Falling nickel concentrations in ambient air in South Wales - 50 years of progress.

Measurement of the composition of ambient air has become increasingly widespread over the last 50 years as the detrimental health effects of some air pollutants have become clearer and requirements for these measurements has been embedded in national and international legislation. The aim of this has been not only to assess exposure of the general population to air pollutants but also to assess the effectiveness of abatement strategies to reduce emissions of these pollutants at source. With a rich industrial heritage, the Swansea Valley (South Wales, UK) has long been associated with the refining and production of metal products, especially nickel. Despite a decline in output during the latter part of the twentieth century there is still sufficient activity to prompt a requirement for targeted air monitoring in the area. This is most important for nickel where there is a local history of measured concentrations exceeding legislative target values. This work demonstrates the effectiveness of nickel emissions abatement strategies over the last 50 years by tracking the falling air concentration of nickel over this period. It also demonstrates how the monitoring network in the Swansea Valley has expanded over this time and become significantly more sensitive to nickel emissions. The data presented represents a significant public health achievement - it is likely that the exposure to nickel in air of the population in the Swansea Valley has decreased more than 100-fold over the last 50 years - and reflects the progress in regulation, industrial efficiency, emissions abatement technology and air quality monitoring science achieved during this period.

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.

Concentration trends of metals in ambient air in the UK: a review.

The monitoring of metals in ambient air has been undertaken for over 40 years on a national basis in the UK. During this period, the UK pollution landscape has continued to evolve in terms of emission sources, and the measurement framework for metals in ambient air, the UK Heavy Metals Monitoring Network, has also been subject to significant configuration changes. Therefore, this work provides a timely review of more recent concentration trends in the context of current emission profiles. Overall, throughout this time period, there has been a significant downward trend in the emissions and consequently, the measured concentrations of most metals in UK ambient air. Ambient concentrations were generally found to be well correlated with emission estimates. Analysis of the sensitivity of measured concentrations to emissions suggests that concentrations have fallen faster than the reduction in emission estimates would have predicted at typical median urban background sites.

Investigation into alternative sample preparation techniques for the determination of heavy metals in stationary source emission samples collected on quartz filters.

Monitoring stationary source emissions for heavy metals generally requires the use of quartz filters to collect samples because of the high temperature and high moisture sampling environment. The documentary standard method sample preparation technique in Europe, EN 14385, uses digestion in hydrofluoric acid and nitric acid (HF/HNO3) followed by complexing with boric acid (H3BO3) prior to analysis. However, the use of this method presents a number of problems, including significant instrumental drift during analysis caused by the matrix components, often leading to instrument breakdown and downtime for repairs, as well as posing significant health and safety risks. The aim of this work was to develop an alternative sample preparation technique for emissions samples on quartz filters. The alternative techniques considered were: (i) acid digestion in a fluoroboric acid (HBF4) and HNO3 mixture and (ii) acid extraction in an aqua regia (AR) mixture (HCl and HNO3). Assessment of the effectiveness of these options included determination of interferences and signal drift, as well as validating the different methods by measurement of matrix certified reference materials (CRMs), and comparing the results obtained from real test samples and sample blanks to determine limits of detection. The results showed that the HBF4/HNO3 mixture provides the most viable alternative to the documentary standard preparation technique.

Observation of a physical matrix effect during cold vapour generation measurement of mercury in emissions samples.

The observation of a physical matrix effect during the cold vapour generation-atomic fluorescence measurement of mercury in emissions samples is reported. The effect is as a result of the different efficiencies of liberation of reduced mercury from solution as the matrix of the solution under test varies. The result of this is that peak area to peak height ratios decease as matrix concentration increases, passing through a minimum, before the ratio then increases as matrix concentration further increases. In the test matrices examined - acidified potassium dichromate and sodium chloride solutions - the possible biases caused by differences between the calibration standard matrix and the test sample matrix were as large as 2.8% (relative) representing peak area to peak height ratios for calibration standards and matrix samples of 45 and 43.75, respectively. For the system considered there is a good correlation between the density of the matrix and point of optimum liberation of dissolved mercury for both matrix types. Several methods employing matrix matching and mathematical correction to overcome the bias are presented and their relative merits discussed; the most promising being the use of peak area, rather than peak height, for quantification.

Improvements to standard methodologies for the analytical determination of metals in stationary-source emissions samples.

Deficiencies with the current European reference method for the analysis using inductively couple plasma-mass spectrometry of metals in samples from stationary emissions sources are presented based on experimental data obtained from real samples. The effect of these deficiencies on the quality and accuracy of data is highlighted with biases of up to 40% being observed in real samples. Suggestions to improve the performance of the standard method are presented. In particular, the beneficial effect of using a drift correction procedure to account for the decrease in instrument sensitivity observed during an analytical measurement series is demonstrated. It is shown that this corrective procedure results in substantial improvements to the accuracy of data produced.

Spatial inhomogeneity of metals in particulate matter on ambient air filters determined by LA-ICP-MS and comparison with acid digestion ICP-MS.

Laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) has been used to examine the spatial distribution of metals in particulate matter on ambient air filters. The implications of the inhomogeneous distribution observed for the sub-sampling of such filters for multiple analyses have been discussed. It has been shown that large biases in measured values may occur unless the position and size of the sub-sample are chosen judiciously. Additionally, LA-ICP-MS has been compared against acid digestion ICP-MS as an alternative method for the determination of metals in particulate matter. It has been shown that the majority of variation in the LA-ICP-MS sensitivity accrues from small differences in the positioning of samples.

Twenty-five years of nationwide ambient metals measurement in the United Kingdom: concentration levels and trends.

Ambient air quality has been an important issue for humans and the environment for hundreds of years. More recently, definitive links have been identified between pollutants and adverse effects on human health and on environmental sustainability. Of particular concern since the last quarter of the twentieth century has been the presence of toxic 'heavy metals' in ambient air. In order to measure the concentrations of pollutants, including 'heavy metals', in ambient air, to assess human and environmental exposure, comply with developing legislation, and assess newly introduced abatement strategies, the UK government established nationwide air quality measurement networks in the late 1970s. The nationwide measurement of 'heavy metals' in ambient air began in the late 1970s, and in 1980 was developed into several national networks, aimed at different metals and different emissions sources. These networks were rationalised into the current UK Heavy Metals Monitoring Network in 2003. The data produced by the current scientific operator of the Network, the National Physical Laboratory (NPL), in 2005, marked 25 years of ambient 'heavy metals' measurement in the UK at a nationwide level. This paper celebrates this milestone and provides a novel and critical examination of Network operations, measured concentration levels, and trends, over the last quarter of a century.

The effect of isotopic composition on the uncertainty of routine metal mass concentration measurements in ambient air.

The main sources of uncertainty encountered during the analysis of the mass concentration of metals in ambient air as part of the operation of the UK Heavy Metals Monitoring Network are presented. It is observed that the uncertainty contribution from possible variation in the isotopic composition of the sample depends on the element in question, but can be significant (e.g., for Pb, Cd, and Hg). The working curve method for the ICP-MS analysis of metals in solution, with a low resolution, high throughput instrument measuring at one m/z ratio per element, relies on the relative abundance of the isotopes under consideration being the same in both the sample and the calibration solution. Calculation of the uncertainty in this analysis assumes that the isotopic composition variation within the sample and calibration solution is limited to a defined range. Therefore, in order to confirm the validity of this quantification methodology and its uncertainty budget, the isotopic composition of the calibration standards used for quantification has been determined. The results of this analysis are presented here.