Comparison of measured ozone production efficiencies in the marine boundary layer at two European coastal sites under different pollution regimes

Ozone production efficiencies (EN), which can be defined as the net number of ozone molecules produced per molecule of NOx oxidised, have been calculated from measurements taken during three intensive field campaigns (one in the spring, EASE 96, and two in the summer, EASE 97 and TIGER 95), at two European coastal sites (Mace Head, Ireland (EASE) and Weyboume, Norfolk (TIGER)) impacted by polluted air masses originating from both the U.K. and continental Europe, as well as relatively clean oceanic air masses from the Arctic and Atlantic. From a detailed wind sector analysis of the EASE 96 and 97 data it is clear that two general types of pollution regime were encountered at Mace Head. The calculated ozone production efficiency in clean oceanic air masses was approximately 65, which contrasted to more polluted air, from the U.K. and the continental European plume, where the efficiency decreased to between 4 and 6. The latter values of EN agree well with literature measurements conducted downwind of various urban centres in the U.S. and Europe, which are summarised in a wide-ranging review table. The EN value calculated for clean oceanic air is effectively an upper limit, owing to the relatively rapid deposition of HNO3 to the ocean. Consideration of the variation of EN With NOx for the three campaigns suggests that ozone production efficiency is relatively insensitive to both geographical location and season. The measured EN values are also compared with values derived from steady-state expressions. An observed anti-correlation between EN and measured ozone tendency is briefly discussed

Long-range transport of ozone and related pollutants over the North Atlantic in spring and summer

This paper presents strong experimental evidence for a major perturbation in ozone concentrations over large parts of the North Atlantic Ocean from the surface to 8 km associated with continental pollutants. The evidence was gathered in the course of 7 flights by the UK Meteorological Office C-130 aircraft based on the Azores, and 4 ferry flights between the UK to the Azores in spring and summer 1997 as a component of the NERC-funded ACSOE project. The total latitude range covered was approximately 55°N–25°N, and the longitude range was approximately 0° to 40°W. Many profiles were made between the sea surface and altitudes up to 9km to survey the composition of the marine atmosphere. The C-130 aircraft was comprehensively equipped to measure many chemical and physical parameters along with standard meteorological instrumentation. Thus it was able to measure ozone and speciated NOy, along with tracers including water vapour, carbon monoxide and condensation nuclei, in near real time. The overall ‘picture’ of the troposphere over large parts of the North Atlantic is of layers of pollution from the continents of different ages interspersed with layers of air uplifted from the marine boundary layer. The lowest ozone concentrations were recorded in the marine boundary layer where there is evidence for extensive ozone destruction in summer. Flights were made to penetrate the outflow of hurricane Erica, to determine the southerly extent of polluted air in summer, to examine the impact of frontal systems on the composition of remote marine air, and to trace long-range pollution from the west coast of the USA interspersed with air with a stratospheric origin. In one of the spring flights it is possible that a plume of polluted air with high ozone and NOy, and with an origin in southeast Asia, was intercepted off the coast of Portugal. The concentrations of NOx in this plume were sufficient for ozone formation to be continuing along its track from west to east. The instrument to measure NOy almost certainly was only measuring the sum of organic nitrates (mostly in the form of PAN) plus NOx. The high correlation between NOy and ozone under these conditions strongly suggests a non-stratospheric source for most of the ozone encountered over large parts of the atmosphere upwind of Europe. There was a marked seasonal variation in the NOy with about twice as much present in the spring flights than in the summer flights. The overall ozone levels in both spring and summer were somewhat similar although the highest ozone concentration encountered ~100 ppbv) was observed in summer in some polluted layers in mid Atlantic with an origin in the boundary layer over the southeastern USA. The bulk of the pollutants, ozone, CO, and NOy, were in the free troposphere at altitudes between 3 and 8 km. The only instances of pollution at lower levels were in the form of ship plumes, which were encountered several times. The data therefore strongly support the need for more in-situ aircraft experiments to quantify and understand the phenomenon of long-range transport of pollution from continent to continent. Observations at ground-based stations are inadequate for this purpose and satellite data is incomplete both in terms of its altitude detail and in the extent of chemical speciation, particularly for ascertaining whether chemical production and destruction processes for ozone are occurring