Significant OH production under surface cleaning and air cleaning conditions: Impact on indoor air quality.

We report measurements of hydroxyl (OH) and hydroperoxy (HO2 ) radicals made by laser-induced fluorescence spectroscopy in a computer classroom (i) in the absence of indoor activities (ii) during desk cleaning with a limonene-containing cleaner (iii) during operation of a commercially available "air cleaning" device. In the unmanipulated environment, the one-minute averaged OH concentration remained close to or below the limit of detection (6.5×105  molecule cm-3 ), whilst that of HO2 was 1.3×107  molecule cm-3 . These concentrations increased to ~4×106 and 4×108  molecule cm-3 , respectively during desk cleaning. During operation of the air cleaning device, OH and HO2 concentrations reached ~2×107 and ~6×108  molecule cm-3 respectively. The potential of these OH concentrations to initiate chemical processing is explored using a detailed chemical model for indoor air (the INDCM). The model can reproduce the measured OH and HO2 concentrations to within 50% and often within a few % and demonstrates that the resulting secondary chemistry varies with the cleaning activity. Whilst terpene reaction products dominate the product composition following surface cleaning, those from aromatics and other VOCs are much more important during the use of the air cleaning device.

Impact of surface ozone interactions on indoor air chemistry: A modeling study.

An INdoor air Detailed Chemical Model was developed to investigate the impact of ozone reactions with indoor surfaces (including occupants), on indoor air chemistry in simulated apartments subject to ambient air pollution. The results are consistent with experimental studies showing that approximately 80% of ozone indoors is lost through deposition to surfaces. The human body removes ozone most effectively from indoor air per square meter of surface, but the most significant surfaces for C6 -C10 aldehyde formation are soft furniture and painted walls owing to their large internal surfaces. Mixing ratios of between 8 and 11 ppb of C6 -C10 aldehydes are predicted to form in apartments in various locations in summer, the highest values are when ozone concentrations are enhanced outdoors. The most important aldehyde formed indoors is predicted to be nonanal (5-7 ppb), driven by oxidation-derived emissions from painted walls. In addition, ozone-derived emissions from human skin were estimated for a small bedroom at nighttime with concentrations of nonanal, decanal, and 4-oxopentanal predicted to be 0.5, 0.7, and 0.7 ppb, respectively. A detailed chemical analysis shows that ozone-derived surface aldehyde emissions from materials and people change chemical processing indoors, through enhanced formation of nitrated organic compounds and decreased levels of oxidants.

Observations and impacts of bleach washing on indoor chlorine chemistry.

Ambient levels of chlorinated gases and aerosol components were measured by online chemical ionization and aerosol mass spectrometers after an indoor floor were repeatedly washed with a commercial bleach solution. Gaseous chlorine (Cl2 , 10's of ppbv) and hypochlorous acid (HOCl, 100's of ppbv) arise after floor washing, along with nitryl chloride (ClNO2 ), dichlorine monoxide (Cl2 O), and chloramines (NHCl2 , NCl3 ). Much higher mixing ratios would prevail in a room with lower and more commonly encountered air exchange rates than that observed in the study (12.7 h-1 ). Coincident with the formation of gas-phase species, particulate chlorine levels also rise. Cl2 , ClNO2 , NHCl2 , and NCl3 exist in the headspace of the bleach solution, whereas HOCl was only observed after floor washing. HOCl decays away 1.4 times faster than the air exchange rate, indicative of uptake onto room surfaces, and consistent with the well-known chlorinating ability of HOCl. Photochemical box modeling captures the temporal profiles of Cl2 and HOCl very well and indicates that the OH, Cl, and ClO gas-phase radical concentrations in the indoor environment could be greatly enhanced (>106 and 105  cm-3 for OH and Cl, respectively) in such washing conditions, dependent on the amount of indoor illumination.

How does exposure to nitrogen dioxide compare between on-road and off-road cycle routes?

This study demonstrates a simple method to estimate the extent to which the exposure of cyclists to NO(2) is reduced by using off-road cycle routes rather than on-road cycle routes. Diffusion tubes were used to measure monthly NO(2) concentrations on three paired sets of on- and off-road cycle journeys in and around the City of York in August and September 2008. These measurements were combined with estimates of journey times to calculate time-weighted average concentration and exposure on each route. The average concentration of NO(2) was significantly reduced by a mean of 37.5% when off-road routes were used in place of on-road routes and, despite the longer journey times for off-road routes, exposure was also significantly reduced by a mean of 25.5%. The method described in this study could be adopted more widely to provide a cost effective and simple means of assessing the benefits of alternative cycle routes that are provided by Local Authorities.

A larger pool of ozone-forming carbon compounds in urban atmospheres

Volatile organic compounds play a central role in the processes that generate both urban photochemical smog and tropospheric ozone. For successful and accurate prediction of these pollution episodes, identification of the dominant reactive species within the volatile organic carbon pool is needed. At present, lack of resolution inherent in single-column chromatographic analysis limits such a detailed chemical characterization of the complex urban atmosphere. Here we present an improved method of peak deconvolution from double-column (orthogonal) gas chromatography. This has enabled us to isolate and classify more than 500 chemical species of volatile organic compounds in urban air, including over 100 multi-substituted monoaromatic and volatile oxygenated hydrocarbons. We suggest that previous assessments of reactive carbon species may therefore have underestimated the contribution made by volatile organic compounds to urban pollution, particularly for compounds with more than six carbon atoms. Incorporating these species in predictive models should greatly improve our understanding of photochemical ozone yields and the formation of harmful secondary organic aerosols.

