Measurements of sulphur dioxide in rural air: data quality issues

Discrepancies between long-term average SO2 concentrations measured by UV-Fluorescence monitors in the AURN and DELTA denuders from AGA-Net are caused by inadequate performance of UV-F monitors at low concentrations. The hourly data are essential for measuring possible exceedances of limit values – for which the AURN was established – and there is no suggestion that they are no longer fit for that purpose. However, as operated at present they should not be used to provide data for assessing long-term average concentrations. The DELTA denuders in AGA-Net were specifically designed for that purpose, and provide the data needed to assess rural (and suburban) concentrations for model evaluation across the UK

Missing data in spatiotemporal datasets: the UK rainfall chemistry network

Rainfall chemistry networks inevitably report some missing data, caused by contamination or loss of samples. However, there are no universally accepted rules about how such data, particularly from samples contaminated in the field, are identified and reported, leading to uncertainties in data usage by third parties, and possible incorrect inferences based on the reported data. This paper describes how the UK rainfall chemistry network data have been analysed for contamination, and how missing values can be estimated based on cross-correlations in time and space, using data from 20 sites over 26 years. The final flagged dataset is available through the CEH Environmental Information Data Centre (EIDC). Erroneous data values are identified through consideration of ion balance (internal consistency), and evidence of contamination by birds or windblown dust based on the reported chemical analysis. Overall data capture with the erroneous data excluded and no replacement of missing data was 86%, but with much smaller data capture at some sites in some years, to less than 30% in some cases. The use of estimated data to replace missing values resulted in an increase in overall data capture to 96%, with only one site having data capture less than 70% in an individual year, and all sites achieving a data capture of 88% or more over the full period. The implications of using the reported ‘official’ annual data, as opposed to the dataset with missing values replaced by estimates, are illustrated by consideration of the temporal trend in nitrate at one site, which shows twice the value in the ‘official’ reported annual data compared with the ‘estimated’ data, part of a consistent pattern across all sites. Use of the uncorrected ‘raw’ sample data leads to large errors

The impact of speciated VOCs on regional ozone increment derived from measurements at the UK EMEP supersites between 1999 and 2012

The impact of 27 volatile organic compounds (VOCs) on the regional O3 increment was investigated using measurements made at the UK EMEP supersites Harwell (1999–2001 and 2010–2012) and Auchencorth (2012). Ozone at these sites is representative of rural O3 in south-east England and northern UK, respectively. The monthly-diurnal regional O3 increment was defined as the difference between the regional and hemispheric background O3 concentrations, respectively, derived from oxidant vs. NOx correlation plots, and cluster analysis of back trajectories arriving at Mace Head, Ireland. At Harwell, which had substantially greater regional O3 increments than Auchencorth, variation in the regional O3 increment mirrored afternoon depletion of anthropogenic VOCs due to photochemistry (after accounting for diurnal changes in boundary layer mixing depth, and weighting VOC concentrations according to their photochemical ozone creation potential). A positive regional O3 increment occurred consistently during the summer, during which time afternoon photochemical depletion was calculated for the majority of measured VOCs, and to the greatest extent for ethene and m+p-xylene. This indicates that, of the measured VOCs, ethene and m+p-xylene emissions reduction would be most effective in reducing the regional O3 increment but that reductions in a larger number of VOCs would be required for further improvement. The VOC diurnal photochemical depletion was linked to anthropogenic sources of the VOC emissions through the integration of gridded anthropogenic VOC emission estimates over 96 h air-mass back trajectories. This demonstrated that one factor limiting the effectiveness of VOC gridded emissions for use in measurement and modelling studies is the highly aggregated nature of the 11 SNAP (Selected Nomenclature for Air Pollution) source sectors in which they are reported, as monthly variation in speciated VOC trajectory emissions did not reflect monthly changes in individual VOC diurnal photochemical depletion. Additionally, the major VOC emission source sectors during elevated regional O3 increment at Harwell were more narrowly defined through disaggregation of the SNAP emissions to 91 NFR (Nomenclature for Reporting) codes (i.e. sectors 3D2 (domestic solvent use), 3D3 (other product use) and 2D2 (food and drink)). However, spatial variation in the contribution of NFR sectors to parent SNAP emissions could only be accounted for at the country level. Hence, the future reporting of gridded VOC emissions in source sectors more highly disaggregated than currently (e.g. to NFR codes) would facilitate a more precise identification of those VOC sources most important for mitigation of the impact of VOCs on O3 formation. In summary, this work presents a clear methodology for achieving a coherent VOC, regional-O3-impact chemical climate using measurement data and explores the effect of limited emission and measurement species on the understanding of the regional VOC contribution to O3 concentrations

