G. P. Mills

Viral infection of Emiliania huxleyi (Prymnesiophyceae) leads to elevated production of reactive oxygen species

The effect of viral infection of Emiliania huxleyi (Lohman) Hay and Mohler on the concentration of intracellular reactive oxygen species (ROS), hydrogen peroxide (H2O2) excretion and cell photosynthetic capacity (CPC) was examined. During the crash of an E. huxleyi culture induced by viruses intracellular ROS concentrations were generally elevated and reached levels of approximately double those observed in non‐infected control cultures. H2O2 concentrations also increased in the media of the infected cultures from background levels of around 130 nM to approximately 580 nM while levels in the controls decreased. These data suggest that oxidative stress is elevated in infected cells. Although the precise mechanism for ROS production was not identified, a traditional defense related oxidative burst was ruled out, as no evidence of a rapid intracellular accumulation of ROS following addition of the virus was found. CPC declined substantially in the infected culture from a healthy 0.6–0 arbitrary units. Clearly infection disrupted normal photosynthetic processes, which could lead to the production of ROS via interruption of the electron transport chain at the PSII level. Alternatively, ROS may also be a necessary requirement for viral replication in E. huxleyi, possibly due to a link with viral‐induced cell death or associated with general death processes.

Chemical composition observed over the mid-atlantic and the detection of pollution signatures far from source regions

The atmospheric composition of the central North Atlantic region has been sampled using the FAAM BAe146 instrumented aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) campaign, part of the wider International Consortium for Atmospheric Research on Transport and Transformation (ICARTT). This paper presents an overview of the ITOP campaign. Between late July and early August 2004, twelve flights comprising 72 hours of measurement were made in a region from approximately 20 to 40°W and 33 to 47°N centered on Faial Island, Azores, ranging in altitude from 50 to 9000 m. The vertical profiles of O3 and CO are consistent with previous observations made in this region during 1997 and our knowledge of the seasonal cycles within the region. A cluster analysis technique is used to partition the data set into air mass types with distinct chemical signatures. Six clusters provide a suitable balance between cluster generality and specificity. The clusters are labeled as biomass burning, low level outflow, upper level outflow, moist lower troposphere, marine and upper troposphere. During this summer, boreal forest fire emissions from Alaska and northern Canada were found to provide a major perturbation of tropospheric composition in CO, PAN, organic compounds and aerosol. Anthropogenic influenced air from the continental boundary layer of the USA was clearly observed running above the marine boundary layer right across the mid-Atlantic, retaining high pollution levels in VOCs and sulfate aerosol. Upper level outflow events were found to have far lower sulfate aerosol, resulting from washout on ascent, but much higher PAN associated with the colder temperatures. Lagrangian links with flights of other aircraft over the USA and Europe show that such signatures are maintained many days downwind of emission regions. Some other features of the data set are highlighted, including the strong perturbations to many VOCs and OVOCs in this remote region.

Gas chromatography negative ion chemical ionization mass spectrometry : Application to the detection of alkyl nitrates and halocarbons in the atmosphere

Alkyl nitrates and very short-lived halocarbon species are important atmospheric trace gas species that are present in the low to sub parts per trillion concentration range. This presents an analytical challenge for their detection and quantification that requires instrumentation with high sensitivity and selectivity. In this paper, we present a new in situ gas chromatograph negative ion chemical ionization mass spectrometer (GC/NICI-MS) coupled to a non-cryogen sample pre-concentration system. This instrument, with detection limits of <0.01 ppt, is capable of detecting and quantifying a large suite of alkyl nitrate and halocarbon species with high sensitivity and precision. The effects of ion source temperature and reagent gas pressure on the ionization efficiency of the NICI mode are investigated and the results are used to optimize the sensitivity. The NICI mode is compared to the more frequently used electron impact (EI) ionization and the enhancements in sensitivity are presented for all the calibrated compounds.

The impact of local surface changes in Borneo on atmospheric composition at wider spatial scales: Coastal processes, land-use change and air quality

We present results from the OP3 campaign in Sabah during 2008 that allow us to study the impact of local emission changes over Borneo on atmospheric composition at the regional and wider scale. OP3 constituent data provide an important constraint on model performance. Treatment of boundary layer processes is highlighted as an important area of model uncertainty. Model studies of land-use change confirm earlier work, indicating that further changes to intensive oil palm agriculture in South East Asia, and the tropics in general, could have important impacts on air quality, with the biggest factor being the concomitant changes in NOx emissions. With the model scenarios used here, local increases in ozone of around 50 per cent could occur. We also report measurements of short-lived brominated compounds around Sabah suggesting that oceanic (and, especially, coastal) emission sources dominate locally. The concentration of bromine in short-lived halocarbons measured at the surface during OP3 amounted to about 7 ppt, setting an upper limit on the amount of these species that can reach the lower stratosphere.