Indoor secondary organic aerosols: Towards an improved representation of their formation and composition in models.

The formation of secondary organic aerosol (SOA) indoors is one of the many consequences of the rich and complex chemistry that occurs therein. Given particulate matter has well documented health effects, we need to understand the mechanism for SOA formation indoors and its resulting composition. This study evaluates some uncertainties that exist in quantifying gas-to-particle partitioning of SOA-forming compounds using an indoor detailed chemical model. In particular, we investigate the impacts of using different methods to estimate compound vapour pressures as well as simulating the formation of highly oxygenated organic molecules (HOM) via auto-oxidation on SOA formation indoors. Estimation of vapour pressures for 136 α-pinene oxidation species by six investigated methods led to standard deviations of 28-216%. Inclusion of HOM formation improved model performance across three of the six assessed vapour pressure estimation methods when comparing against experimental data, particularly when the NO2 concentration was relatively high. We also explored the predicted SOA composition using two product classification methods, the first assuming the molecule is dominated by one functionality according to its name, and the second accounting for the fractional weighting of each functional group within a molecule. The SOA composition was dominated by the HOM species when the NO2-to-α-terpineol ratio was high for both product classification methods, as these conditions promoted formation of the nitrate radical and hence formation of HOM monomers. As the NO2-to-α-terpineol ratio decreased, peroxides and acids dominated the simple classification, whereas for the fractional classification, carbonyl and alcohol groups became more important.

Reactive indoor air chemistry and health-A workshop summary.

The chemical composition of indoor air changes due to the reactive nature of the indoor environment. Historically, only the stable parent compounds were investigated due to their ease of measurement by conventional methods. Today, however, scientists can better characterize oxidation products (gas and particulate-phase) formed by indoor chemistry. An understanding of occupant exposure can be developed through the investigation of indoor oxidants, the use of derivatization techniques, atmospheric pressure detection, the development of real-time technologies, and improved complex modeling techniques. Moreover, the connection between exposure and health effects is now receiving more attention from the research community. Nevertheless, a need still exists for improved understanding of the possible link between indoor air chemistry and observed acute or chronic health effects and long-term effects such as work-related asthma.

Measurement and modelling of air pollution and atmospheric chemistry in the U.K. West Midlands conurbation: overview of the PUMA Consortium project.

The PUMA (Pollution of the Urban Midlands Atmosphere) Consortium project involved intensive measurement campaigns in the Summer of 1999 and Winter of 1999/2000, respectively, in which a wide variety of air pollutants were measured in the UK West Midlands conurbation including detailed speciation of VOCs and major component analysis of aerosol. Measurements of the OH and HO2 free radicals by the FAGE technique demonstrated that winter concentrations of OH were approximately half of those measured during the summer despite a factor of 15 reduction in production through the photolysis of ozone. Detailed box modelling of the fast reaction chemistry revealed the decomposition of Criegee intermediates formed from ozone-alkene reactions to be responsible for the majority of the formation of hydroxyl in both the summer and winter campaigns, in contrast to earlier rural measurements in which ozone photolysis was predominant. The main sinks for hydroxyl are reactions with NO2, alkenes and oxygenates. Concentrations of the more stable hydrocarbons were found to be relatively invariant across the conurbation, but the impacts of photochemistry were evident through analyses of formaldehyde which showed the majority to be photochemical in origin as opposed to emitted from road traffic. Measurements on the upwind and downwind boundaries of the conurbation revealed substantial enhancements in NOx as a result of emissions within the conurbation, especially during westerly winds which carried relatively clean air. Using calcium as a tracer for crustal particles, it proved possible to reconstruct aerosol mass from the major chemical components with a fairly high degree of success. The organic to elemental carbon ratios showed a far greater influence of photochemistry in summer than winter, presumably resulting mainly from the greater availability of biogenic precursors during the summer campaign. Two urban airshed models were developed and applied to the conurbation, one Eulerian, the other Lagrangian. Both were able to give a good simulation of concentrations of both primary and secondary pollutants at urban background locations.

Long-term exposure to ambient ozone and mortality: a quantitative systematic review and meta-analysis of evidence from cohort studies.

OBJECTIVES: While there is good evidence for associations between short-term exposure to ozone and a range of adverse health outcomes, the evidence from narrative reviews for long-term exposure is suggestive of associations with respiratory mortality only. We conducted a systematic, quantitative evaluation of the evidence from cohort studies, reporting associations between long-term exposure to ozone and mortality. METHODS: Cohort studies published in peer-reviewed journals indexed in EMBASE and MEDLINE to September 2015 and PubMed to October 2015 and cited in reviews/key publications were identified via search strings using terms relating to study design, pollutant and health outcome. Study details and estimate information were extracted and used to calculate standardised effect estimates expressed as HRs per 10 ppb increment in long-term ozone concentrations. RESULTS: 14 publications from 8 cohorts presented results for ozone and all-cause and cause-specific mortality. We found no evidence of associations between long-term annual O3 concentrations and the risk of death from all causes, cardiovascular or respiratory diseases, or lung cancer. 4 cohorts assessed ozone concentrations measured during the warm season. Summary HRs for cardiovascular and respiratory causes of death derived from 3 cohorts were 1.01 (95% CI 1.00 to 1.02) and 1.03 (95% CI 1.01 to 1.05) per 10 ppb, respectively. CONCLUSIONS: Our quantitative review revealed a paucity of independent studies regarding the associations between long-term exposure to ozone and mortality. The potential impact of climate change and increasing anthropogenic emissions of ozone precursors on ozone levels worldwide suggests further studies of the long-term effects of exposure to high ozone levels are warranted.