ALBERT

Description: During the TORCH campaign a zero dimensional box model based on the Master Chemical Mechanism was used to model concentrations of OH radicals. The model provided a close overall fit to measured concentrations but with some significant deviations. In this research, an approach was established for applying Generalized Additive Models to atmospheric concentration data. Two GAM models were fitted to OH radical concentrations using TORCH data, the first using measured OH data and the second using MCM model results. GAM models with five smooth functions provided a close fit to the data with 78% of the deviance explained for measured OH and 83% for modelled OH. The GAM model for measured OH produced substantially better predictions of OH concentrations than the original MCM model results. The diurnal profile of OH concentration was reproduced and the predicted mean diurnal OH concentration was only 0.2% less than the measured concentration compared to 16.3% over-estimation by the MCM model. Photolysis reactions were identified as most important in explaining concentrations of OH. The GAM models combined both primary and secondary pollutants and also anthropogenic and biogenic species to explain changes in OH concentrations. Differences identified in the dependencies of modelled and measured OH concentrations, particularly for aromatic and biogenic species, may help to understand why the MCM model predictions sometimes disagree with measurements of atmospheric species.

Description: The Tropospheric ORganic CHemistry experiment (TORCH) took place during the heatwave of summer 2003 at Writtle College, a site 2 miles west of Chelmsford in Essex and 25 miles north east of London. The experiment was one of the most highly instrumented to date. A combination of a large number of days of simultaneous, collocated measurements, a consequent wealth of model constraints and a highly detailed chemical mechanism, allowed the atmospheric chemistry of this site to be studied in detail. The concentrations of the hydroxyl radical, the hydroperoxy radical and the sum of peroxy radicals, were measured between 25 July and 31 August using laser-induced fluorescence at low pressure and the peroxy radical chemical amplifier techniques. The concentrations of the radical species were predicted using a zero-dimensional box model based on the Master Chemical Mechanism version 3.1, which was constrained with the observed concentrations of relatively long-lived species. The model included a detailed parameterisation to account for heterogeneous loss of hydroperoxy radicals onto aerosol particles. Quantile-quantile plots were used to assess the model performance in respect of the measured radical concentrations. On average, measured hydroxyl radical concentrations were over-predicted by 24%. Modelled and measured hydroperoxy radical concentrations agreed very well, with the model over-predicting on average by only 7%. The sum of peroxy radicals was under-predicted when compared with the respective measurements by 22%. OH initiation was dominated by the reactions of excited oxygen atoms with water, nitrous acid photolysis and the ozone reaction with alkene species. Photolysis of aldehyde species was the main initiation route for HO2 and RO2. Termination, under all conditions, primarily involved reactions with NOx for OH and heterogeneous chemistry on aerosol surfaces for HO2. The OH chain length varied between 2 and 8 cycles, the longer chain lengths occurring before and after the most polluted part of the campaign. Peak local ozone production of 17 ppb hr−1 occurred on 3 and 5 August, signifying the importance of local chemical processes to ozone production on these days. On the whole, agreement between model and measured radicals is good, giving confidence that our understanding of atmospheres influenced by nearby urban sources is adequate.

Description: The Tropospheric ORganic CHemistry experiment (TORCH) took place during the heatwave of summer 2003 at Writtle College, a site 2 miles west of Chelmsford in Essex and 25 miles north east of London. The experiment was one of the most highly instrumented to date. A combination of a large number of days of simultaneous, collocated measurements, a consequent wealth of model constraints and a highly detailed chemical mechanism, allowed the atmospheric chemistry of this site to be studied in detail. Between 25 July and 31 August, the concentrations of the hydroxyl radical and the hydroperoxy radical were measured using laser-induced fluorescence at low pressure and the sum of peroxy radicals was measured using the peroxy radical chemical amplifier technique. The concentrations of the radical species were predicted using a zero-dimensional box model based on the Master Chemical Mechanism version 3.1, which was constrained with the observed concentrations of relatively long-lived species. The model included a detailed parameterisation to account for heterogeneous loss of hydroperoxy radicals onto aerosol particles. Quantile-quantile plots were used to assess the model performance in respect of the measured radical concentrations. On average, measured hydroxyl radical concentrations were over-predicted by 24%. Modelled and measured hydroperoxy radical concentrations agreed very well, with the model over-predicting on average by only 7%. The sum of peroxy radicals was under-predicted when compared with the respective measurements by 22%. Initiation via OH was dominated by the reactions of excited oxygen atoms with water, nitrous acid photolysis and the ozone reaction with alkene species. Photolysis of aldehyde species was the main route for initiation via HO2 and RO2. Termination, under all conditions, primarily involved reactions with NOx for OH and heterogeneous chemistry on aerosol surfaces for HO2. The OH chain length varied between 2 and 8 cycles, the longer chain lengths occurring before and after the most polluted part of the campaign. Peak local ozone production of 17 ppb hr−1 occurred on 3 and 5 August, signifying the importance of local chemical processes to ozone production on these days. On the whole, agreement between model and measured radicals is good, giving confidence that our understanding of atmospheres influenced by nearby urban sources is adequate.