Laser-powered homogeneous pyrolysis of triisobutylgallane and tri-tert-butylgallane

The gas-phase pyrolysis of tri-tert-butylgallane and triisobutylgallane has been studied using infrared laser-powered homogeneous pyrolysis. Identification of products by infrared and NMR spectroscopies confirmed that the predominant reaction pathway is β-hydride elimination in both cases, but that the pyrolysis proceeds at a significantly lower temperature than that of triethylgallium.

Mechanisms of pyrolysis of organometallic deposition precursors

The gas-phase pyrolysis mechanisms of a number of potential transition-metal deposition precursors have been investigated using the techniques of: (i) infrared laser powered homogeneous pyrolysis coupled with product identification by FTIR, NMR and GC-MS; (ii) stirred Flow Reactor kinetic measurements; (iii) EPR spectroscopy of matrix-isolated free radicals. Preliminary results are presented for: (a) MeMn(CO)5 and AcMn(CO)5, both alone and in the presence of Me3SiH; (b) C5H5Mn(CO)3 and MeC5H4Mn(CO)3; (c) C4H6Fe(CO)3; and (d)(C5H5)2Fe, all of which provide clear evidence that purely homogeneous pathways can be very different from those of surface-catalysed decomposition.

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

Summary Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate.

Chemical composition observed over the mid-Atlantic and the detection of pollution signatures far from source regions

The atmospheric composition of the central North Atlantic region has been sampled using the FAAM BAe146 instrumented aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) campaign, part of the wider International Consortium for Atmospheric Research on Transport and Transformation (ICARTT). This paper presents an overview of the ITOP campaign. Between late July and early August 2004, twelve flights comprising 72 hours of measurement were made in a region from approximately 20 to 40°W and 33 to 47°N centered on Faial Island, Azores, ranging in altitude from 50 to 9000 m. The vertical profiles of O3 and CO are consistent with previous observations made in this region during 1997 and our knowledge of the seasonal cycles within the region. A cluster analysis technique is used to partition the data set into air mass types with distinct chemical signatures. Six clusters provide a suitable balance between cluster generality and specificity. The clusters are labeled as biomass burning, low level outflow, upper level outflow, moist lower troposphere, marine and upper troposphere. During this summer, boreal forest fire emissions from Alaska and northern Canada were found to provide a major perturbation of tropospheric composition in CO, PAN, organic compounds and aerosol. Anthropogenic influenced air from the continental boundary layer of the USA was clearly observed running above the marine boundary layer right across the mid-Atlantic, retaining high pollution levels in VOCs and sulfate aerosol. Upper level outflow events were found to have far lower sulfate aerosol, resulting from washout on ascent, but much higher PAN associated with the colder temperatures. Lagrangian links with flights of other aircraft over the USA and Europe show that such signatures are maintained many days downwind of emission regions. Some other features of the data set are highlighted, including the strong perturbations to many VOCs and OVOCs in this remote region.

Seasonal Variation of the Photochemical Control of Ozone in the Lower Free Troposphere Based on Observations from the Free Tropospheric Experiments at Jungfraujoch in the Swiss Alps

Ozone is one of the most important trace gases in the troposphere being on the one hand an integral element in the control of the oxidizing capacity of the troposphere and on the other hand a climate gas. Although there is still a debate on the relative contribution from photochemistry and stratospheric intrusions to the origin of tropospheric ozone, the current consensus view is that photochemistry is the major contributor to the observed ozone levels [1, 2]. The ozone in the troposphere displays a clear seasonal cycle, which depends on a multitude of factors, such as the proximity to large source areas of ozone precursors, the geographical location and meteorological factors. In certain locations such as in the free troposphere or unpolluted sites in the Northern hemisphere tropospheric ozone shows a spring maximum but there has been much debate as to the origins of this phenomenon mainly due to the problems rising from the interpretation of measurements and the interactions of processes occurring on differing scales from the local to the global scale [3]. Several chemical theories were developed to explain the observed spring ozone maximum in the free troposphere of the Northern midlatitudes [4, 5].

Subproject TOR-2 Origins and Observations of the Spring Ozone Maximum. Theory and Experiment

Measurements of ozone throughout the troposphere clearly show an annual cycle. Over the last couple of decades it has become apparent that the measured annual cycle of ozone in certain locations shows a distinct maximum during spring and that the magnitude of the maximum seems to have increased. There has been much debate as to the origins of this phenomenon. There is broad agreement that much of the ozone found in the troposphere is of photochemical origin. In contrast, there is still no over-arching consensus as to the mechanisms that lead to the formation of the spring ozone maximum. Part of the problem would seem to lie in the interpretation of measurements and the interactions of processes occurring on differing scales from the local to the global scale.