Measurements at appropriate spatial and temporal scales are essential for understanding and monitoring spatially heterogeneous environments with complex and highly variable emission sources, such as in urban areas. However, the costs and complexity of conventional air quality measurement methods means that measurement networks are generally extremely sparse. In this paper we show that miniature, low-cost electrochemical gas sensors, traditionally used for sensing at parts-per-million (ppm) mixing ratios can, when suitably configured and operated, be used for parts-per-billion (ppb) level studies for gases relevant to urban air quality. Sensor nodes, in this case consisting of multiple individual electrochemical sensors, can be low-cost and highly portable, thus allowing the deployment of scalable high-density air quality sensor networks at fine spatial and temporal scales, and in both static and mobile configurations. In this paper we provide evidence for the performance of electrochemical sensors at the parts-per-billion level, and then outline results obtained from deployments of networks of sensor nodes in both an autonomous, high-density, static network in the wider Cambridge (UK) area, and as mobile networks for quantification of personal exposure. Examples are presented of measurements obtained with both highly portable devices held by pedestrians and cyclists, and static devices attached to street furniture. The widely varying mixing ratios reported by this study confirm that the urban environment cannot be fully characterised using sparse, static networks, and that measurement networks with higher resolution (both spatially and temporally) are required to quantify air quality at the scales which are present in the urban environment. We conclude that the instruments described here, and the low-cost/high-density measurement philosophy which underpins it, have the potential to provide a far more complete assessment of the high-granularity air quality structure generally observed in the urban environment, and could ultimately be used for quantification of human exposure as well as for monitoring and legislative purposes.

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[1] The analysis for BrO using the technique of differential optical absorption spectroscopy as applied to spectra of light scattered from the zenith sky has historically presented something of a challenge, leading to uncertainty about the accuracy of measurements. This has largely been due to the large sensitivity of the measurement to many analysis parameters and due to the small size of the absorption features being measured. BrO differential slant columns have been measured by six different groups taking part in an intercomparison exercise at Observatoire de Haute-Provence in France from 23 to 27 June 1996. The data are analyzed in a collaborative attempt to improve the overall analysis for BrO through investigation of a series of sources of errors in the instrumentation, calibration, input to the analysis, and the spectral analysis itself. The study included comprehensive sensitivity tests performed using both actual measurements and synthetic data. The latter proved invaluable for assessing several aspects of the spectral analysis without the limitations of spectral quality and instrument variability. The most significant sources of error are identified as the wavelength calibration of several of the absorption cross sections fitted and of the measured spectra themselves, the wavelength region of the fitting, the temperature dependence of the O 3 absorption cross sections, failure to adequately account for the so-called I 0 effect, inadequate offset correction, and inadequate measurement of the individual instrument slit functions. Recommendations for optimal analysis settings are presented, and comparing the results from the analysis of the campaign data shows BrO differential slant column observations from the various groups to be in agreement to within 4% on average between 87°and 90°s olar zenith angle, with a scatter of 16%.

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