Weybourne Atmospheric Observatory Research Articles

12 years of continuous atmospheric O2, CO2 and APO data from Weybourne Atmospheric Observatory in the United Kingdom

Abstract. We present a 12-year time series of continuous atmospheric measurements of O2 and CO2 at the Weybourne Atmospheric Observatory in the United Kingdom. These measurements are combined into the term atmospheric potential oxygen (APO), a tracer that is invariant to terrestrial biosphere fluxes. The CO2, O2 and APO datasets discussed are hourly averages between May 2010 and December 2021. We include details of our measurement system and calibration procedures, and describe the main long-term and seasonal features of the time series. The 2 min repeatability of the measurement system is approximately ±3 per meg for O2 and approximately ±0.005 ppm for CO2. The time series shows average long-term trends of 2.40 ppm yr−1 (2.38 to 2.42) for CO2, −24.0 per meg yr−1 for O2 (−24.3 to −23.8) and −11.4 per meg yr−1 (−11.7 to −11.3) for APO, over the 12-year period. The average seasonal cycle peak-to-peak amplitudes are 16 ppm for CO2, 134 per meg for O2 and 68 per meg for APO. The diurnal cycles of CO2 and O2 vary considerably between seasons. The datasets are publicly available at https://doi.org/10.18160/Z0GF-MCWH (Adcock et al., 2023) and have many current and potential scientific applications in constraining carbon cycle processes, such as investigating air–sea exchange of CO2 and O2 and top-down quantification of fossil fuel CO2.

Novel quantification of regional fossil fuel CO2 reductions during COVID-19 lockdowns using atmospheric oxygen measurements.

It is not currently possible to quantify regional-scale fossil fuel carbon dioxide (ffCO2) emissions with high accuracy in near real time. Existing atmospheric methods for separating ffCO2 from large natural carbon dioxide variations are constrained by sampling limitations, so that estimates of regional changes in ffCO2 emissions, such as those occurring in response to coronavirus disease 2019 (COVID-19) lockdowns, rely on indirect activity data. We present a method for quantifying regional signals of ffCO2 based on continuous atmospheric measurements of oxygen and carbon dioxide combined into the tracer “atmospheric potential oxygen” (APO). We detect and quantify ffCO2 reductions during 2020–2021 caused by the two U.K. COVID-19 lockdowns individually using APO data from Weybourne Atmospheric Observatory in the United Kingdom and a machine learning algorithm. Our APO-based assessment has near–real-time potential and provides high-frequency information that is in good agreement with the spread of ffCO2 emissions reductions from three independent lower-frequency U.K. estimates.

Two decades of flask observations of atmospheric <i>δ</i>(O<sub>2</sub>∕N<sub>2</sub>), CO<sub>2</sub>, and APO at stations Lutjewad (the Netherlands) and Mace Head (Ireland), and 3 years from Halley station (Antarctica)

Abstract. We present 20-year flask sample records of atmospheric CO2, δ(O2/N2), and atmospheric potential oxygen (APO) from the stations Lutjewad (the Netherlands) and Mace Head (Ireland), and a 3-year record from Halley station (Antarctica). We include details of our calibration procedures and the stability of our calibration scale over time, which we estimate to be 3 per meg over the 11 years of calibration, and our compatibility with the international Scripps O2 scale. The measurement records from Lutjewad and Mace Head show similar long-term trends during the period 2002–2018 of 2.31 ± 0.07 ppm yr−1 for CO2 and −21.2 ± 0.8 per meg yr−1 for δ(O2/N2) at Lutjewad, and 2.22 ± 0.04 ppm yr−1 for CO2 and −21.3 ± 0.9 per meg yr−1 for δ(O2/N2) at Mace Head. They also show a similar δ(O2/N2) seasonal cycle with an amplitude of 54 ± 4 per meg at Lutjewad and 61 ± 5 per meg at Mace Head, while the CO2 seasonal amplitude at Lutjewad (16.8 ± 0.5 ppm) is slightly higher than that at Mace Head (14.8 ± 0.3 ppm). We show that the observed long-term trends and seasonal cycles are in good agreement with the measurements from various other stations, especially the measurements from the Weybourne Atmospheric Observatory (United Kingdom). However, there are remarkable differences in the progression of annual trends between the Mace Head and Lutjewad records for δ(O2/N2) and APO, which might in part be caused by sampling differences, but also by environmental effects, such as North Atlantic Ocean oxygen ventilation changes to which Mace Head is more sensitive. The Halley record shows clear trends and seasonality in δ(O2/N2) and APO, the latter agreeing especially well with continuous measurements at the same location made by the University of East Anglia (UEA), while CO2 and δ(O2/N2) present slight disagreements, most likely caused by small leakages during sampling. From our 2002–2018 records, we find a good agreement with Global Carbon Budget 2021 (Friedlingstein et al. (2021) for the global ocean carbon sink: 2.1 ± 0.8 PgC yr−1, based on the Lutjewad record. The data presented in this work are available at https://doi.org/10.18160/qq7d-t060 (Nguyen et al., 2021).