Long-term trends in rain and cloud chemistry in a region of complex topography

Rain and cloud water from a high-elevation site and an adjacent lower-level site in the northern Pennines of England were sampled and analysed between 1994 and 2008. The comparison of wet deposition and rainfall depth at the high and low-level sites has been used to estimate the additional deposition of pollutants arising from ‘seeder–feeder’ enhancement by washout of the orographic cap cloud that forms over the high-level site. The derived ‘orographic scavenging ratio’ for different ions is used to map the orographic enhancement of wet deposition across the U.K. The ratio of ion concentrations in cloud and in rain at the high-level site is also important for estimating the input of pollutants through the direct capture of cloud water droplets at high elevation sites. Long-term trends in ion concentrations in cloud and rain showed significant downward trends in non-sea sulphate, and a weaker downward trend in nitrate, but no trend in other ions. There was also no trend in the orographic scavenging ratios, implying that the methods used to estimate orographic enhancement across the U.K. are robust over time

Influences on and patterns in total gaseous mercury (TGM) at Harwell, England

Total gaseous mercury (TGM) was monitored during 2013 at the rural monitoring site, Harwell, England using the Tekran 2537A monitoring system. Average TGM for the year was 1.45 ± 0.24 ng m−3. This is comparable to other northern hemisphere studies, but on average 0.5 ng m−3 higher than at its sister monitoring station at Auchencorth Moss, Scotland, but 14% lower than that found in a similar study at the same location of 1.68 ng m−3 in 1995/6. Using wind sector analysis we show the important influence of local emissions, with our data showing that the largest influence on TGM observed is that of the adjacent Science & Innovation campus, making the site more a ‘suburban background’. By using co-located measurements of black carbon and sulphur dioxide as tracers, we present an initial investigation into the impact of the closure of Didcot A coal fired power station, which ceased operating in March 2013. Further analysis using air mass back trajectories shows the long-range contribution to TGM from continental Europe, and that the lowest levels are associated with marine air masses from the west

Patterns and source analysis for atmospheric mercury at Auchencorth Moss, Scotland

Gaseous elemental (GEM), particulate bound (PBM) and gaseous oxidised (GOM) mercury species were monitored between 2009-2011 at the rural monitoring site, Auchencorth Moss, Scotland using the Tekran speciation monitoring system. GEM average for the three year period was 1.40 ± 0.19 ng m-3 which is comparable with other northern hemisphere studies. PBM and GOM concentrations are very low in 2009 and 2010 with geometric mean (x/÷ Standard Deviation) PBM values of 2.56 (x/÷ 3.44) and 0.03 (x/÷ 17.72) pg m-3 and geometric mean (x/÷ Standard Deviation) GOM values of 0.11 (x/÷ 4.94) and 0.09 (x/÷ 8.88) pg m-3 respectively. Using wind sector analysis and air mass back trajectories, the importance of local and regional sources on speciated mercury are investigated and we show the long range contribution to GEM from continental Europe, and that the lowest levels are associated with polar and marine air masses from the north west sector

Operation of EMEP ‘supersites’ in the United Kingdom. Annual report for 2008.

