Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments

The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv. Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

Does reactive surface area depend on grain size? Results from pH 3, 25 circle C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 mu m were dissolved in pH 3, HCl at 25 degrees C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 X 10(-10) mol(feldspar) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 X 10(-10) mol(feldspar) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol(feldspar) g(-1) s(-1). For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 x 10(-12) mol(biotite) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 X 10(-12) mol(biotite) g(-1) s(-1). For all normalising terms rates varied significantly (p <= 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over wich they would change significantly. (c) 2006 Elsevier Inc. All rights reserved.

Reactive crisis management in construction projects

Patterns of communication and behaviour emerge within a construction project in response to a construction crisis. This paper investigates, within a grounded theory framework, the nature of these patterns, the sociological and psychological forces which shape them and their relationship with crisis management efficiency. A grounded theory is presented in four parts. The first part conceives a construction crisis as a period of social instability, arising from conflicting interest groups, seeking to exercise power in the pursuit of social structures which suit their political and economic interests. The second part sees a construction crisis as a de-sensitizing phenomenon which results in a period of behavioural instability and conflict which is self-perpetuating. The third part cites social structure as an important influence upon construction crisis management efficiency, in determining the efficiency of information flow, and the level of uncertainty between those affected. The fourth part points to the in-built defence mechanisms which construction crises have and to three managerial ironies which make construction crisis management difficult.

Bjerknes compensation and the decadal variability of the energy transports in a coupled climate model

In the 1960s, Jacob Bjerknes suggested that if the top-of-the-atmosphere (TOA) fluxes and the oceanic heat storage did not vary too much, then the total energy transport by the climate system would not vary too much either. This implies that any large anomalies of oceanic and atmospheric energy transport should be equal and opposite. This simple scenario has become known as Bjerknes compensation. A long control run of the Third Hadley Centre Coupled Ocean-Atmosphere General Circulation Model (HadCM3) has been investigated. It was found that northern extratropical decadal anomalies of atmospheric and oceanic energy transports are significantly anticorrelated and have similar magnitudes, which is consistent with the predictions of Bjerknes compensation. ne degree of compensation in the northern extratropics was found to increase with increasing, time scale. Bjerknes compensation did not occur in the Tropics, primarily as large changes in the surface fluxes were associated with large changes in the TOA fluxes. In the ocean, the decadal variability of the energy transport is associated with fluctuations in the meridional overturning circulation in the Atlantic Ocean. A stronger Atlantic Ocean energy transport leads to strong warming of surface temperatures in the Greenland-Iceland-Norwegian (GIN) Seas. which results in a reduced equator-to-pole surface temperature gradient and reduced atmospheric baroclinicity. It is argued that a stronger Atlantic Ocean energy transport leads to a weakened atmospheric transient energy transport.

Reactive uptake coefficients for heterogeneous reaction of N2O5 with submicron aerosols of NaCl and natural sea salt

The kinetics of uptake of gaseous N2O5 on submicron aerosols containing NaCl and natural sea salt have been investigated in a flow reactor as a function of relative humidity (RH) in the range 30-80% at 295±2K and a total pressure of 1bar. The measured uptake coefficients, γ, were larger on the aerosols containing sea salt compared to those of pure NaCl, and in both cases increased with increasing RH. These observations are explained in terms of the variation in the size of the salt droplets, which leads to a limitation in the uptake rate into small particles. After correction for this effect the uptake coefficients are independent of relative humidity, and agree with those measured previously on larger droplets. A value of γ=0.025 is recommended for the reactive uptake coefficient for N2O5 on deliquesced sea salt droplets at 298K and RH>40%.

Noise, predation risk compensation and vigilance in the chaffinch Fringilla coelebs

Background noise should in theory hinder detection of auditory cues associated with approaching danger. We tested whether foraging chaffinches Fringilla coelebs responded to background noise by increasing vigilance, and examined whether this was explained by predation risk compensation or by a novel stimulus hypothesis. The former predicts that only inter-scan interval should be modified in the presence of background noise, not vigilance levels generally. This is because noise hampers auditory cue detection and increases perceived predation risk primarily when in the head-down position, and also because previous tests have shown that only interscan interval is correlated with predator detection ability in this system. Chaffinches only modified interscan interval supporting this hypothesis. At the same time they made significantly fewer pecks when feeding during the background noise treatment and so the increased vigilance led to a reduction in intake rate, suggesting that compensating for the increased predation risk could indirectly lead to a fitness cost. Finally, the novel stimulus hypothesis predicts that chaffinches should habituate to the noise, which did not occur within a trial or over 5 subsequent trials. We conclude that auditory cues may be an important component of the trade-off between vigilance and feeding, and discuss possible implications for anti-predation theory and ecological processes

Molybdenum eta(3)-allyl dicarbonyl complexes as a new class of precursors for highly reactive epoxidation catalysts with tert-butyl hydroperoxide