Ground and Airborne U.K. Measurements of Nitryl Chloride: An Investigation of the Role of Cl Atom Oxidation at Weybourne Atmospheric Observatory

AbstractNitryl chloride (ClNO2) measurements from the Weybourne Atmospheric Observatory (WAO) are reported from March to April 2013 using a quadruple chemical ionization mass spectrometer with the I− ionization scheme. WAO is a rural coastal site with generally low NOx concentrations, a type of location poorly studied for ClNO2 production. Concentrations of ClNO2 exceeded that of the limit of detection (0.8 ppt) on each night of the campaign, as did concentrations of N2O5, which was also measured simultaneously with the Cambridge Broadband Cavity Enhanced Absorption Spectrometer. A peak concentration of 65 ppt of ClNO2 is reported here. Vertical profiles of ClNO2 from early‐ to middle‐morning flights in close proximity to WAO are also reported, showing elevated concentrations at low altitude. The photolysis of observed ClNO2 and a box model utilizing the Master Chemical Mechanism modified to include chlorine chemistry was used to calculate Cl atom concentrations. This model utilized numerous VOCs from the second Tropospheric Organic Chemistry project in 2004, at the same location and time of year. From this the relative importance of the oxidation of three groups of measured VOCs (alkanes, alkenes, and alkynes) by OH radicals, Cl atoms, and O3 is compared. Cl atom oxidation was deemed generally insignificant at this time and location for total oxidation due to the much lower concentration of ClNO2 observed, even following the night of greatest ClNO2 production.

Effects of halogens on European air-quality.

Halogens (Cl, Br) have a profound influence on stratospheric ozone (O3). They (Cl, Br and I) have recently also been shown to impact the troposphere, notably by reducing the mixing ratios of O3 and OH. Their potential for impacting regional air-quality is less well understood. We explore the impact of halogens on regional pollutants (focussing on O3) with the European grid of the GEOS-Chem model (0.25° × 0.3125°). It has recently been updated to include a representation of halogen chemistry. We focus on the summer of 2015 during the ICOZA campaign at the Weybourne Atmospheric Observatory on the North Sea coast of the UK. Comparisons between these observations together with those from the UK air-quality network show that the model has some skill in representing the mixing ratios/concentration of pollutants during this period. Although the model has some success in simulating the Weybourne ClNO2 observations, it significantly underestimates ClNO2 observations reported at inland locations. It also underestimates mixing ratios of IO, OIO, I2 and BrO, but this may reflect the coastal nature of these observations. Model simulations, with and without halogens, highlight the processes by which halogens can impact O3. Throughout the domain O3 mixing ratios are reduced by halogens. In northern Europe this is due to a change in the background O3 advected into the region, whereas in southern Europe this is due to local chemistry driven by Mediterranean emissions. The proportion of hourly O3 above 50 nmol mol-1 in Europe is reduced from 46% to 18% by halogens. ClNO2 from N2O5 uptake onto sea-salt leads to increases in O3 mixing ratio, but these are smaller than the decreases caused by the bromine and iodine. 12% of ethane and 16% of acetone within the boundary layer is oxidised by Cl. Aerosol response to halogens is complex with small (∼10%) reductions in PM2.5 in most locations. A lack of observational constraints coupled to large uncertainties in emissions and chemical processing of halogens make these conclusions tentative at best. However, the results here point to the potential for halogen chemistry to influence air quality policy in Europe and other parts of the world.

