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Nitrous acid, HONO , is a key net photolytic precursor to OH radicals in the atmospheric boundary layer. As OH is the dominant atmospheric oxidant, driving the removal of many primary pollutants and the formation of secondary species, a quantitative understanding of HONO sources is important to predict atmospheric oxidising capacity. While a number of HONO formation mechanisms have been identified, recent work has ascribed significant importance to the dark, ocean-surface-mediated conversion of NO2 to HONO in the coastal marine boundary layer. In order to evaluate the role of this mechanism, here we analyse measurements of HONO and related species obtained at two contrasting coastal locations – Cabo Verde (Atlantic Ocean, denoted Cape Verde herein), representative of the clean remote tropical marine boundary layer, and Weybourne (United Kingdom), representative of semi-polluted northern European coastal waters. As expected, higher average concentrations of HONO (70 ppt) were observed in marine air for the more anthropogenically influenced Weybourne location compared to Cape Verde (HONO < 5 ppt). At both sites, the approximately constant HONO/NO2 ratio at night pointed to a low importance for the dark, ocean-surface-mediated conversion of NO2 into HONO , whereas the midday maximum in the HONO/NO2 ratios indicated significant contributions from photo-enhanced HONO formation mechanisms (or other sources). We obtained an upper limit to the rate coefficient of dark, ocean-surface HONO -to- NO2 conversion of CHONO = 0.0011 ppb h -1 from the Cape Verde observations; this is a factor of 5 lower than the slowest rate reported previously. These results point to significant geographical variation in the predominant HONO formation mechanisms in marine environments and indicate that caution is required when extrapolating the importance of such mechanisms from individual study locations to assess regional and/or global impacts on oxidising capacity. As a significant fraction of atmospheric processing occurs in the marine boundary layer, particularly in the tropics, better constraint of the possible ocean surface source of HONO is important for a quantitative understanding of chemical processing of primary trace gases in the global atmospheric boundary layer and associated impacts upon air pollution and climate. [ABSTRACT FROM AUTHOR]

Atmospheric nitrogen oxides (NO + NO 2 = NO x) have been measured at the Cape Verde Atmospheric Observatory (CVAO) in the tropical Atlantic (16 ∘ 51 ′ N, 24 ∘ 52 ′ W) since October 2006. These measurements represent a unique time series of NO x in the background remote troposphere. Nitrogen dioxide (NO 2) 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 NO 2 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 NO 2 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 NO 2 artefact from the original BLC, the two NO 2 converters are shown to give comparable NO 2 mixing ratios (BLC = 0.99 × PLC + 0.7 ppt, linear least-squares regression), giving confidence in the quantitative measurement of NO x at very low levels. Data analysis methods for the NO x 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 ∼ 0 ppt during the night. NO 2 shows a fairly flat diurnal signal, although a small increase in daytime NO x is evident in some months. Monthly average mixing ratios of NO 2 vary between 5 and 30 ppt depending on the season. Clear seasonal trends in NO and NO 2 levels can be observed with a maximum in autumn and winter and a minimum in spring and summer. [ABSTRACT FROM AUTHOR]

Atmospheric nitrogen oxides (NO + NO2 = NO x) have been measured at the Cape Verde Atmospheric Observatory (CVAO) in the tropical Atlantic (16° 51' N, 24° 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 ultra violet 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 2006-2015 and of 385 nm from 2015. 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 (PLC = 0.92 x BLC, R2 = 0.92), 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 pptV during the day depending on the season and ~0 pptV 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 pptV depending on the season. Clear seasonal trends in NO and NO2 levels can be observed with a maximum in autumn/winter and a minimum in spring/summer. [ABSTRACT FROM AUTHOR]