Urban flask measurements of CO2ff and CO to identify emission sources at different site types in Auckland, New Zealand.

As part of the CarbonWatch-NZ research programme, air samples were collected at 28 sites around Auckland, New Zealand, to determine the atmospheric ratio (RCO) of excess (local enhancement over background) carbon monoxide to fossil CO2 (CO2ff). Sites were categorized into seven types (background, forest, industrial, suburban, urban, downwind and motorway) to observe RCO around Auckland. Motorway flasks observed RCO of 14 ± 1 ppb ppm-1 and were used to evaluate traffic RCO. The similarity between suburban (14 ± 1 ppb ppm-1) and traffic RCO suggests that traffic dominates suburban CO2ff emissions during daytime hours, the period of flask collection. The lower urban RCO (11 ± 1 ppb ppm-1) suggests that urban CO2ff emissions are comprised of more than just traffic, with contributions from residential, commercial and industrial sources, all with a lower RCO than traffic. Finally, the downwind sites were believed to best represent RCO for Auckland City overall (11 ± 1 ppb ppm-1). We demonstrate that the initial discrepancy between the downwind RCO and Auckland's estimated daytime inventory RCO (15 ppb ppm-1) can be attributed to an overestimation in inventory traffic CO emissions. After revision based on our observed motorway RCO, the revised inventory RCO (12 ppb ppm-1) is consistent with our observations. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

Short-term variations in the oxidizing power of the atmosphere.

The hydroxyl radical is the predominant atmospheric oxidant, responsible for removing a wide range of trace gases, including greenhouse gases, from the atmosphere. Determination of trends and variability in hydroxyl radical concentrations is critical to understanding whether the 'cleansing' properties of the atmosphere are changing. The variability in hydroxyl radical concentrations on annual to monthly timescales, however, is difficult to quantify. Here we show records of carbon monoxide containing radiocarbon (14CO), which is oxidized by hydroxyl radicals, from clean-air sites at Baring Head, New Zealand, and Scott Base, Antarctica, spanning 13 years. Using a model study, we correct for known variations in production of 14CO (refs 6, 7), allowing us to exploit this species as a diagnostic for short term changes in hydroxyl radical concentrations. We find no significant long-term trend in hydroxyl radical concentrations but provide evidence for recurring short-term variations of around ten per cent persisting for a few months. We also find decreases in hydroxyl radical concentrations of up to 20 per cent, apparently triggered by the eruption of Mt Pinatubo in 1991 and by the occurrence of extensive fires in Indonesia in 1997.