A year of H2 measurements at Weybourne Atmospheric Observatory, UK

ABSTRACTWe present a year-long high precision time series of atmospheric molecular hydrogen (H2) measured at the UK North Sea coast from March 2008 to February 2009. We observed a pronounced seasonal cycle in H2 with mean values in late winter/early spring~40 ppb higher than those in late summer/early autumn. Background-subtracted molar H2/CO ratios (ΔH2/ΔCO) averaged 0.35±0.002 for all data combined and 0.25±0.002 when ΔH2 was above 10 ppb. The ΔH2/ΔCO ratio was highest in summer, possibly as a result of larger photochemical production. Using simultaneous measurements of ozone, we estimated the deposition velocity of H2 during nocturnal inversion events to average 3.5±0.7×10−4 m s−1 for June 2008 and 1.9±1×10−4 m s−1 for July 2008, in good agreement with other reported estimates. In May 2008, we observed an episode of exceptionally clean air being transported from the tropics but arriving from the north, in which H2 was slightly elevated indicating minimal surface loss. On another occasion with south-easterly winds, we believe we detected emissions from H2 production facilities in the near-continent characterised by H2 mixing ratios reaching 1450 ppb.

Measurement and calculation of OH reactivity at a United Kingdom coastal site

Measurements of OH reactivity were made at the Weybourne Atmospheric Observatory on the North Norfolk coast, UK in May 2004. A wide range of supporting species was also measured concurrently as part of the TORCH-2 field campaign, allowing a detailed study of the OH oxidation chemistry to be carried out. Measurements were made in a variety of air masses, with the 3 most prevalent being air from the Atlantic that arrived at the site from over mainland UK in a South Westerly direction, and much cleaner Northerly air that originated over the far North Sea or Arctic, passed over the North Sea and arrived at the site from a North/North Easterly direction. Direct OH reactivity measurements were made on 6 days during the campaign and with influence of 2 of the 3 air masses prevalent during the study period. The average, minimum and maximum measured OH reactivity are: 4.9, 1.3 and 9.7 respectively. The measured OH reactivity was compared to key OH sinks such as NO2 and CO and a general positive correlation was observed. OH reactivity (k′) was then calculated using the full range of OH sinks species that were measured (including >30 NMHCs) and their pseudo first order rate constants for reaction with OH. For much of the measurement period there is a significant difference between the measured and calculated k′, with an average value of k′meas- k′calc = 1.9 s-1, indicative of unmeasured OH sinks. A zero-dimensional box model containing a subset of the Master Chemical Mechanism was used to calculate the OH reactivity more accurately. The simultaneously measured trace species were used as inputs to the model and their oxidative degradation was described by a chemical mechanism containing ~5,000 species. The extra OH sinks species produced by the model, resulted in an improvement in the agreement between k′meas and k′calc, however the averaged missing OH reactivity across the entire measurement period remained at 1.4 s-1. Speculation is made as to the source of this missing reactivity, including reference to studies showing that a potentially large number of high molecular weight aromatic species could be unmeasured by standard instrumentation.

A flow-tube based laser-induced fluorescence instrument to measure OH reactivity in the troposphere

Abstract. A field instrument utilising the artificial generation of OH radicals in a sliding injector flow-tube reactor with detection by laser-induced fluorescence spectroscopy has been developed to measure the rate of decay of OH by reaction with its atmospheric sinks. The OH reactivity instrument has been calibrated using known concentrations of CO, NO2 and single hydrocarbons in a flow of zero air, and the impact of recycling of OH via the reaction HO2+NO→OH+NO2 on the measured OH reactivity has been quantified. As well as a detailed description of the apparatus, the capabilities of the new instrument are illustrated using representative results from deployment in the semi-polluted marine boundary layer at the Weybourne Atmospheric Observatory, UK, and in a tropical rainforest at the Bukit Atur Global Atmospheric Watch station, Danum Valley, Borneo.

