Preparation of nanomagnetic absorbent for partition coefficient measurement

In this paper, we report a new method based on supercritical carbon dioxide (scCO(2)) to fill and distribute the porous magnetic nanoparticles with n-octanol in a homogeneous manner. The high solubility of n-octanol in scCO(2) and high diffusivity and permeability of the fluid allow efficient delivery of n-octanol into the porous magnetic nanoparticles. Thus, the n-octanol-loaded magnetic nanoparticles can be readily dispersed into aqueous buffer (pH 7.40) to form a homogenous suspension consisting of nano-sized n-octanol droplets. We refer this suspension as the n-octanol stock solution. The n-octanol stock solution is then mixed with bulk aqueous phase (pH 7.40) containing an organic compound prior to magnetic separation. The small-size of the particles and the efficient mixing enable a rapid establishment of the partition equilibrium of the organic compound between the solid supported n-octanol nano-droplets and the bulk aqueous phase. UV-vis spectrophotometry is then applied to determine the concentration of the organic compound in the aqueous phase both before and after partitioning (after magnetic separation). As a result, log D values of organic compounds of pharmaceutical interest determined by this modified method are found to be in excellent agreement with the literature data. (c) 2006 Elsevier B.V. All rights reserved.

Principles and calibration of solid phase microextraction fibre (passive sampler) for measurements of airflow and air infiltration in dwellings

Tracer gas techniques have been the most appropriate experimental method of determining airflows and ventilation rates in houses. However, current trends to reduce greenhouse gas effects have prompted the need for alternative techniques, such as passive sampling. In this research passive sampling techniques have been used to demonstrate the potential to fulfil these requirements by using solutions of volatile organic compounds (VOCs) and solid phase microextraction (SPME) fibres. These passive sampling techniques have been calibrated against tracer gas decay techniques and measurements from a standard orifice plate. Two constant sources of volatile organic compounds were diffused into two sections of a humidity chamber and sampled using SPME fibres. From a total of four SPME fibres (two in each section), reproducible results were obtained. Emission rates and air movement from one section to the other were predicted using developed algorithms. Comparison of the SPME fibre technique with that of the tracer gas technique and measurements from an orifice plate showed similar results with good precision and accuracy. With these fibres, infiltration rates can be measured over grab samples in a time weighted averaged period lasting from 10 minutes up to several days. Key words: passive samplers, solid phase microextraction fibre, tracer gas techniques, airflow, air infiltration, houses.

Gas-phase reactions of NO3 and N2O5 with (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol

The night-time atmospheric chemistry of the biogenic volatile organic compounds (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these stress-induced plant emissions were measured using the discharge-flow technique. We employed off-axis continuous-wave cavity-enhanced absorption spectroscopy (CEAS) for the detection of NO3, which enabled us to work in excess of the hexenol compounds over NO3. The rate coefficients determined were (2.93 +/- 0.58) x 10(-13) cm(3) molecule(-1) s(-1), (2.67 +/- 0.42) x 10(-13) cm(3) molecule(-1) s(-1), (4.43 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1), (1.56 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1), and (1.30 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1) for (Z)-hex-4-en-1-ol, (Z)-hex-3en-1-ol, (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol. The rate coefficient for the reaction of NO3 with (Z)-hex-3-en-1-ol agrees with the single published determination of the rate coefficient using a relative method. The other rate coefficients have not been measured before and are compared to estimated values. Relative-rate studies were also performed, but required modification of the standard technique because N2O5 (used as the source of NO3) itself reacts with the hexenols. We used varying excesses of NO2 to determine simultaneously rate coefficients for reactions of NO3 and N2O5 with (E)-hex-3-en-1-ol of (5.2 +/- 1.8) x 10(-13) cm(3) molecule(-1) s(-1) and (3.1 +/- 2.3) x 10(-18) cm(3) molecule(-1) s(-1). Our new determinations suggest atmospheric lifetimes with respect to NO3-initiated oxidation of roughly 1-4 h for the hexenols, comparable with lifetimes estimated for the atmospheric degradation by OH and shorter lifetimes than for attack by O-3. Recent measurements of [N2O5] suggest that the gas-phase reactions of N2O5 with unsaturated alcohols will not be of importance under usual atmospheric conditions, but they certainly can be in laboratory systems when determining rate coefficients.