New Mo(II) diimine derivatives of [Mo(q (3)allyl)X(CO)(2)(CH3CN)(2)] (allyl = C3H5 and C5H5O; X = Cl, Br) were prepared, and [MO(eta(3)-C3H5)Cl(CO)(2)(BIAN)] (BIAN = 1,4-(4-chloro)phenyl-2,3-naphthalene-diazabutadiene) (7) was structurally characterized by single-crystal X-ray diffraction. This complex adopted an equatorial-axial arrangement of the bidentate ligand (axial isomer), in contrast with the precursors, found as the equatorial isomer in the solid and fluxional in solution. The new complexes of the type [Mo(eta(3)-allyl)X(CO)(2)(N-N)l (N-N is a bidentate chelating dinitrogen ligand) were tested for the catalytic epoxidation of cyclooctene using tert-butyl hydroperoxide as oxidant. All catalytic systems were 100% selective toward epoxide formation. While their turnover frequencies paralleled those of related Mo(eta) carbonyl compounds or Mo(VI) compounds bearing similar N-donor ligands, they exhibited similar olefin conversions in consecutive catalytic runs. The acetonitrile precursors were generally more active than the diimine complexes, and the chloro derivatives more active than the bromo ones. Combined vibrational and NMR spectroscopy and computational studies (DFT) were used to investigate the nature of the molybdenum species formed in the catalytic system with [Mo(eta(3)-C3H5)Cl(CO)(2){1,4-(2,6-dimethyl)phenyl-2.3-dimethyldiazabuta diene}] (4) and to propose that the resulting species may be dimeric bearing oxide bridges.

Influence of apolipoprotein E genotype and dietary alpha-tocopherol on redox status and C-reactive protein levels in apolipoprotein E3 and E4 targeted replacement mice

The molecular basis of the positive association between apoE4 genotype and CVD remains unclear. There is direct in vitro evidence indicating that apoE4 is a poorer antioxidant relative to the apoE3 isoform, with some indirect in vivo evidence also available. Therefore it was hypothesised that apoE4 carriers may benefit from alpha-tocopherol (alpha-Toc) supplementation. Targeted replacement mice expressing the human apoE3 and apoE4 were fed with a diet poor (0 mg/kg diet) or rich (200 mg/kg diet) in alpha-Toc for 12 weeks. Neither apoE genotype nor dietary alpha-Toc exerted any effects on the antioxidant defence system, including glutathione, catalase, superoxide dismutase, glutathione peroxidase and glutathione reductase activities. In addition, no differences were observed in mitogen-induced lymphocyte proliferation. alpha-Toc concentrations were modestly higher in plasma and lower in tissues of apoE4 compared with apoE3 mice, with the greatest differences evident in the lung, suggesting that an apoE4 genotype may reduce alpha-Toc delivery to tissues. A tendency towards increased plasma F-2-isoprostanes in apoE4 mice was observed, while liver thiobarbituric acid-reactive substances did not differ between apoE3 and apoE4 mice. In addition, C-reactive protein (CRP) concentrations were reduced in apoE4 mice indicating that this positive effect on CRP may in part negate the increased CVD risk associated with an apoE4 genotype.

Targeting C-reactive protein for the treatment of cardiovascular disease

Complement-mediated inflammation exacerbates the tissue injury of ischaemic necrosis in heart attacks and strokes, the most common causes of death in developed countries. Large infarct size increases immediate morbidity and mortality and, in survivors of the acute event, larger non-functional scars adversely affect long-term prognosis. There is thus an important unmet medical need for new cardioprotective and neuroprotective treatments. We have previously shown that human C-reactive protein (CRP), the classical acute-phase protein that binds to ligands exposed in damaged tissue and then activates complement(1), increases myocardial and cerebral infarct size in rats subjected to coronary or cerebral artery ligation, respectively(2,3). Rat CRP does not activate rat complement, whereas human CRP activates both rat and human complement(4). Administration of human CRP to rats is thus an excellent model for the actions of endogenous human CRP2,3. Here we report the design, synthesis and efficacy of 1,6-bis(phosphocholine)-hexane as a specific small-molecule inhibitor of CRP. Five molecules of this palindromic compound are bound by two pentameric CRP molecules, crosslinking and occluding the ligand-binding B-face of CRP and blocking its functions. Administration of 1,6-bis(phosphocholine)-hexane to rats undergoing acute myocardial infarction abrogated the increase in infarct size and cardiac dysfunction produced by injection of human CRP. Therapeutic inhibition of CRP is thus a promising new approach to cardioprotection in acute myocardial infarction, and may also provide neuroprotection in stroke. Potential wider applications include other inflammatory, infective and tissue-damaging conditions characterized by increased CRP production, in which binding of CRP to exposed ligands in damaged cells may lead to complement-mediated exacerbation of tissue injury.