Seasonal dependence of peroxy radical concentrations at a Northern hemisphere marine boundary layer site during summer and winter: evidence for radical activity in winter

Abstract. Peroxy radicals (HO2+Σ RO2) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer was higher than winter (1.51±0.5 ppbv h−1 and 1.11±0.47 ppbv h−1, respectively). The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5 min in summer and 21 minutes in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and that significant oxidant levels are sustained in winter. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state.

An improved dual channel PERCA instrument for atmospheric measurements of peroxy radicals

This paper describes a new dual-channel PEroxy RadiCal Amplification (PERCA) instrument, which has been designed to improve the time resolution and signal to noise and to reduce the interference caused by variations in ambient ozone concentrations. The instrument was run at the Weybourne Atmospheric Observatory (WAO), North Norfolk, during WAOWEX (Weybourne Atmospheric Observatory Winter Experiment) in January/February 2002 and INSPECTRO (Influence of clouds on the spectral actinic flux in the lower troposphere) in September 2002. The performance of the instrument is assessed and compared to that of a single channel instrument. In particular, it is shown how the precision is greatly improved in fluctuating background ozone conditions. In addition the improved time response of the instrument allows changes in peroxy radical concentrations to be related to rapid changes in nitric oxide concentrations and the ozone photolysis frequency, j(O(1)D).

Aerosol modulation of small ion growth in coastal air

Molecular cluster ions are produced throughout the troposphere by radon isotopes and cosmic rays, causing the slight electrical conductivity ( σ ) of atmospheric air. In a field campaign at the Weybourne Atmospheric Observatory on the Norfolk coast of the UK (52°57′23′′N 1°7′40′′E), aerosol size spectra were obtained simultaneously with σ measurements and background radioactivity, from 11th to 17th May 2004. σ varied with wind direction, from the modulation of the total aerosol number concentration Z rather than changes in ion production from radioactivity. σ was at its greatest when the air originated over the sea. Cluster ion properties were deduced using the σ data and the ion balance equation. The ion mobility μ decreased as Z decreased, corresponding to an increase in average cluster ion size. Using the attachment timescale of ions to aerosol as the typical time during which the ions can grow, negative ion growth occurred at ∼3 nm hr −1 . Aerosol concentration changes modulate the time in which the ions can grow and the availability of condensable vapour.

Atmospheric nitrogen inputs into the North Sea: effect on productivity

The ANICE (Atmospheric Nitrogen Inputs into the Coastal Ecosystem) project addressed the atmospheric deposition of nitrogen to the North Sea, with emphasis on coastal effects. ANICE focused on quantifying the deposition of inorganic nitrogen compounds to the North Sea and the governing processes. An overview of the results from modelling and experimental efforts is presented. They serve to identify the role of the atmosphere as a source of biologically essential chemical species to the marine biota. Data from the Weybourne Atmospheric Observatory (UK) are used to evaluate the effect of short episodes with very high atmospheric nitrogen concentrations. One such episode resulted in an average deposition of 0.8 mmol N m −2 day −1, which has the potential to promote primary productivity of 5.3 mmol C m −2 day −1. This value is compared to long-term effects determined from model results. The total calculated atmospheric deposition to the North Sea in 1999 is 948 kg N km −1, i.e. 0.19 mmol N m −2 day −1 which has the potential to promote primary productivity of 1.2 mmol C m −2 day −1. Detailed results for August 1999 show strong gradients across the North Sea due to adjacent areas where emissions of NO x and NH 3 are among the highest in Europe. The average atmospheric deposition to the southern part of the North Sea in August 1999 could potentially promote primary production of 2.0 mmol C m −2 day −1, i.e. ∼5.5% of the total production at this time of the year in this area of the North Sea. For the entire study area the atmospheric contribution to the primary production per m 2 is about two-third of this value. Most of the deposition occurs during short periods with high atmospheric concentrations. This atmospheric nitrogen is almost entirely anthropogenic in origin and thus represents a human-induced perturbation of the ecosystem.