Chemical and aerosol characterisation of the troposphere over West Africa during the monsoon period as part of AMMA

During June, July and August 2006 five aircraft took part in a campaign over West Africa to observe the aerosol content and chemical composition of the troposphere and lower stratosphere as part of the African Monsoon Multidisciplinary Analysis (AMMA) project. These are the first such measurements in this region during the monsoon period. In addition to providing an overview of the tropospheric composition, this paper provides a description of the measurement strategy (flights performed, instrumental payloads, wing-tip to wing-tip comparisons) and points to some of the important findings discussed in more detail in other papers in this special issue. The ozone data exhibits an "S" shaped vertical profile which appears to result from significant losses in the lower troposphere due to rapid deposition to forested areas and photochemical destruction in the moist monsoon air, and convective uplift of ozone-poor air to the upper troposphere. This profile is disturbed, particularly in the south of the region, by the intrusions in the lower and middle troposphere of air from the southern hemisphere impacted by biomass burning. Comparisons with longer term data sets suggest the impact of these intrusions on West Africa in 2006 was greater than in other recent wet seasons. There is evidence for net photochemical production of ozone in these biomass burning plumes as well as in urban plumes, in particular that from Lagos, convective outflow in the upper troposphere and in boundary layer air affected by nitrogen oxide emissions from recently wetted soils. This latter effect, along with enhanced deposition to the forested areas, contributes to a latitudinal gradient of ozone in the lower troposphere. Biogenic volatile organic compounds are also important in defining the composition both for the boundary layer and upper tropospheric convective outflow. Mineral dust was found to be the most abundant and ubiquitous aerosol type in the atmosphere over Western Africa. Data collected within AMMA indicate that injection of dust to altitudes favourable for long-range transport (i.e. in the upper Sahelian planetary boundary layer) can occur behind the leading edge of mesoscale convective system (MCS) cold-pools. Research within AMMA also provides the first estimates of secondary organic aerosols across the West African Sahel and have shown that organic mass loadings vary between 0 and 2 μg m−3 with a median concentration of 1.07 μg m−3. The vertical distribution of nucleation mode particle concentrations reveals that significant and fairly strong particle formation events did occur for a considerable fraction of measurement time above 8 km (and only there). Very low concentrations were observed in general in the fresh outflow of active MCSs, likely as the result of efficient wet removal of aerosol particles due to heavy precipitation inside the convective cells of the MCSs. This wet removal initially affects all particle size ranges as clearly shown by all measurements in the vicinity of MCSs.

Rifaximin modulates the colonic microbiota of patients with Crohn's disease: an in vitro approach using a continuous culture colonic model system.

Rifaximin, a rifamycin derivative, has been reported to induce clinical remission of active Crohn's disease (CD), a chronic inflammatory bowel disorder. In order to understand how rifaximin affects the colonic microbiota and its metabolism, an in vitro human colonic model system was used in this study. We investigated the impact of the administration of 1800 mg/day of rifaximin on the faecal microbiota of four patients affected by colonic active CD [Crohn's disease activity index (CDAI > 200)] using a continuous culture colonic model system. We studied the effect of rifaximin on the human gut microbiota using fluorescence in situ hybridization, quantitative PCR and PCR–denaturing gradient gel electrophoresis. Furthermore, we investigated the effect of the antibiotic on microbial metabolic profiles, using 1H-NMR and solid phase microextraction coupled with gas chromatography/mass spectrometry, and its potential genotoxicity and cytotoxicity, using Comet and growth curve assays. Rifaximin did not affect the overall composition of the gut microbiota, whereas it caused an increase in concentration of Bifidobacterium, Atopobium and Faecalibacterium prausnitzii. A shift in microbial metabolism was observed, as shown by increases in short-chain fatty acids, propanol, decanol, nonanone and aromatic organic compounds, and decreases in ethanol, methanol and glutamate. No genotoxicity or cytotoxicity was attributed to rifaximin, and conversely rifaximin was shown to have a chemopreventive role by protecting against hydrogen peroxide-induced DNA damage. We demonstrated that rifaximin, while not altering the overall structure of the human colonic microbiota, increased bifidobacteria and led to variation of metabolic profiles associated with potential beneficial effects on the host.