Steady-spectrum contexts and perceptual compensation for reverberation in speech identification

Perceptual compensation for reverberation was measured by embedding test words in contexts that were either spoken phrases or processed versions of this speech. The processing gave steady-spectrum contexts with no changes in the shape of the short-term spectral envelope over time, but with fluctuations in the temporal envelope. Test words were from a continuum between "sir" and "stir." When the amount of reverberation in test words was increased, to a level above the amount in the context, they sounded more like "sir." However, when the amount of reverberation in the context was also increased, to the level present in the test word, there was perceptual compensation in some conditions so that test words sounded more like "stir" again. Experiments here found compensation with speech contexts and with some steady-spectrum contexts, indicating that fluctuations in the context's temporal envelope can be sufficient for compensation. Other results suggest that the effectiveness of speech contexts is partly due to the narrow-band "frequency-channels" of the auditory periphery, where temporal-envelope fluctuations can be more pronounced than they are in the sound's broadband temporal envelope. Further results indicate that for compensation to influence speech, the context needs to be in a broad range of frequency channels. (c) 2007 Acoustical Society of America.

Perceptual compensation for reverberation in speech identification: effects of single-band, multiple-band and wideband noise contexts

Perceptual effects of room reverberation on a "sir" or "stir" test-word can be observed when the level of reverberation in the word is increased, while the reverberation in a surrounding 'context I utterance remains at a minimal level. The result is that listeners make more "sit" identifications. When the context's reverberation is also increased, to approach the level in the test word, extrinsic perceptual compensation is observed, so that the number of listeners' "sir" identifications reduces to a value similar to that found with minimal reverberation. Thus far, compensation effects have only been observed with speech or speech-like contexts in which the short-term spectrum changes as the speaker's articulators move. The results reported here show that some noise contexts with static short-term spectra can also give rise to compensation. From these experiments it would appear that compensation requires a context with a temporal envelope that fluctuates to some extent, so that parts of it resemble offsets. These findings are consistent with a rather general kind of perceptual compensation mechanism; one that is informed by the 'tails' that reverberation adds at offsets. Other results reported here show that narrow-band contexts do not bring about compensation, even when their temporal-envelopes are the same as those of the more effective wideband contexts. These results suggest that compensation is confined to the frequency range occupied by the context, and that in a wideband sound it might operate in a 'band by band' manner.

Perceptual compensation for effects of reverberation in speech identification

Listeners were asked to identify modified recordings of the words "sir" and "stir," which were spoken by an adult male British-English speaker. Steps along a continuum between the words were obtained by a pointwise interpolation of their temporal-envelopes. These test words were embedded in a longer "context" utterance, and played with different amounts of reverberation. Increasing only the test-word's reverberation shifts the listener's category boundary so that more "sir"-identifications are made. This effect reduces when the context's reverberation is also increased, indicating perceptual compensation that is informed by the context. Experiment I finds that compensation is more prominent in rapid speech, that it varies between rooms, that it is more prominent when the test-word's reverberation is high, and that it increases with the context's reverberation. Further experiments show that compensation persists when the room is switched between the context and the test word, when presentation is monaural, and when the context is reversed. However, compensation reduces when the context's reverberation pattern is reversed, as well as when noise-versions of the context are used. "Tails" that reverberation introduces at the ends of sounds and at spectral transitions may inform the compensation mechanism about the amount of reflected sound in the signal. (c) 2005 Acoustical Society of America.

Perceptual compensation for effects of echo and of reverberation on speech identification

In an ideal "reverberant" room, the energy of the impulse responses decays smoothly, at a constant rate of dB/s, so that gradually-decaying tails are added at the ends of sounds. Conversely, a single echo gives a flat energy-decay up to the echo's arrival time, which then drops abruptly, so that sounds with only echoes lack the decaying-tail feature of reverberation. The perceptual effects of these types of reflection pattern were measured with test-words from a continuum of steps between "sir" and "stir", which were each embedded in a carrier phrase. When the proportion of reflected sound in test-words is increased, to a level above the amount in the carrier, the test words sound more like "sir". However, when the proportion of reflected sound in the carrier is also increased, to match the amount in the test word, there can be a perceptual compensation where test words sound more like "stir" again. A reference condition used real-room reverberation from recordings at different source to receiver distances. In a synthetic-reverberation condition, the reflection pattern was from a "colorless" impulse response, comprising exponentially-decaying reflections that were spaced at intervals. In a synthetic-echo condition, the reflection pattern was obtained from the synthetic reverberation by removing the intervals between reflections before delaying the resulting cluster relative to the direct sound. Compensation occurred in the reference condition and in different types of synthetic reverberation, but not in synthetic-echo conditions. This result indicates that the presence of tails from reverberation informs the compensation mechanism.