Determination of antimony and barium in UK air quality samples as indicators of non-exhaust traffic emissions.

The aim of this study was to determine concentrations of antimony and barium in air quality samples and assess the potential suitability of these metals as tracer elements for non-exhaust traffic emissions sources. Air quality filters sampled at monitoring sites around the UK for the purposes of the UK Heavy Metals Monitoring Network were subjected to microwave digestion in hydrogen peroxide and nitric acid, then analysed by ICP-MS for a suite of metals including antimony and barium. The average antimony concentration found across all the network sites was 1.84 ng m-3; the average barium concentration was 6.33 ng m-3. The range of antimony concentrations observed was 0.13-8.02 ng m-3; barium concentrations ranged from levels below the detection limit of 0.18 to 39.9 ng m-3. There are no legislative limits for antimony and barium in ambient air, but the maximum concentrations found are well below the Workplace Exposure Limits specified by the UK Health and Safety Executive. The highest concentrations were found at roadside sites situated to monitor traffic environments, supporting the suitability of antimony and barium to be considered tracer elements for traffic emissions sources. Strong correlations were observed between antimony, barium and copper, indicating they share a common traffic-related source. Based on the strong correlation with copper at urban and traffic locations, indicative annual UK atmospheric emission estimates for antimony and barium in brake and tyre wear were calculated as 6 and 19 tonnes respectively.

Lithographical gap-size engineered nanoarrays for surface-enhanced Raman probing of biomarkers.

Engineered gold nanostructured arrays with feature separation in the sub-10-nm range were fabricated and used for highly sensitive surface enhanced Raman scattering (SERS) detection of biomarkers. Nanostructuring is achieved by combining electron beam lithography with the so-called shadow evaporation technique which involves a two-step Au vapor deposition through a suspended Ge mask while the substrate is tilted in opposite directions. This results in a regular triangular surface pattern with extremely small gap distances that allow positive enhancement of the local electric fields by enabling improvements in the electromagnetic coupling between adjacent nanoparticles. The resulting SERS active surfaces are suitable for the realization of reference procedures for quantifying marker molecules like urea or creatinine at physiologically relevant concentrations.

Intelligent routes to the controlled synthesis of nanoparticles.

We describe an autonomous 'black-box' system for the controlled synthesis of fluorescent nanoparticles. The system uses a microfluidic reactor to carry out the synthesis and an in-line spectrometer to monitor the emission spectra of the emergent particles. The acquired data is fed into a control algorithm which reduces each spectrum to a scalar 'dissatisfaction coefficient' and then intelligently updates the reaction conditions in an effort to minimise this coefficient and so drive the system towards a desired goal. In the tests reported here, CdSe nanoparticles were prepared by separately injecting solutions of CdO and Se into the two inlets of a heated y-shaped microfluidic reactor. A noise-tolerant global search algorithm was then used to efficiently identify-without any human intervention-the injection rates and temperature that yielded the optimum intensity for a chosen emission wavelength.

Resonance contributions to anti-Stokes/Stokes ratios under surface enhanced Raman scattering conditions.

Anti-Stokes/Stokes asymmetries under surface enhanced Raman scattering (SERS) conditions are studied for a wide variety of SERS-active media and different analytes. Evidence is provided for the existence of underlying resonances that create these asymmetries. We show here that these resonances are associated with the electromagnetic coupling between the analyte (probe) and the metal. The work demonstrates the use of the anti-Stokes/Stokes ratio as a tool to understand the hierarchy of resonances in the SERS problem, which is essential for quantification purposes.

Physics of single molecule fluctuations in surface enhanced Raman spectroscopy active liquids.

Surface enhanced Raman spectroscopy (SERS) of dyes in solution allows the study of the differences between ensemble averaged spectroscopic signals and single molecular events. We address several outstanding issues in single molecule detection via SERS; in particular, evidence for single molecule vibrational pumping and/or single molecule laser heating, the statistics of hotspots in the liquid, and anti-Stokes/Stokes anomalies. We demonstrate that anti-Stokes/Stokes ratios are a very unreliable measure of temperature, because the two processes are affected differently by the underlying frequency-dependent plasmon resonances. Subtle hints of vibrational pumping and/or heating in single molecules can only obtained via careful cross correlations between the parameters (frequency position, width, and intensity) of the Stokes signals for different excitation lasers. We introduce the use of single-peak parameter cross correlations for the study of these phenomena.

Stokes/anti-Stokes anomalies under surface enhanced Raman scattering conditions.

The possibility of achieving anti-Stokes stimulation and/or pumping under surface enhanced Raman scattering conditions has been the source of intense controversies in the literature. With the aim of clarifying some of the aspects of this problem, we study theoretically and experimentally the situation in a model system which highlights some of the difficulties in the interpretation of the data. We show that many of the assumptions often presumed in the literature need to be assessed with care in each case. Through careful experiments we show, in particular, that the anti-Stokes/Stokes ratio for a specific mode in the same sample can depend on the chosen laser wavelength. This latter effect is a manifestation of the influence of the internal plasmon resonances (hot spots) in the result. Different possibilities and further research directions are highlighted and discussed.