Night-time tropospheric chemistry of the unsaturated alcohols (Z)-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions

The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO3 in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO3. The rate coefficients were determined to be (1.53 +/- 0.23) x 10(-13) and (1.39 +/- 0.19) x 10(-14) cm(3) molecule(-1) s(-1) for reactions of NO3 with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N2O5 as source of NO3 resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO2 allowed us to determine the rate coefficients for the N2O5 reactions to be (5.0 +/- 2.8) x 10(-19) cm(3) molecule(-1) s(-1) for (Z)-pent-2-en-1-ol, and (9.1 +/- 5.8) x 10(-19) cm(3) molecule(-1) s(-1) for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.

Measurements and modelling of airflows in houses using passive sampling and HAM software

Passive samplers have been predominantly used to monitor environmental conditions in single volumes. However, measurements using a calibrated passive sampler- Solid Phase Microextraction (SPME) fibre, in three houses with cold pitched roof, successfully demonstrated the potential of the SPME fibre as a device for monitoring air movement in two volumes. The roofs monitored were pitched at 15° - 30° with insulation thickness varying between 200-300 mm on the ceiling. For effective analysis, two constant sources of volatile organic compounds were diffused steadily in the house. Emission rates and air movement from the house to the roof was predicted using developed algorithms. The airflow rates which were calibrated against conventional tracer gas techniques were introduced into a HAM software package to predict the effects of air movement on other varying parameters. On average it was shown from the in situ measurements that about 20-30% of air entering the three houses left through gaps and cracks in the ceiling into the roof. Although these field measurements focus on the airflows, it is associated with energy benefits such that; if these flows are reduced then significantly energy losses would also be reduced (as modelled) consequently improving the energy efficiency of the house. Other results illustrated that condensation formation risks were dependent on the airtightness of the building envelopes including configurations of their roof constructions.

Characterization of safe nanostructured polymeric materials

The addition of small quantities of nanoparticles to conventional and sustainable thermoplastics leads to property enhancements with considerable potential in many areas of applications including food packaging 1, lightweight composites and high performance materials 2. In the case of sustainable polymers 3, the addition of nanoparticles may well sufficiently enhance properties such that the portfolio of possible applications is greatly increased. Most engineered nanoparticles are highly stable and these exist as nanoparticles prior to compounding with the polymer resin. They remain as nanoparticles during the active use of the packaging material as well as in the subsequent waste and recycling streams. It is also possible to construct the nanoparticles within the polymer films during processing from organic compounds selected to present minimal or no potential health hazards 4. In both cases the characterisation of the resultant nanostructured polymers presents a number of challenges. Foremost amongst these are the coupled challenges of the nanoscale of the particles and the low fraction present in the polymer matrix. Very low fractions of nanoparticles are only effective if the dispersion of the particles is good. This continues to be an issue in the process engineering but of course bad dispersion is much easier to see than good dispersion. In this presentation we show the merits of a combined scattering (neutron and x-ray) and microscopy (SEM, TEM, AFM) approach. We explore this methodology using rod like, plate like and spheroidal particles including metallic particles, plate-like and rod-like clay dispersions and nanoscale particles based on carbon such as nanotubes and graphene flakes. We will draw on a range of material systems, many explored in partnership with other members of Napolynet. The value of adding nanoscale particles is that the scale matches the scale of the structure in the polymer matrix. Although this can lead to difficulties in separating the effects in scattering experiments, the result in morphological studies means that both the nanoparticles and the polymer morphology are revealed.

