Articles | Volume 9, issue 10
Atmos. Meas. Tech., 9, 4891–4900, 2016
Atmos. Meas. Tech., 9, 4891–4900, 2016

Research article 06 Oct 2016

Research article | 06 Oct 2016

An automated online instrument to quantify aerosol-bound reactive oxygen species (ROS) for ambient measurement and health-relevant aerosol studies

Francis P. H. Wragg1, Stephen J. Fuller1, Ray Freshwater1, David C. Green2, Frank J. Kelly2, and Markus Kalberer1 Francis P. H. Wragg et al.
  • 1Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK
  • 2MRC-PHE Centre for Environment and Health, King's College London, Franklin-Wilkins Building, 150 Stamford Street, London SE1 9NH, UK

Abstract. The adverse health effects associated with ambient aerosol particles have been well documented, but it is still unclear which aerosol properties are most important for their negative health impact. Some studies suggest the oxidative effects of particle-bound reactive oxygen species (ROS) are potential major contributors to the toxicity of particles. Traditional ROS measurement techniques are labour-intensive, give poor temporal resolution and generally have significant delays between aerosol sampling and ROS analysis. However, many oxidising particle components are reactive and thus potentially short-lived. Thus, a technique to quantify particle-bound ROS online would be beneficial to quantify also the short-lived ROS components.

We introduce a new portable instrument to allow online, continuous measurement of particle-bound ROS using a chemical assay of 2′7′-dichlorofluorescein (DCFH) with horseradish peroxidase (HRP), via fluorescence spectroscopy. All components of the new instrument are attached to a containing shell, resulting in a compact system capable of automated continuous field deployment over many hours or days.

From laboratory measurements, the instrument was found to have a detection limit of ∼  4 nmol [H2O2] equivalents per cubic metre (m3) air, a dynamic range up to at least ∼  2000 nmol [H2O2] equivalents per m3 air and a time resolution of ≤  12 min. The instrument allows for ∼  16 h automated measurement if unattended and shows a fast response to changes in concentrations of laboratory-generated oxidised organic aerosol. The instrument was deployed at an urban site in London, and particulate ROS levels of up to 24 nmol [H2O2] equivalents per m3 air were detected with PM2.5 concentrations up to 28 µg m−3.

The new and portable Online Particle-bound ROS Instrument (OPROSI) allows fast-response quantification; this is important due to the potentially short-lived nature of particle-bound ROS as well as fast-changing atmospheric conditions, especially in urban environments. The instrument design allows for automated operation and extended field operation with twice-daily presence of an operator. As well as having sensitivity suitable for ambient level measurement, the instrument is also suitable at concentrations such as those required for laboratory and chamber toxicological studies.

Short summary
A new portable, online instrument was designed, built and characterised to quantify reactive oxygen species (ROS) in atmospheric aerosols for laboratory and field deployment. ROS are potentially major contributors to the toxicity of particles. Our new instrument allows automated quantification of ROS over days with a detection limit of about 4 nmol [H2O2] equivalents per cubic metre of air, allowing for continuous atmospheric measurements of this important aerosol toxicity parameter.