Assessment of the performance of a compact concentric spectrometer system for Atmospheric Differential Optical Absorption Spectroscopy

A breadboard demonstrator of a novel UV/VIS grating spectrometer has been developed based upon a concentric arrangement of a spherical meniscus lens, concave spherical mirror and curved diffraction grating suitable for a range of atmospheric remote sensing applications from the ground or space. The spectrometer is compact and provides high optical efficiency and performance benefits over traditional instruments. The concentric design is capable of handling high relative apertures, owing to spherical aberration and comma being near zero at all surfaces. The design also provides correction for transverse chromatic aberration and distortion, in addition to correcting for the distortion called "smile", the curvature of the slit image formed at each wavelength. These properties render this design capable of superior spectral and spatial performance with size and weight budgets significantly lower than standard configurations. This form of spectrometer design offers the potential for exceptionally compact instrument for differential optical absorption spectroscopy (DOAS) applications from LEO, GEO, HAP or ground-based platforms. The breadboard demonstrator has been shown to offer high throughput and a stable Gaussian line shape with a spectral range from 300 to 450 nm at 0.5 nm resolution, suitable for a number of typical DOAS applications

Distribution of gaseous and particulate organic composition during dark ɑ-pinene ozonolysis

Secondary Organic Aerosol (SOA) affects atmospheric composition, air quality and radiative transfer, however major difficulties are encountered in the development of reliable models for SOA formation. Constraints on processes involved in SOA formation can be obtained by interpreting the speciation and evolution of organics in the gaseous and condensed phase simultaneously. In this study we investigate SOA formation from dark α-pinene ozonolysis with particular emphasis upon the mass distribution of gaseous and particulate organic species. A detailed model for SOA formation is compared with the results from experiments performed in the EUropean PHOtoREactor (EUPHORE) simulation chamber, including on-line gas-phase composition obtained from Chemical-Ionization-Reaction Time-Of-Flight Mass-Spectrometry measurements, and off-line analysis of SOA samples performed by Ion Trap Mass Spectrometry and Liquid Chromatography. The temporal profile of SOA mass concentration is relatively well reproduced by the model. Sensitivity analysis highlights the importance of the choice of vapour pressure estimation method, and the potential influence of condensed phase chemistry. Comparisons of the simulated gaseous- and condensed-phase mass distributions with those observed show a generally good agreement. The simulated speciation has been used to (i) propose a chemical structure for the principal gaseous semi-volatile organic compounds and condensed monomer organic species, (ii) provide evidence for the occurrence of recently suggested radical isomerisation channels not included in the basic model, and (iii) explore the possible contribution of a range of accretion reactions occurring in the condensed phase. We find that oligomer formation through esterification reactions gives the best agreement between the observed and simulated mass spectra

Oxidation photochemistry in the Southern Atlantic boundary layer: Unexpected deviations of photochemical steady state

Ozone (O[subscript 3]) is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL) is considered an important region in terms of chemical O[subscript 3] loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO[subscript 2], O[subscript 3], J[subscript NO2], J(O[superscript 1]D), HO[subscript 2], OH, RO[subscript x] and a range of meteorological parameters were carried out. The concentrations of NO and NO[subscript 2] measured on board the French research vessel Marion-Dufresne (28° S–57° S, 46° W–34° E) in March 2007, are among the lowest yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions, and the calculations indicate substantial deviations from PSS (Φ>1). The deviations observed under low NO[subscript x] conditions (5–25 pptv) demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS) with increasing NO[subscript x] mixing ratio and J[subscript NO2] intensity. It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NO[subscript x] (NO + NO[subscript 2]) conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO[subscript 2] radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical conditions observed at 40°–60° S over the Atlantic Ocean

Development and chamber evaluation of the MCM v3.2 degradation scheme for β-caryophyllene

