Challenges and policy implications of long-term changes in mass absorption cross-section derived from equivalent black carbon and elemental carbon measurements in London and south-east England in 2014-2019.

Determining the concentration of carbonaceous particles in ambient air is important for climate modelling, source attribution and air quality management. This study presents the difficulties associated with the interpretation of apparent long-term changes in the mass absorption cross section (MAC) of carbonaceous particles in London and south-east England based on equivalent black carbon (eBC) and elemental carbon (EC) measurements between 2014 and 2019. Although these two measurement techniques were used to determine the concentration of carbonaceous aerosols, the concentrations of eBC and EC changed at different rates at all sites, and exhibited different long-term trends. eBC measurements obtained using aethalometer instruments for traffic and urban background sites demonstrated consistent trends, showing decreases in concentrations of up to -12.5% y-1. The EC concentrations showed no change at the urban background location, a similar change to eBC at the traffic site and a significant upward trend of +10% y-1 was observed at the rural site. Despite these differences, the trends in the MAC values decreased at all sites in a similar way, with rates of change from -5.5% y-1 to -10.1% y-1. The different trends and magnitudes of change for the eBC and EC concentrations could lead to uncertainty in quantifying the efficacy of intervention measures and to different conclusions for policy making. This paper provides possible explanations of the observed decrease in MAC values over time.

Standardisation of a European measurement method for organic carbon and elemental carbon in ambient air: results of the field trial campaign and the determination of a measurement uncertainty and working range.

The European Committee for Standardisation (CEN) Technical Committee 264 'Air Quality' has recently produced a standard method for the measurements of organic carbon and elemental carbon in PM2.5 within its working group 35 in response to the requirements of European Directive 2008/50/EC. It is expected that this method will be used in future by all Member States making measurements of the carbonaceous content of PM2.5. This paper details the results of a laboratory and field measurement campaign and the statistical analysis performed to validate the standard method, assess its uncertainty and define its working range to provide clarity and confidence in the underpinning science for future users of the method. The statistical analysis showed that the expanded combined uncertainty for transmittance protocol measurements of OC, EC and TC is expected to be below 25%, at the 95% level of confidence, above filter loadings of 2 µg cm-2. An estimation of the detection limit of the method for total carbon was 2 µg cm-2. As a result of the laboratory and field measurement campaign the EUSAAR2 transmittance measurement protocol was chosen as the basis of the standard method EN 16909:2017.

The contributions to long-term health-relevant particulate matter at the UK EMEP supersites between 2010 and 2013: Quantifying the mitigation challenge.

Human health burdens associated with long-term exposure to particulate matter (PM) are substantial. The metrics currently recommended by the World Health Organization for quantification of long-term health-relevant PM are the annual average PM10 and PM2.5 mass concentrations, with no low concentration threshold. However, within an annual average, there is substantial variation in the composition of PM associated with different sources. To inform effective mitigation strategies, therefore, it is necessary to quantify the conditions that contribute to annual average PM10 and PM2.5 (rather than just short-term episodic concentrations). PM10, PM2.5, and speciated water-soluble inorganic, carbonaceous, heavy metal and polycyclic aromatic hydrocarbon components are concurrently measured at the two UK European Monitoring and Evaluation Programme (EMEP) 'supersites' at Harwell (SE England) and Auchencorth Moss (SE Scotland). In this work, statistical analyses of these measurements are integrated with air-mass back trajectory data to characterise the 'chemical climate' associated with the long-term health-relevant PM metrics at these sites. Specifically, the contributions from different PM concentrations, months, components and geographic regions are detailed. The analyses at these sites provide policy-relevant conclusions on mitigation of (i) long-term health-relevant PM in the spatial domain for which these sites are representative, and (ii) the contribution of regional background PM to long-term health-relevant PM. At Harwell the mean (±1 sd) 2010-2013 annual average concentrations were PM10=16.4±1.4µgm(-3) and PM2.5=11.9±1.1µgm(-3) and at Auchencorth PM10=7.4±0.4µgm(-3) and PM2.5=4.1±0.2µgm(-3). The chemical climate state at each site showed that frequent, moderate hourly PM10 and PM2.5 concentrations (defined as approximately 5-15µgm(-3) for PM10 and PM2.5 at Harwell and 5-10µgm(-3) for PM10 at Auchencorth) determined the magnitude of annual average PM10 and PM2.5 to a greater extent than the relatively infrequent high, episodic PM10 and PM2.5 concentrations. These moderate PM10 and PM2.5 concentrations were derived across the range of chemical components, seasons and air-mass pathways, in contrast to the highest PM concentrations which tended to associate with specific conditions. For example, the largest contribution to moderate PM10 and PM2.5 concentrations - the secondary inorganic aerosol components, specifically NO3(-) - were accumulated during the arrival of trajectories traversing the spectrum of marine, UK, and continental Europe areas. Mitigation of the long-term health-relevant PM impact in the regions characterised by these two sites requires multilateral action, across species (and hence source sectors), both nationally and internationally; there is no dominant determinant of the long-term PM metrics to target.

Characterisation of the de-agglomeration effects of bovine serum albumin on nanoparticles in aqueous suspension.

This paper describes the use of nanoparticle characterisation tools to evaluate the interaction between bovine serum albumin (BSA) and dispersed nanoparticles in aqueous media. Dynamic light scattering, zeta-potential measurements and scanning electron microscopy were used to probe the state of zinc oxide (ZnO) and titanium dioxide (TiO(2)) nanoparticles in the presence of various concentrations of BSA, throughout a three-day period. BSA was shown to adhere to ZnO but not to TiO(2). The adsorption of BSA led to subsequent de-agglomeration of the sub-micron ZnO clusters into smaller fragments, even breaking them up into individual isolated nanoparticles. We propose that certain factors, such as adsorption kinetics of BSA on to the surface of ZnO, as well as the initial agglomerated state of the ZnO, prior to BSA addition, are responsible for promoting the de-agglomeration process. Hence, in the case of TiO(2) we see no de-agglomeration because: (a) the nanoparticles are more highly agglomerated to begin with and (b) BSA does not adsorb effectively on the surface of the nanoparticles. The zeta-potential results show that, for either ZnO or TiO(2), the presence of BSA resulted in enhanced stability. In the case of ZnO, the enhanced stability is limited to BSA concentrations below 0.5 wt.%. Steric and electrostatic repulsion are thought to be responsible for improved stability of the dispersion.

Ambient air particulate matter PM10 and PM2.5: developments in European measurement methods and legislation.

The measure of airborne particulate matter PM10 is effectively defined for European regulatory purposes by the European Committee for Standardisation (CEN) standard EN 12341:1998--a gravimetric filter-based method. However, compared with the reference methods written for other pollutants, specifically to address the needs of the Air Quality Directives, EN 12341 falls short in areas such as ongoing Quality Assurance and Quality Control. Also, scientific knowledge about PM has moved on considerably since 1998, so that we now realize that implementations of variations allowed within EN 12341:1998 can lead to substantial differences in results obtained. These issues were partially addressed within the CEN standard for PM2.5, EN 14907:2005, which, for example, included tighter control of the handling of sampled filters to reduce losses of semi-volatile material. CEN Technical Committee 264 Working Group 15 is currently revising EN 12341, and has the opportunity to improve the reference method further, for example by tighter specification of the filter material, or by changing the specification for the humidity at which the filters are brought to equilibrium. Any changes must, however, be considered in the context of the regulatory implications of the standard, so that improvements in scientific quality must be balanced with the effect of a step change in reference method, and with associated costs. The paper outlines the present position of the EN 12341 revision and recent changes to EU Air Quality legislation.