Veränderungen des NO/NO2-Verhältnisses in Nordrhein-Westfalen (1984–2004) und mögliche Ursachen

Objective and Background

The nitrogen oxides NO and NO₂ and, in particular, their ratio (NO/NO₂), play important roles in the radical-system of the atmospheric boundary layer. There were various indications upon a dropping NO/NO₂-ratio in citiex over the last years, however, no proof has been given yet Especially in densely populated areas such as the federal state of North Rhine-Westphalia (NRW), such a change can have significant influences upon various atmospheric reactions. The objective of this investigation was to prove the existence of a systematic change of the NO/NO₂-ratio, to describe the development of NO_x over the past 2 decades at different locations and to determine the causes for this development.

Methods

To detect changes of the NO/NO₂-ratio we processed the data of 11 continuously operating air quality stations of the State Environment Agency (LUA NRW) with time series reaching back up to 20 years. We investigated rural stations, stations in the urban background and heavily traffic influenced locations. It was possible to calculate and assess the NO/NO₂-ratio under consideration of the fast reaction of ozone with NO. There were clear indications towards existing trends and they could be determined as statistically significant using the nonparametric Mann-Kendall Test. The analysis of possible causes for the change of the NO/NO₂-ratio focused upon the change of the global radiation, the change of the patterns of the atmosphetic circulation, and the frequency of cyclones and anticyclones meteorological conditions in Central Europe, the introduction of automotive catalytic converters, and the development of the atmospheric oxidation-capacity.

Results and conclusions

The results are indicating a decline of the ratio at traffic-influenced stations with a statistical significance over 95%. The negative trend can also be detected at most urban background stations. It was problematic to perform the trend-analysis of the rural background station in the Egge-Mountains because of the fragmentary character of the dataset. Regional differences in the development of the NO/NO₂-ratio indicate towards various causes. Crucial for the situation at the rural areas are the changed trajectories of cyclones and anticyclones as well as the decline of the atmospheric oxidation-capacity, while the traffic plays another important role at urban stations. The negative trend at the traffic-stations was intensified by the introduction of catalytic converters, which lead to a reduction in emissions of NO_x

Recommendations and prospects

The significance of the NO/NO₂-ratio for the oxidation capacity of the atmosphere shows the necessity to further monitor this development. Previous investigations detected a decline in total NO_x without examining the relative development of the two nitrogen oxides towards each other. Gaining insight into the local differences of this ratio helps to allocate sources and to develop understanding of the atmospheric processes.     

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