Global and regional temperature-change potentials for near-term climate forcers

We examine the climate effects of the emissions of near-term climate forcers (NTCFs) from 4 continental regions (East Asia, Europe, North America and South Asia) using radiative forcing from the task force on hemispheric transport of air pollution source-receptor global chemical transport model simulations. These simulations model the transport of 3 aerosol species (sulphate, particulate organic matter and black carbon) and 4 ozone precursors (methane, nitric oxides (NOx), volatile organic compounds and carbon monoxide). From the equilibrium radiative forcing results we calculate global climate metrics, global warming potentials (GWPs) and global temperature change potentials (GTPs) and show how these depend on emission region, and can vary as functions of time. For the aerosol species, the GWP(100) values are −37±12, −46±20, and 350±200 for SO2, POM and BC respectively for the direct effects only. The corresponding GTP(100) values are −5.2±2.4, −6.5±3.5, and 50±33. This analysis is further extended by examining the temperature-change impacts in 4 latitude bands. This shows that the latitudinal pattern of the temperature response to emissions of the NTCFs does not directly follow the pattern of the diagnosed radiative forcing. For instance temperatures in the Arctic latitudes are particularly sensitive to NTCF emissions in the northern mid-latitudes. At the 100-yr time horizon the ARTPs show NOx emissions can have a warming effect in the northern mid and high latitudes, but cooling in the tropics and Southern Hemisphere. The northern mid-latitude temperature response to northern mid-latitude emissions of most NTCFs is approximately twice as large as would be implied by the global average.

Geochemical changes recorded in Lynch's Crater, Northeastern Australia, over the past 50 ka

There are many geochemical reconstructions of environmental change in the mid and high latitudes but relatively few in the tropical latitudes, despite their considerable potential for reconstructing environmental processes that cannot be identified using more traditional proxies. Here we present one reconstruction of environmental change for the tropics. This reconstruction covers the past 50 ka using a suite of geochemical data from the high-resolution sequence of Lynch's Crater in northeast Queensland, Australia, a region highly sensitive to El Niño-Southern Oscillation (ENSO) activity. The 23 major oxides and trace elements measured could be summarised by extracting three axes using principal components analysis (accounting for 72% of the variability). The data indicate that the greatest variability in the geochemical data accounted for erosional activity within the catchment that was associated with past changes in the frequency of ENSO activity (though this was less sensitive during wetter periods, probably as a result of buffering by high vegetation cover). The remaining variability was largely explained by elements that form complexes with organic compounds (e.g., humic acids) and those that are important nutrients for specific vegetation types (and therefore a measure of vegetation distribution). For more detailed reconstructions, further work is required to disentangle the complex controls of elements within sedimentary sequences.

A Lagrangian model of air-mass photochemistry and mixing using a trajectory ensemble: the Cambridge Tropospheric Trajectory model of Chemistry And Transport (CiTTyCAT) version 4.2

A Lagrangian model of photochemistry and mixing is described (CiTTyCAT, stemming from the Cambridge Tropospheric Trajectory model of Chemistry And Transport), which is suitable for transport and chemistry studies throughout the troposphere. Over the last five years, the model has been developed in parallel at several different institutions and here those developments have been incorporated into one "community" model and documented for the first time. The key photochemical developments include a new scheme for biogenic volatile organic compounds and updated emissions schemes. The key physical development is to evolve composition following an ensemble of trajectories within neighbouring air-masses, including a simple scheme for mixing between them via an evolving "background profile", both within the boundary layer and free troposphere. The model runs along trajectories pre-calculated using winds and temperature from meteorological analyses. In addition, boundary layer height and precipitation rates, output from the analysis model, are interpolated to trajectory points and used as inputs to the mixing and wet deposition schemes. The model is most suitable in regimes when the effects of small-scale turbulent mixing are slow relative to advection by the resolved winds so that coherent air-masses form with distinct composition and strong gradients between them. Such air-masses can persist for many days while stretching, folding and thinning. Lagrangian models offer a useful framework for picking apart the processes of air-mass evolution over inter-continental distances, without being hindered by the numerical diffusion inherent to global Eulerian models. The model, including different box and trajectory modes, is described and some output for each of the modes is presented for evaluation. The model is available for download from a Subversion-controlled repository by contacting the corresponding authors.