Deposition of nitrogen into the North Sea

The flux of nitrogen species from the atmosphere into the ocean, with emphasis on coastal waters, was addressed during the ANICE project (Atmospheric Nitrogen Inputs into the Coastal Ecosystem). ANICE focused on quantifying the deposition of atmospheric inputs of inorganic nitrogen compounds (HNO3, NO3-, NH3 and NH4+) into the North Sea and the processes governing this deposition. The Southern North Sea was studied as a prototype. Because the physical and chemical processes are described, as opposed to empirical relations, the results can potentially be transferred to other regional seas like the Mediterranean, the North Atlantic continental shelf area and the Baltic. Two intensive field experiments were undertaken, centred around the offshore tower Meetpost Noordwijk and the Weybourne Atmospheric Observatory in East Anglia (UK). Long-term measurements were made on a ferry sailing between Hamburg and Harwich/Newcastle. These measurements provided data for sensitivity studies of a variety of problems associated with the coastal region that are not easily evaluated with larger scale models, to constrain models and to test model results. Concentrations of nitrogen compounds over the North Sea and the resulting deposition presented in this paper were obtained with the Lagrangian transport-chemistry model ACDEP. The average annual deposition in 1999 was 906kg Nkm-2. The results are compared with experimental data from the ferry. Effects of temporal and spatial variations are evaluated based on experimental results and small-scale model studies. In particular, effects of the aerosol size distribution on the nitrogen deposition are discussed. © 2003 Elsevier Ltd. All rights reserved.

Clinical benefits of low serum digoxin concentrations in heart failure

The flux of nitrogen species from the atmosphere into the ocean, with emphasis on coastal waters, was addressed during the ANICE project (Atmospheric Nitrogen Inputs into the Coastal Ecosystem). ANICE focused on quantifying the deposition of atmospheric inputs of inorganic nitrogen compounds (HNO3, NO3−, NH3 and NH4+) into the North Sea and the processes governing this deposition. The Southern North Sea was studied as a prototype. Because the physical and chemical processes are described, as opposed to empirical relations, the results can potentially be transferred to other regional seas like the Mediterranean, the North Atlantic continental shelf area and the Baltic. Two intensive field experiments were undertaken, centred around the offshore tower Meetpost Noordwijk and the Weybourne Atmospheric Observatory in East Anglia (UK). Long-term measurements were made on a ferry sailing between Hamburg and Harwich/Newcastle. These measurements provided data for sensitivity studies of a variety of problems associated with the coastal region that are not easily evaluated with larger scale models, to constrain models and to test model results. Concentrations of nitrogen compounds over the North Sea and the resulting deposition presented in this paper were obtained with the Lagrangian transport-chemistry model ACDEP. The average annual deposition in 1999 was 906 kg N km−2. The results are compared with experimental data from the ferry. Effects of temporal and spatial variations are evaluated based on experimental results and small-scale model studies. In particular, effects of the aerosol size distribution on the nitrogen deposition are discussed.

