Long-term NOx measurements in the remote marine tropical troposphere

Atmospheric nitrogen oxides (NO + NO2 = NOx) have been measured at the Cape Verde Atmospheric Observatory (CVAO) in the tropical Atlantic (16 degrees 51' N, 24 degrees 52' W) since October 2006. These measurements represent a unique time series of NOx in the background remote troposphere. Nitrogen dioxide (NO2) is measured via photolytic conversion to nitric oxide (NO) by ultraviolet light-emitting diode arrays followed by chemiluminescence detection. Since the measurements began, a blue light converter (BLC) has been used for NO2 photolysis, with a maximum spectral output of 395 nm from 2006 to 2015 and of 385 nm from 2015 onwards. The original BLC used was constructed with a Teflon-like material and appeared to cause an overestimation of NO2 when illuminated. To avoid such interferences, a new additional photolytic converter (PLC) with a quartz photolysis cell (maximum spectral output also 385 nm) was implemented in March 2017. Once corrections are made for the NO2 artefact from the original BLC, the two NO2 converters are shown to give comparable NO2 mixing ratios (BLC = 0.99 x PLC + 0.7 ppt, linear least-squares regression), giving confidence in the quantitative measurement of NOx at very low levels. Data analysis methods for the NOx measurements made at CVAO have been developed and applied to the entire time series to produce an internally consistent and high-quality long-term data set. NO has a clear diurnal pattern with a maximum mixing ratio of 2-10 ppt during the day depending on the season and similar to 0 ppt during the night. NO2 shows a fairly flat diurnal signal, although a small increase in daytime NOx is evident in some months. Monthly average mixing ratios of NO2 vary between 5 and 30 ppt depending on the season. Clear seasonal trends in NO and NO2 levels can be observed with a maximum in autumn and winter and a minimum in spring and summer.