Nicola Carslaw

Modeling OH, HO2, and RO2 radicals in the marine boundary layer: 1. Model construction and comparison with field measurements

An observationally constrained box model has been constructed in order to investigate the chemistry of the marine boundary layer at Mace Head, a remote location on the west coast of Ireland. The primary aim of the model is to reproduce concentrations of the hydroxyl (OH) and hydroperoxy (HO2) radicals measured by an in situ fluorescence assay by gas expansion (PAGE) instrument, and the sum of peroxy radicals ∑([HO2]+[RO2]) determined by a peroxy radical chemical amplification (PERCA) instrument. The model has been constructed based on observed concentrations of a suite of non-methane hydrocarbons, measured in situ by gas chromatography. The chemical mechanism for the model is a subset of a comprehensive master chemical mechanism (MCM). This paper describes in detail the construction of the model, as well as the underlying approach. Comparisons of modeled and measured concentrations of radical species, from a recent field campaign held at the Mace Head Atmospheric Observatory during July and August 1996 (EASE 96), are also presented. For the limited OH data available from this campaign, the model tends to overestimate the observations by about 40%, although this discrepancy is within the uncertainties of the model (±31%, 2σ) and the PAGE measurements (±75% on average, 2σ). For HO2 the model reproduces the concentrations well on one day but less well on another. Low HOx concentrations compared to model results have been observed previously, with greater than expected heterogeneous losses invoked to explain the differences. Comparisons between measurements of peroxy radicals made by chemical amplification and model predictions show good agreement over a wide range of conditions.

Simultaneous observations of nitrate and peroxy radicals in the marine boundary layer

This paper describes the most extensive set of simultaneous measurements of the concentrations of nitrate (NO3) and peroxy (sum of HO2 + RO2, R = alkyl and acyl) radicals to date. The measurements were made in the coastal marine boundary layer over the North Sea, at the Weybourne Atmospheric Observatory on the North Norfolk coast during the spring and autumn of 1994. In spring the average nighttime concentration of NO3 measured by differential optical absorption spectroscopy, was about 10 parts per trillion (ppt) (maximum 25 ppt). The corresponding peroxy radical concentration, measured by the chemical amplifier technique, averaged about 2 ppt (maximum 6 ppt), although this is likely to be an underestimate of the total radical concentration. There is a significant positive correlation between the two sets of radicals, which has not been reported previously. A box model of the marine boundary layer is used to show that this correlation arises from the processing of reactive organic species by NO3. During spring the relatively long lifetime of NO3 (up to 18 min) at night is controlled by reaction with dimethyl sulfide (DMS), and the model predicts significant production of HNO3, methyl tiomethylen (CH3SCH2O2) and other peroxy radicals, HCHO, and eventually sulfate. A nighttime production rate for the hydroxyl (OH) of about 2 x 10(4) molecules cm(-3) s(-1) is estimated. During one night in autumn the NO3 lifetime of about 3 min is too short to be explained by reaction with unsaturated hydrocarbons, but is satisfactorily accounted for by the heterogeneous loss of N2O5 on deliquesced aerosols in relatively polluted conditions.

Production of peroxy radicals at night via reactions of ozone and the nitrate radical in the marine boundary layer

In this paper, a substantial set of simultaneous measurements of the sum of peroxy radicals, [HO2 + RO2], NO3, hydrocarbons (HCs), and ozone, taken at Mace Head on the Atlantic coast of Ireland in spring 1997, is presented. Conditions encountered during the experiment ranged from semipolluted air masses advected from Britain and continental Europe to clean air masses off the North and mid-Atlantic, where mixing ratios of pollution tracers approached Northern Hemispheric background mixing ratios. Average mixing ratios of peroxy radicals varied from 2.5 to 5.5 parts per trillion by volume (pptv) at night depending on wind sector, and were observed to decay only very slowly from late afternoon to early morning (0.1–0.5 pptv h−1). Measurements of OH and HO2 on two nights using the Fluorescence Assay by Gas Expansion (FAGE) technique give an upper limit for [OH] of 2.5×105 molecules cm−3 and an average upper limit [HO2]/[HO2 + RO2] ratio of 0.27. A modeling study of the 1/e lifetimes of the peroxy radicals, assuming no radical production at night, yielded mean lifetimes of between ∼8–23 min for HO2 and 3–18 min for CH3O2. Given these lifetimes, it may be concluded that the peroxy-radical mixing ratios observed could not be maintained without substantial production at night. No significant correlation is observed between measured [HO2 + RO2] and [NO3] under any conditions. Calculation of the reaction rates for ozone and NO3 with hydrocarbons (HCs) shows that the ozone-initiated oxidation routes of HCs outweighed those of NO3 in the NE, SE and NW wind sectors. In the SW sector, however, the two mechanisms operated at similar rates on average, and oxidation by NO3 was the dominant route in the westerly sector. The oxidation of alkenes at night by ozone was greater by a factor of 4 than that by NO3 over the whole data set. The HC degradation rates from the three “westerly” sectors, where tracer mixing ratios were relatively low, may be representative of the nighttime oxidative capacity of the marine boundary layer throughout the background Northern Hemisphere. Further calculations using literature values for OH yields and inferred RO2 yields from the ozone-alkene reactions show that peroxy radicals derived from the ozone reactions were likely to make up the major part of the peroxy-radical signal at night (mean value 66%). However, the NO3 source was of similar magnitude in the middle of the night, when [NO3] was generally at its maximum. The estimated total rates of formation of peroxy radicals are much higher under semipolluted conditions (mean 8.0×104 molecules cm−3 s−1 in the SE wind sector) than under cleaner conditions (mean 2.4×104 molecules cm−3 s−1 in the westerly wind sector). A model study using a campaign-tailored box model (CTBM) for semipolluted conditions shows that the major primary sources of OH, HO2, and CH3O2 (the most abundant organic peroxy radical) were the Criegee biradical intermediates formed in the reactions of ozone with alkenes.