A degradation mechanism for β-caryophyllene has recently been released as part of version 3.2 of the Master Chemical Mechanism (MCM v3.2), describing the gas phase oxidation initiated by reaction with ozone, OH radicals and NO[subscript 3] radicals. A detailed overview of the construction methodology is given, within the context of reported experimental and theoretical mechanistic appraisals. The performance of the mechanism has been evaluated in chamber simulations in which the gas phase chemistry was coupled to a representation of the gas-to-aerosol partitioning of 280 multi-functional oxidation products. This evaluation exercise considered data from a number of chamber studies of either the ozonolysis of β-caryophyllene, or the photo-oxidation of β-caryophyllene/NO[subscript x] mixtures, in which detailed product distributions have been reported. This includes the results of a series of photo-oxidation experiments performed in the University of Manchester aerosol chamber, also reported here, in which a comprehensive characterization of the temporal evolution of the organic product distribution in the gas phase was carried out, using Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS), in conjunction with measurements of NO[subscript x], O[subscript 3] and SOA mass loading. The CIR-TOF-MS measurements allowed approximately 45 time-resolved product ion signals to be detected, which were assigned on the basis of the simulated temporal profiles of the more abundant MCM v3.2 species, and their probable fragmentation patterns. The evaluation studies demonstrate that the MCM v3.2 mechanism provides an acceptable description of β-caryophyllene degradation under the chamber conditions considered, with the temporal evolution of the observables identified above generally being recreated within the uncertainty bounds of key parameters within the mechanism. The studies have highlighted a number of areas of uncertainty or discrepancy, where further investigation would be valuable to help interpret the results of chamber studies and improve detailed mechanistic understanding. These particularly include: (i) quantification of the yield and stability of the secondary ozonide (denoted BCSOZ in MCM v3.2), formed from β-caryophyllene ozonolysis, and elucidation of the details of its further oxidation, including whether the products retain the "ozonide" functionality; (ii) investigation of the impact of NO[subscript x] on the β-caryophyllene ozonolysis mechanism, in particular its effect on the formation of β-caryophyllinic acid (denoted C137CO2H in MCM v3.2), and elucidation of its formation mechanism; (iii) routine independent identification of β-caryophyllinic acid, and its potentially significant isomer β-nocaryophyllonic acid (denoted C131CO2H in MCM v3.2); (iv) more precise quantification of the primary yield of OH (and other radicals) from β-caryophyllene ozonolysis; (v) quantification of the yields of the first-generation hydroxy nitrates (denoted BCANO3, BCBNO3 and BCCNO3 in MCM v3.2) from the OH-initiated chemistry in the presence of NO[subscript x]; and (vi) further studies in general to improve the identification and quantification of products formed from both ozonolysis and photo-oxidation, including confirmation of the simulated formation of multifunctional species containing hydroperoxide groups, and their important contribution to SOA under NO[subscript x]-free conditions

Isoprene oxidation mechanisms: Measurements and modelling of OH and HO[subscript 2] over a South-East Asian tropical rainforest during the OP3 field campaign

Forests are the dominant source of volatile organic compounds into the atmosphere, with isoprene being the most significant species. The oxidation chemistry of these compounds is a significant driver of local, regional and global atmospheric composition. Observations made over Borneo during the OP3 project in 2008, together with an observationally constrained box model are used to assess our understanding of this oxidation chemistry. In line with previous work in tropical forests, we find that the standard model based on MCM chemistry significantly underestimates the observed OH concentrations. Geometric mean observed to modelled ratios of OH and HO[subscript 2] in airmasses impacted with isoprene are 5.32[subscript −4.43,superscript +3.68] and 1.18[subscript −0.30,superscript +0.30] respectively, with 68 % of the observations being within the specified variation. We implement a variety of mechanistic changes into the model, including epoxide formation and unimolecular decomposition of isoprene peroxy radicals, and assess their impact on the model success. We conclude that none of the current suggestions can simultaneously remove the bias from both OH and HO[subscript 2] simulations and believe that detailed laboratory studies are now needed to resolve this issue

Quantifying the magnitude of a missing hydroxyl radical source in a tropical rainforest

