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Despite widespread use for more than two decades, the SERS phenomenon has defied accurate physical and chemical explanation. The relative contributions from electronic and chemical mechanisms are difficult to quantify and are often not reproduced under nominally similar experimental conditions. This work has used electromagnetic modelling to predict the Raman enhancement expected from three configurations: metal nanoparticles, structured metal surfaces, and sharp metal tips interacting with metal surfaces. In each case, parameters such as artefact size, artefact separation and incident radiation wavelength have been varied and the resulting electromagnetic field modelled. This has yielded an electromagnetic description of these configurations with predictions of the maximum expected Raman enhancement, and hence a prediction of the optimum substrate configuration for the SERS process. When combined with experimental observations of the dependence of Raman enhancement with changing ionic strength, the modelling results have allowed a novel estimate of the size of the chemical enhancement mechanism to be produced.

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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.