-1 for nitroethane. All amines predominantly underwent oxygen-transfer pathways to form major transformation products containing nitrogen-oxygen bonds: triethylamine N-oxide (88% per abated triethylamine) and nitroethane (69% per abated diethylamine and 100% per abate ethylamine). N,N-diethylhydroxylamine was a potential primary transformation product during the diethylamine-ozone reaction. Its formation was not confirmed due to its high ozone reactivity, but supported by measurements of reactive oxygen species, kinetic simulations, and quantum chemical computations. Pyrrole and imidazole reacted fast (kO3 > 10^3 M-1 s-1 at pH 1 â 12), whereas pyrazole reacted moderately fast with ozone (kO3 = 56 M-1 s-1 at pH 7). All studied azoles underwent an addition of ozone to the C-C double bond in the ring. Subsequent pathways after the initial ozone addition varied considerably among the azoles. Pyrrole reacted with ozone via a Criegee-type and an oxygen-addition mechanism. The major identified products (yield per abated pyrrole) were maleimide (34%), formamide (14%) and formate (54%). Imidazole predominantly reacted via a Criegee-type mechanism with ring cleavage and formation of the three fragments, formamide, cyanate, and formate (~100 % yields, respectively), completely closing the mass balance. For pyrazole, only carbonous products were identified (126% formate and 34% glyoxal per abated pyrazole). Products containing hydroxypyrazole and hydrazide moieties were postulated, possibly formed via an oxygen addition and a Criegee-type mechanism, respectively. The nitrogenous transformation products identified during this study may have different environmental implications. Some of them (e.g., nitroalkanes, N-formyl compounds) require further efforts to understand their impact on the aquatic environment and human health.

EPFL2020

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.

EPFL2000

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