As part of its commitment to the UN-ECE Convention on Long-range Transboundary Air Pollution the United Kingdom operates two ‘supersites’ reporting data to the Co-operative Programme for Monitoring and Evaluation of the Long-range Transmission of Air Pollutants in Europe (EMEP). This report provides the annual summary for 2008, the second full calendar year of operation of the first EMEP ‘supersite’ to be established in the United Kingdom. Detailed operational reports have been submitted to Defra every 3 months, with unratified data. This annual report contains a summary of the ratified data for 2008. The EMEP ‘supersite’ is located in central southern Scotland at Auchencorth (3.2oW, 55.8oN), a remote rural moorland site ~20 km south-west of Edinburgh. Monitoring operations started formally on 1 June 2006. In addition to measurements made specifically under this contract, the Centre for Ecology & Hydrology also acts as local site operator for measurements made under other UK monitoring networks: the Automated Urban and Rural Network (AURN), the UK Eutrophication and Acidification Network (UKEAP), the UK Hydrocarbons Network, and the UK Heavy Metals Rural Network. Some measurements were also made under the auspices of the ‘Air Pollution Deposition Processes’ contract. All these associated networks are funded by Defra. This report summarises the measurements made between January and December 2008, and presents summary statistics on average concentrations. The site is dominated by winds from the south-west, but wind direction data highlight potential sources of airborne pollutants (power stations, conurbations). The average diurnal patterns of gases and particles are consistent with those expected for a remote rural site. The frequency distributions are presented for data where there was good data capture throughout the whole period. Some components (e.g. black carbon) show log-normal frequency distributions, while other components (e.g. ozone) have more nearly normal frequency distributions. A case study is presented for a period in June 2008, showing the influence of regional air pollutants at this remote rural site. All the data reported under the contract are shown graphically in the Appendix

Experimental field estimation of organic nitrogen formation in tree canopies

The content of organic N has been shown in many studies to increase during the passage of rain water through forest canopies. The source of this organic N is unknown, but generally assumed to come from canopy processing of wet or dry-deposited inorganic N. There have been very few experimental studies in the field to address the canopy formation or loss of organic N. We report two studies: a Scots pine canopy exposed to ammonia gas, and a Sitka spruce canopy exposed to ammonium and nitrate as wet deposition. In both cases, organic N deposition in throughfall was increased, but only represented a small fraction (<10%) of the additional inorganic N supplied, suggesting a limited capacity for net organic N production, similar in both conifer canopies under Scottish summertime conditions, of less than 1.6 mmol Nm2 mth1 (equivalent to 3 kg N ha1 y1)

Governing processes for reactive nitrogen compounds in the atmosphere in relation to ecosystem climatic and human health impacts

Reactive nitrogen (Nr) compounds have different fates in the atmosphere due to differences in governing processes of physical transport, deposition and chemical transformation. Nr compounds addressed here include reduced nitrogen (NHx: ammonia (NH3) and its reaction product ammonium (NH4+)), oxidized nitrogen (NOy: nitrogen monoxide (NO) + nitrogen dioxide (NO2) and their reaction products) as well as organic nitrogen compounds (organic N). Pollution abatement strategies need to take into account these differences in the governing processes of these compounds when assessing their impact on ecosystem services, biodiversity, human health and climate. NOx (NO + NO2) emitted from traffic affects human health in urban areas where the presence of buildings increases the residence time in streets. In urban areas this leads to enhanced exposure of the population to NOx concentrations. NOx emissions have little impact on nearby ecosystems because of the small dry deposition rates of NOx. These compounds need to be converted into nitric acid (HNO3) before removal through deposition is efficient. HNO3 sticks quickly to any surface and is thereby either dry deposited or incorporated into aerosols as nitrate (NO3−). In contrast to NOx compounds, NH3 has potentially high impacts on ecosystems near the main agricultural sources of NH3 because of its large ground-level concentrations along with large dry deposition rates. Aerosol phase NH4+ and NO3− contribute significantly to background PM2.5 and PM10 (mass of aerosols with a diameter of less than 2.5 and 10 μm, respectively) with an impact on radiation balance as well as potentially on human health. Little is known quantitatively and qualitatively about organic N in the atmosphere, other than that it contributes a significant fraction of wet-deposited N, and is present in both gaseous and particulate forms in the atmosphere. Further studies are needed to characterize the sources, air chemistry and removal rates of organic N emissions