Isoprene emissions and climate

Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry and the carbon cycle. Isoprene is quantitatively the most important of the non-methane BVOCs (NMBVOCs), with an annual emission of about 400–600 TgC; about 90% of this is emitted by terrestrial plants. Incorporating a mechanistic treatment of isoprene emissions within land-surface schemes has recently become a focus for the modelling community, the aim being to quantify the potential magnitude of associated climate feedbacks. However, these efforts are hampered by major uncertainties about why plants emit isoprene and the relative importance of different environmental controls on isoprene emission. The availability and reliability of observations of isoprene fluxes from different types of vegetation is limited, and this also imposes constraints on model development. Nevertheless, progress is being made towards the development of mechanistic models of isoprene emission which, in conjunction with atmospheric chemistry models, will ultimately allow improved quantification of the feedbacks between the terrestrial biosphere and climate under past and future climate states.

Meteorology, air quality, and health in London: the ClearfLo project

The ClearfLo project provides integrated measurements of the meteorology, composition and particulate loading of London's urban atmosphere to improve predictive capability for air quality. Air quality and heat are strong health drivers and their accurate assessment and forecast are important in densely populated urban areas. However, the sources and processes leading to high concentrations of main pollutants such as ozone, nitrogen dioxide, and fine and coarse particulate matter in complex urban areas are not fully understood, limiting our ability to forecast air quality accurately. This paper introduces the ClearfLo project's interdisciplinary approach to investigate the processes leading to poor air quality and elevated temperatures. Within ClearfLo (www.clearflo.ac.uk), a large multi-institutional project funded by the UK Natural Environment Research Council (NERC), integrated measurements of meteorology, gaseous and particulate composition/loading within London's atmosphere were undertaken to understand the processes underlying poor air quality. Long-term measurement infrastructure installed at multiple levels (street and elevated), and at urban background, kerbside and rural locations were complemented with high-resolution numerical atmospheric simulations . Combining these (measurement/modeling) enhances understanding of seasonal variations in meteorology and composition together with the controlling processes. Two intensive observation periods (winter 2012 and summer Olympics 2012) focus upon the vertical structure and evolution of the urban boundary layer, chemical controls on nitrogen dioxide and ozone production, in particular the role of volatile organic compounds, and processes controlling the evolution, size, distribution and composition of particulate matter. The paper shows that mixing heights are deeper over London than in the rural surroundings and the seasonality of the urban boundary layer evolution controls when concentrations peak. The composition also reflects the seasonality of sources such as domestic burning and biogenic emissions.

Atmospheric chemistry and physics in the atmosphere of a developed megacity (London): an overview of the REPARTEE experiment and its conclusions

The REgents PARk and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size fractions in the atmosphere of London derived both from bulk chemical analysis and aerosol mass spectrometry with two instrument types.

Parasitoids select plants more heavily infested with their caterpillar hosts: a new approach to aid interpretation of plant headspace volatiles

Plants produce volatile organic compounds (VOCs) in response to herbivore attack, and these VOCs can be used by parasitoids of the herbivore as host location cues. We investigated the behavioural responses of the parasitoid Cotesia vestalis to VOCs from a plant–herbivore complex consisting of cabbage plants (Brassica oleracea) and the parasitoids host caterpillar, Plutella xylostella. A Y-tube olfactometer was used to compare the parasitoids' responses to VOCs produced as a result of different levels of attack by the caterpillar and equivalent levels of mechanical damage. Headspace VOC production by these plant treatments was examined using gas chromatography–mass spectrometry. Cotesia vestalis were able to exploit quantitative and qualitative differences in volatile emissions, from the plant–herbivore complex, produced as a result of different numbers of herbivores feeding. Cotesia vestalis showed a preference for plants with more herbivores and herbivore damage, but did not distinguish between different levels of mechanical damage. Volatile profiles of plants with different levels of herbivores/herbivore damage could also be separated by canonical discriminant analyses. Analyses revealed a number of compounds whose emission increased significantly with herbivore load, and these VOCs may be particularly good indicators of herbivore number, as the parasitoid processes cues from its external environment