Atmospheric input of nitrogen into the North Sea: ANICE project overview

The aim of the atmospheric nitrogen inputs into the coastal ecosystem (ANICE) project is to improve transport–chemistry models that estimate nitrogen deposition to the sea. To achieve this, experimental and modelling work is being conducted which aims to improve understanding of the processes involved in the chemical transformation, transport and deposition of atmospheric nitrogen compounds. Of particular emphasis within ANICE is the influence of coastal zone processes. Both short episodes with high deposition and chronic nitrogen inputs are considered in the project. The improved transport–chemistry models will be used to assess the atmospheric inputs of nitrogen compounds into the European regional seas (the North Sea is studied as a prototype) and evaluate the impact of various emission reduction strategies on the atmospheric nitrogen loads. Assessment of the impact of atmospheric nitrogen on coastal ecosystems will be based on comparisons of phytoplankton nitrogen requirements, other external nitrogen inputs to the ANICE area of interest and the direct nitrogen fluxes provided by ANICE. Selected results from both the experimental and modelling components are presented here. The experimental results show the large spatial and temporal variability in the concentrations of gaseous nitrogen compounds, and their influences on fluxes. Model calculations show the strong variation of both concentrations and gradients of nitric acid at fetches of up to 25 km. Aerosol concentrations also show high temporal variability and experimental evidence for the reaction between nitric acid and sea salt aerosol is provided by size-segregated aerosol composition measured at both sides of the North Sea. In several occasions throughout the experimental period, air mass back trajectory analysis showed connected flow between the two sampling sites (the Weybourne Atmospheric Observatory on the North Norfolk coast of the UK and Meetpost Noordwijk, a research tower at 9 km off the Dutch coast). Results from the METRAS/SEMA mesoscale chemistry transport model system for one of these cases are presented. Measurements of aerosol and rain chemical composition, using equipment mounted on a commercial ferry, show variations in composition across the North Sea. These measurements have been compared to results obtained with the transport–chemistry model ACDEP which calculates the atmospheric inputs into the whole North Sea area. Finally, the results will be made available for the assessment of the impact of atmospheric nitrogen on coastal ecosystems.

Ozone deposition to coastal waters

AbstractThe air‐sea exchange rate of ozone to a coastal region on the North Sea was measured using the eddy correlation technique at the UK Weybourne Atmospheric Observatory. The average measured surface resistance to ozone uptake, rs[O3], was found to be 950 ± 70 s m−1. This exchange rate for coastal waters is very close to that recommended for open ocean conditions by Galbally and Roy of 1000 s m−1. The results are discussed in the light of currently accepted exchange rates and the rather small micrometeorological measurement database available for trace gas exchange to sea surfaces. Although more data are needed to confirm the observations, a tentative dependence on the surface uptake with friction speed, u*, was found, given by rs[O3] ≈︁ –574 In(u*) + 282 s m−1, possibly explaining the variation in previous measurements presented in the literature which were mostly obtained using chamber techniques.

Budget of [formula omitted] species measured at a coastal site

Concentrations of total NO y as well as the major individual species comprising NO y , i.e. NO, NO 2, PAN, HNO 3, HONO and aerosol nitrate, have been measured in three campaigns at the Weybourne Atmospheric Observatory on the north Norfolk coast in Eastern England. The sum of the individual NO y species ( ∑NO yi ) accounted for a high proportion (typically 96%) of total NO y in the two Winter campaigns carried out, but considerably less (about 79%) in a Summer campaign. It was found that the apparent deficit in ∑NO yi in the summer campaign samples correlated closely with the concentration of NH x (sum of gaseous ammonia and particulate ammonium) and it appears that excessive cleaning of the converter led to a sensitivity to these species. Subtraction of the NH x interference leads to a high degree of closure, close to 100% in morning and nighttime samples and 95% in afternoon samples. Thus, unlike many published studies, there is no substantial “missing” NO y and the small deficit in afternoon samples is probably explicable in terms of unmeasured photochemically generated organic nitrates. The magnitude of the ratio ∑NO yi/ NO y appeared largely independent of the NO y concentration. The NO x/ NO y ratio tended to increase with increased NO y in the full dataset consistent with lesser oxidation of NO x in the more polluted airmasses. This facet was not obvious, however, in a subset of marine airmass samples. On a short timescale, however, the NO x/ NO y ratio can exhibit a strong diurnal cycle. An attempt to simulate this cycle of NO x/ NO y by means of a numerical model was fairly successful, though there was some lowering of the midpoint of the oscillation towards the end of the run. It was also demonstrated that if the rate of diurnally averaged nitric acid deposition were to match its rate of formation from NO 2, a relatively constant NO x/ NO y ratio in time-averaged samples could be explained without invoking atmospheric conversion of HNO 3 to NO 2. Nevertheless, the latter remains a possible explanation for the relative constancy of the NO x/ NO y ratio.