Description: During the TORCH campaign a zero dimensional box model based on the Master Chemical Mechanism was used to model concentrations of OH radicals. The model provided a close overall fit to measured concentrations but with some significant deviations. In this research, an approach was established for applying Generalized Additive Models (GAM) to atmospheric concentration data. Two GAM models were fitted to OH radical concentrations using TORCH data, the first using measured OH data and the second using MCM model results. GAM models with five smooth functions provided a close fit to the data with 78% of the deviance explained for measured OH and 83% for modelled OH. The GAM model for measured OH produced substantially better predictions of OH concentrations than the original MCM model results. The diurnal profile of OH concentration was reproduced and the predicted mean diurnal OH concentration was only 0.2% less than the measured concentration compared to 16.3% over-estimation by the MCM model. Photolysis reactions were identified as most important in explaining concentrations of OH. The GAM models combined both primary and secondary pollutants and also anthropogenic and biogenic species to explain changes in OH concentrations. Differences identified in the dependencies of modelled and measured OH concentrations, particularly for aromatic and biogenic species, may help to understand why the MCM model predictions sometimes disagree with measurements of atmospheric species.

Description: A seasonal-trend decomposition technique based on a locally-weighted regression smoothing (Loess) approach has been used to decompose monthly ozone concentrations at Mace Head (Ireland) into trend, seasonal and irregular components. The trend component shows a steady increase from 1990–2004, which is confirmed by statistical testing which shows that ozone concentrations at Mace Head have increased at the p=0.06 level by 0.18±0.04 ppb yr−1. By considering different air mass origins using a trajectory analysis, it has been possible to separate air masses into "polluted" and "unpolluted" origins. The seasonal-trend decomposition technique confirms the different seasonal cycles of these air mass origins with unpolluted air mass maxima in April and polluted air mass maxima in July/August. A detailed consideration of the seasonal component reveals different behaviour depending on the air mass origin. For baseline unpolluted air arriving at Mace Head there has been a gradual increase in the seasonal amplitude, driven by a declining summertime component. The amplitude of the seasonal component of baseline air is controlled by a maximum in April and a minimum in July. For polluted air mass trajectories, there was a substantial reduction in the amplitude of the seasonal component from 1990–1997. However, post-1997 results indicate that the seasonal amplitude in polluted air masses arriving at Mace Head is increasing. Furthermore, there has been a shift in the months controlling the size of the seasonal amplitude in polluted air from a maximum in May and minimum in January in 1990 to a maximum in April and a minimum in July by 2001. This finding suggests that there has been a steadily decreasing influence of polluted air masses arriving from Europe. These air masses have therefore increasingly taken on the attributes of baseline air.

Description: A seasonal-trend decomposition technique based on a locally-weighted regression smoothing (Loess) approach has been used to decompose monthly ozone concentrations at Mace Head (Ireland) into trend, seasonal and irregular components. The trend component shows a steady increase from 1990–2004, which is confirmed by statistical testing that shows that ozone concentrations at Mace Head have increased at the p=0.06 level by 0.18±0.04 ppb yr−1. By considering different air mass origins using a trajectory analysis, it has been possible to separate air masses into "polluted" and "unpolluted" origins. The seasonal-trend decomposition technique confirms the different seasonal cycles of these air mass origins with unpolluted air mass maxima in April and polluted air mass maxima in July/August. A detailed consideration of the seasonal component reveals different behaviour depending on the air mass origin. For baseline unpolluted air arriving at Mace Head there has been a gradual increase in the seasonal amplitude, driven by a declining summertime component. The amplitude of the seasonal component of baseline air is controlled by a maximum in April and a minimum in July. For polluted air mass trajectories, there was a substantial reduction in the amplitude of the seasonal component from 1990–1997. However, post-1997 results indicate that the seasonal amplitude in polluted air masses arriving at Mace Head is increasing. Furthermore, there has been a shift in the months controlling the size of the seasonal amplitude in polluted air from a maximum in May and minimum in January in 1990 to a maximum in April and a minimum in July by 2001. These results indicate that the characteristics of baseline air are becoming more important in polluted air masses arriving at this location.