Modeling OH, HO2, and RO2 radicals in the marine boundary layer: 2. Mechanism reduction and uncertainty analysis

An observationally constrained box model has been constructed to investigate radical chemistry at the Mace Head Atmospheric Observatory, a remote marine location on the west coast of Ireland. The primary aim of the model has been to model concentrations of the hydroxyl (OH), hydroperoxy (HO2), and the sum of peroxy ∑([HO2]+[RO2]) radicals measured by in situ instruments at this location. The model used in these studies consists of about 1670 reactions and 500 species, and model predictions of radical concentrations have been evaluated against field data. In order to further understand the chemistry, the model has been reduced using sensitivity analysis on both a clean and a semipolluted day. For reduced mechanisms that predict the concentrations of OH and HO2 to within 5% of the full mechanism, the semipolluted day can be represented using 279 species and 986 reactions, and the clean day using 249 species and 894 reactions. A further reduction has been applied whereby the reduced mechanisms predict concentrations of OH and HO2 to within 20% of the full mechanism for the daytime hours. In this way, the OH and HO2 concentrations on the semipolluted day can be represented by 42 species and 64 reactions, and the clean day by 17 species and 25 reactions. We show that these reduced mechanisms are generally applicable for this location under broadly similar conditions. Simple steady state expressions have also been derived to represent the chemistry at this location, allowing the concentrations of OH and HO2 to be deduced analytically. The expressions are based on the reduced mechanisms and on a further analysis of the reaction rates. Finally, an uncertainty analysis has been carried out to quantify the effects of propagation of uncertainties in the rate parameters and constrained concentrations through to the calculated radical concentrations in the model. For model concentrations of OH, HO2 and ∑([HO2]+[RO2]) radicals, the 2σ uncertainties are 31, 21, and 25%, respectively for clean air, and 42, 25, and 27% for semipolluted air.

The origin of high particulate concentrations over the United Kingdom, March 2000

Abstract An episode of exceptionally high PM10 and PM2.5 levels was observed during the night of the 2–3 March 2000 throughout England and Wales. The weather was characterised by strong westerly winds and widespread rainfall associated with a low pressure system to the north of Scotland, conditions usually associated with relatively clean, unpolluted air. Possible sources included volcanic ash from an eruption on 26 February 2000 in Iceland, or dust from large sandstorms over the Sahara. A combination of atmospheric transport modelling using the Lagrangian dispersion model NAME, an analyses of satellite imagery and observational data from Mace Head has shown that the most likely origin of the episode was long range transport of dust from the Sahara region of North Africa. Further modelling studies have revealed a number of previously unidentified dust episodes, and indicate that transport of dust from the Sahara can occur several times a year. Dust episodes are of interest for a number of reasons, particulate levels can be elevated over a wide area and in some instances can significantly exceeded current air quality standards. If a natural source is identified over which there can be no control, there are implications for the setting of air quality standards.

Diurnal cycles of short-lived tropospheric alkenes at a north Atlantic coastal site

Abstract Observation of diurnal cycles in atmospheric concentrations of reactive alkenes are reported from measurements performed at a North Atlantic coastal site (Mace Head, Eire 53°19′34″N; 9°54′14″W). Species seen to exhibit distinct cycles included isoprene, ethene, propene, 1-butene, iso-butene and a substituted C6 alkene. Five hundred and thirty air mass classified measurements were performed over a 4 week period at approximately hourly frequency and demonstrate that during periods when air flow resulted from unpolluted oceanic regions a clear daily cycle in concentrations existed, peaking at around solar noon for all species. These observations support the proposed mechanism of production via photochemical degradation of organic carbon in sea water. The observed concentrations showed strong correlation (propene R2>0.75) with solar flux, with little relationship to other meteorological or chemical parameters. The species’ short atmospheric lifetimes indicate that the source of emission was from local coastal waters within close proximity of the sampling site. At solar noon concentrations of reactive alkenes from oceanic sources were responsible for up to 88% of non-methane hydrocarbon reaction with the hydroxyl radical at this coastal marine site.