Studies of Oxidant Production at the Weybourne Atmospheric Observatory in Summer and Winter Conditions

Detailed studies have been made of the behaviour of gases and radicals involved in the production of oxidants at the Weybourne Atmospheric Observatory in both summertime and wintertime conditions. In June 1995 the range of meteorological conditions experienced varied such that ozone destruction was observed in clean northerly air flows reaching Weybourne down the North Sea from the Arctic, and ozone production was observed in varying degrees in air with different loadings of nitrogen oxides and other precursors. The transition point for ozone destruction to ozone production occurred at a nitric oxide concentration of the order of 50 pptv. Plumes of polluted air from various urban areas in the U.K. were experienced in the June campaign at Weybourne. Quantitative studies of ozone production in a plume from the Birmingham conurbation on 18 June 1995 showed that the measurement of ozone production agreed well with calculated production rates from the product of the nitric oxide and peroxy radical concentrations (r2=0.9). In wintertime conditions (October–November 1994) evidence was also found for oxidant production, defined as the sum of O3+NO2. At this time of year the peroxy radical concentrations (RO2) were much lower than observed in the summertime and the nitric oxide (NO) was much higher. There was still sufficient RO2 during the day, however, for a slow accumulation of oxidant. Confirmatory evidence for this comes from the diurnal co-variance of (O3+NO2) with PAN, an excellent tracer of tropospheric photochemistry. The same type of covariance occurs in summer between PAN and ozone. The results obtained in these series of measurements are pertinent to understanding the measures necessary to control production of regional photochemical air pollution, and to the production of ozone throughout the northern hemisphere in winter.

Measurement of the Diurnal Variation of the OH Radical Concentration and Analysis of the Data by Modelling

Daily variations of the hydroxyl radical concentration have been measured during a campaign at the Weybourne Atmospheric Observatory (WAO) in June 1995. These measurements are compared with box model calculations, based on a slightly modified, second generation Regional Acid Deposition Model (RADM2). Results from eight days of the comparison are presented. A detailed analysis and discussion of the different source and sink terms is given for two days: Julian Day (JD) 170 (19 June, and 178 (27 June). In both cases excellent agreement between the measurements and the calculation is obtained, indicating that the model describes the OH chemistry sufficiently well. Furthermore, the analysis of these days demonstrate that JD 170 is dominated by the NOx catalysed OH production, whereas JD 178 is influenced by OH formation via ozone photolysis.

Observations of the Nitrate Radical in the Marine Boundary Layer

A study of the nitrate radical (NO3) has been conducted through a series of campaigns held at the Weybourne Atmospheric Observatory, located on the coast of north Norfolk, England. The NO3 concentration was measured in the lower boundary layer by the technique of differential optical absorption spectroscopy (DOAS). Although the set of observations is limited, seasonal patterns are apparent. In winter, the NO3 concentration in semi-polluted continental air masses was found to be of the order of 10 ppt, with an average turnover lifetime of 2.4 minutes. During summer in clean northerly air flows, the concentration was about 6 ppt with a lifetime of 7.2 minutes. The major loss mechanisms for the radical were investigated in some detail by employing a chemical box model, constrained by a suite of ancillary measurements. The model indicates that during the semi-polluted conditions experienced in winter, the major loss of NO3 occurred indirectly through reactions of N2O5, either in the gas-phase with H2O, or through uptake on aerosols. The most important direct loss was via reactions of NO3 with a number of unsaturated nonmethane hydrocarbons. The cleaner air masses observed during the summer were of marine origin and contained elevated concentrations of dimethyl sulfide (DMS), which provided the major loss route for NO3. The box model was then used to investigate the conditions in the remote marine boundary layer under which DMS will be oxidised more rapidly at night (by NO3) than during the day (by OH). This should occur if the concentration of NO2 is more than about 60% that of DMS.