Consistency and uncertainty of UK measurements of mercury in precipitation.

A novel method to assess the uncertainty of measurement of mercury in precipitation for the UK's Heavy Metals Monitoring Network is presented. The method makes use of the fact that, because of the high risk of sample contamination, samples are taken in duplicate in order to ensure valid data is available for as many sampling periods as possible. Where both samples are valid a good opportunity is afforded to use the statistical differences in the rain volumes sampled and the mercury concentrations measured to assess the overall uncertainty of the measurement. This process has produced estimated uncertainties in good agreement with previous studies and well within the limits specified by European legislation. The work also highlighted an effective method to spot outliers in the paired samples at the data ratification stage.

Predicting the frequency of extreme air quality events.

A new method for predicting the frequency of extreme air quality events is proposed. The method is based on knowing the number of times a pollutant is measured at different concentrations during a period of data collection and fitting this data to a Weibull-type function. Extrapolation of the function to higher concentrations then allows the frequency of extreme events that did not occur during the collection period to be predicted, albeit with an unspecified uncertainty. Prediction of the frequency of events over a given concentration, which was exceeded during the period of data collection, has also been performed assuming Poisson statistics. The assumption of Poisson statistics enables the provision of an uncertainty statement to accompany the prediction. The methods are trialled on a data set of daily average PM10 mass concentrations recorded at Marylebone Road in London between 2007 and 2016, inclusive. Using the method it was predicted that a daily average PM10 mass concentration of over 100 µg m-3, corresponding to the highest UK Daily Air Quality Index band, should be expected once in just over three years and this agreed well with real observations, demonstrating the utility of this new technique.

Standardisation of a European measurement method for organic carbon and elemental carbon in ambient air: results of the field trial campaign and the determination of a measurement uncertainty and working range.

The European Committee for Standardisation (CEN) Technical Committee 264 'Air Quality' has recently produced a standard method for the measurements of organic carbon and elemental carbon in PM2.5 within its working group 35 in response to the requirements of European Directive 2008/50/EC. It is expected that this method will be used in future by all Member States making measurements of the carbonaceous content of PM2.5. This paper details the results of a laboratory and field measurement campaign and the statistical analysis performed to validate the standard method, assess its uncertainty and define its working range to provide clarity and confidence in the underpinning science for future users of the method. The statistical analysis showed that the expanded combined uncertainty for transmittance protocol measurements of OC, EC and TC is expected to be below 25%, at the 95% level of confidence, above filter loadings of 2 µg cm-2. An estimation of the detection limit of the method for total carbon was 2 µg cm-2. As a result of the laboratory and field measurement campaign the EUSAAR2 transmittance measurement protocol was chosen as the basis of the standard method EN 16909:2017.

Standardisation of a European measurement method for the determination of anions and cations in PM2.5: results of field trial campaign and determination of measurement uncertainty.

European Committee for Standardisation (CEN) Technical Committee 264 'Air Quality' has recently produced a standard method for the measurements of anions and cations in PM2.5 within its Working Group 34 in response to the requirements of European Directive 2008/50/EC. It is expected that this method will be used in future by all Member States making measurements of the ionic content of PM2.5. This paper details the results of a field measurement campaign and the statistical analysis performed to validate this method, assess its uncertainty and define its working range to provide clarity and confidence in the underpinning science for future users of the method. The statistical analysis showed that, except for the lowest range of concentrations, the expanded combined uncertainty is expected to be below 30% at the 95% confidence interval for all ions except Cl-. However, if the analysis is carried out on the lower concentrations found at rural sites the uncertainty can be in excess of 50% for Cl-, Na+, K+, Mg2+ and Ca2+. An estimation of the detection limit for all ions was also calculated and found to be 0.03 µg m-3 or below.

An investigation of the matrix sensitivity of refinery gas analysis using gas chromatography with flame ionisation detection.

The response of a flame ionisation detector (FID) on a gas chromatograph to methane, ethane, propane, i-butane and n-butane in a series of multi-component refinery gas standards was investigated to assess the matrix sensitivity of the instrument. High-accuracy synthetic gas standards, traceable to the International System of Units, were used to minimise uncertainties. The instrument response exhibited a small dependence on the component amount fraction: this behaviour, consistent with that of another FID, was thoroughly characterised over a wide range of component amount fractions and was shown to introduce a negligible bias in the analysis of refinery gas samples, provided a suitable reference standard is employed. No significant effects of the molar volume, density and viscosity of the gas mixtures on the instrument response were observed, indicating that the FID is suitable for the analysis of refinery gas mixtures over a wide range of component amount fractions provided that appropriate drift-correction procedures are employed.

Assessing the performance of standard methods to predict the standard uncertainty of air quality data having incomplete time coverage.

As a result of the complex nature of operating multi-station national air quality networks it is rare that complete data sets are produced from these networks. The reliance of most air quality legislation on the assessment of measured annual average concentrations against target or limit concentrations necessitates the use of methods to calculate an annual average value and the uncertainty in this value in the absence of a complete data set for the year in question. Standard procedures exist for performing these calculations, but it is not clear how effective these are when data having low time resolution are collected and missing data accounts for large periods of the year. This paper investigates the influence of these deficiencies using data from UK air quality networks in the form of monthly average concentrations for polycyclic aromatic hydrocarbons and for metals in the PM10 phase of ambient air. Whilst the standard methods currently employed produce good results on average, for individual cases the uncertainty in the annual average calculated when data is missing may be appreciably different from that obtained when full knowledge of the distribution of the data is known. These effects become more apparent as the quantity of missing data increases.

Improved strategies for calculating annual averages of ambient air pollutants in cases of incomplete data coverage.

The consequences of missing data during air quality monitoring activities and the calculation of the annual average mass concentration of ambient pollutants are discussed. Possible strategies for mitigating totally and partially missing data during given measurement periods are presented and evaluated. A mathematical description of a preferred method for the determination of annual average concentration using the simple mean, and not using time weighting to account for missing data, is justified. It is hoped this discussion paper will provoke debate in the air quality community about the best way to assess measured concentrations of ambient pollutants against legislative values.