Improved model predictions of HO2 with gas to particle mass transfer rates calculated using aerosol number size distributions

[i] Hydroperoxy radical (HO 2 ) measurements made during the second Southern Ocean Atmospheric Photochemistry Experiment (SOAPEX-2) were used as a modeling case study to investigate the role of aerosol uptake of free radicals in remote marine boundary layer (MBL) air. The SOAPEX-2 campaign was held at the Cape Grim Baseline Atmospheric Pollution Station on the northwestern tip of Tasmania during austral summer from 18 January to 18 February 1999. A box model based on the Master Chemical Mechanism (MCMv3) was tailored to campaign conditions. With no aerosol uptake of HO 2 the model overestimated the midday (1100-1400 hours) HO 2 measurements by 74-83% on two clean marine air days with HO 2 measurements. Two different methods were used to simulate aerosol uptake of free radicals. The first method used a simple first-order rate coefficient for interfacial mass transport (kinetic regime), k kin , with two treatments of the aerosol surface area, estimated from clean MBL Californian air and calculated by analysis of lognormal aerosol number versus size distributions from the first Aerosol Characterization Experiment (ACE-1). The second method used a rate coefficient which takes into account diffusion to the surface as well as interfacial mass transport (transition regime), k trans , integrated over most of the aerosol size range (up to 2.5 μm diameter) using aerosol number size distribution data from ACE-1. With the simple uptake rate the model to measured overestimation of HO 2 was on average 63 and 20% with uptake coefficients of 0.2 and 1, respectively. With k trans the overestimation was 60 and 44%, respectively. These overestimations are upper limits because the calculations did not take into account the largest sea salt mode (which was not measured). An estimate of the aerosol in the largest sea salt modes was calculated and used to recalculate the values of k trans , reducing the overestimation to 58 and 25%, respectively. The variation in the available literature values for the HO 2 uptake coefficient is a large source of uncertainty in the calculated rate of uptake. Another source of uncertainty exists in the values assumed for the aerosol volume in this work. As these data did not exist for SOAPEX-2, we calculated k trans from ACE-1 aerosol volume data and used a constant averaged value of k trans ; in reality there will be a significant degree of temporal variation in this parameter. Given these uncertainties, we conclude that aerosol uptake of the hydroperoxy radical (HO 2 ) could be a significant process in clean MBL environments and its incorrect parameterization or absence in atmospheric models could contribute to overestimation of measured concentrations.

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.

A significant role for nitrate and peroxide groups on indoor secondary organic aerosol.

This paper reports indoor secondary organic aerosol, SOA, composition based on the results from an improved model for indoor air chemistry. The model uses a detailed chemical mechanism that is near-explicit to describe the gas-phase degradation of relevant indoor VOC species. In addition, gas-to-particle partitioning is included for oxygenated products formed from the degradation of limonene, the most ubiquitous terpenoid species in the indoor environment. The detail inherent in the chemical mechanism permits the indoor SOA composition to be reported in greater detail than currently possible using experimental techniques. For typical indoor conditions in the suburban UK, SOA concentrations are ~1 μg m(-3) and dominated by nitrated material (~85%), with smaller contributions from peroxide (12%), carbonyl (3%), and acidic (1%) material. During cleaning activities, SOA concentrations can reach 20 μg m(-3) with the composition dominated by peroxide material (73%), with a smaller contribution from nitrated material (21%). The relative importance of these different moieties depends crucially (in order) on the outdoor concentration of O(3), the deposition rates employed and the scaling factor value applied to the partitioning coefficient. There are currently few studies that report observation of aerosol composition indoors, and most of these have been carried out under conditions that are not directly relevant. This study highlights the need to investigate SOA composition in real indoor environments. Further, there is a need to measure deposition rates for key indoor air species on relevant indoor surfaces and to reduce the uncertainties that still exist in gas-to-particle phase parametrization for both indoor and outdoor air chemistry models.

The gas-phase chemistry of urban atmospheres

This paper reviews the chemistry of urban atmospheres,using recent measurement data to highlight the key concepts. We briefly summarise historical reports of air pollution and the impact that human activities have had on urban atmospheres since the IndustrialRevolution. Although pollution events in the first half of the 20th century were caused by high concentrations of smoke and sulphur dioxide, photochemical pollution has become the major problem in most of the major citiesaround the world. The chemistry of photochemical pollution episodes is discussed in some detail, particularly the crucial role played by volatile organic carbon and nitrogen oxides. Issues to be considered when modelling the chemistry of urban areas are briefly summarised, such as the uncertainties in chemical mechanisms and emission inventories, as well as the complexities of dynamical processes. Finally, we present some recent issues in urban chemistry, including the discovery that the amount of volatile organic carbon in urban atmospheres may be grossly under-estimated. We also use modelling resultsto show the importance of the reaction of ozone with reactive hydrocarbons as a radical source in urban atmospheres. Finally, the use of NOX-NO2 relationships to predict annual mean NO2 concentrations is discussed.