The lifetime of methane is controlled to a very large extent by the abundance of the OH radical. The tropics are a key region for methane removal, with oxidation in the lower tropical troposphere dominating the global methane removal budget (Bloss et al., 2005). In tropical forested environments where biogenic VOC emissions are high and NO[subscript x] concentrations are low, OH concentrations are assumed to be low due to rapid reactions with sink species such as isoprene. New, simultaneous measurements of OH concentrations and OH reactivity, k'[subscript OH'], in a Borneo rainforest are reported and show much higher OH than predicted, with mean peak concentrations of ~2.5×10[superscript 6] molecule cm[superscript −3] (10 min average) observed around solar noon. Whilst j(O[superscript 1]D) and humidity were high, low O[subscript 3] concentrations limited the OH production from O[subscript 3] photolysis. Measured OH reactivity was very high, peaking at a diurnal average of 29.1±8.5 s[superscript −1], corresponding to an OH lifetime of only 34 ms. To maintain the observed OH concentration given the measured OH reactivity requires a rate of OH production approximately 10 times greater than calculated using all measured OH sources. A test of our current understanding of the chemistry within a tropical rainforest was made using a detailed zero-dimensional model to compare with measurements. The model over-predicted the observed HO[subscript 2] concentrations and significantly under-predicted OH concentrations. Inclusion of an additional OH source formed as a recycled product of OH initiated isoprene oxidation improved the modelled OH agreement but only served to worsen the HO2 model/measurement agreement. To replicate levels of both OH and HO[subscript 2], a process that recycles HO[subscript 2] to OH is required; equivalent to the OH recycling effect of 0.74 ppbv of NO. This recycling step increases OH concentrations by 88% at noon and has wide implications, leading to much higher predicted OH over tropical forests, with a concomitant reduction in the CH[subscript 4] lifetime and increase in the rate of VOC degradation

Measurements of iodine monoxide at a semi polluted coastal location

Point source measurements of IO by laser induced fluorescence spectroscopy were made at a semi-polluted coastal location during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) campaign in September 2006. The site, on the NW French coast in Roscoff, was characterised by extensive intertidal macroalgae beds which were exposed at low tide. The closest known iodine active macroalgae beds were at least 300m from the measurement point. From 20 days of measurements, IO was observed above the instrument limit of detection on 14 days, of which a clear diurnal profile was observed on 11 days. The maximum IO mixing ratio was 30.0 pptv (10 s integration period) during the day, amongst the highest concentrations ever observed in the atmosphere, and 1–2 pptv during the night. IO concentrations were strongly dependent on tidal height, the intensity of solar irradiation and meteorological conditions. An intercomparison of IO measurements made using point source and spatially averaged DOAS instruments confirms the presence of hot-spots of IO caused by an inhomogeneous distribution of macroalgae. The co-incident, point source measurement of IO and ultra fine particles (2.5 nm≥d≥10 nm) displayed a strong correlation, providing evidence that IO is involved in the production pathway of ultra fine particles at coastal locations. Finally, a modelling study shows that high IO concentrations which are likely to be produced in a macrolagae rich environment can significantly perturb the concentrations of OH and HO[subscript x] radicals. The effect of IO on HO[subscript x] is reduced as NO[subscript x] concentrations increase

HO[subscript x] observations over West Africa during AMMA: impact of isoprene and NO[subscript x]

Aircraft OH and HO[subscript 2] measurements made over West Africa during the AMMA field campaign in summer 2006 have been investigated using a box model constrained to observations of long-lived species and physical parameters. "Good" agreement was found for HO[subscript 2] (modelled to observed gradient of 1.23 ± 0.11). However, the model significantly overpredicts OH concentrations. The reasons for this are not clear, but may reflect instrumental instabilities affecting the OH measurements. Within the model, HO[subscript x] concentrations in West Africa are controlled by relatively simple photochemistry, with production dominated by ozone photolysis and reaction of O([superscript 1]D) with water vapour, and loss processes dominated by HO[subscript 2] + HO[subscript 2] and HO[subscript 2] + RO[subscript 2]. Isoprene chemistry was found to influence forested regions. In contrast to several recent field studies in very low NO[subscript x] and high isoprene environments, we do not observe any dependence of model success for HO[subscript 2] on isoprene and attribute this to efficient recycling of HO[subscript x] through RO[subscript 2] + NO reactions under the moderate NO[subscript x] concentrations (5–300 ppt NO in the boundary layer, median 76 ppt) encountered during AMMA. This suggests that some of the problems with understanding the impact of isoprene on atmospheric composition may be limited to the extreme low range of NO[subscript x] concentrations