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.

Influence of molecular composition on the development of microstructure from sheared polyethylene melts: Molecular and lamellar templating

A combination of in situ and ex situ X-ray scattering techniques and transmission electron microscopy has been used to study the crystallization behaviour of polyethylene, following the imposition of melt shear. In the case of a branched material, the imposition of shear flow up to a rate of 30 s(-1) was found to induce no anisotropy. Although shearing the linear material only ever induced a very small degree of anisotropy in the melt, for shear rates > 0.15 s(-1), subsequent crystallization resulted in increasing anisotropy. Blends of the above two polyethylenes were produced, in which the linear material constituted the minority fraction (similar to 10%). Isothermal crystallization at temperatures where extensive crystallization of the branched material does not occur demonstrated that the behaviour of the linear component of the sheared blend mirrored that of the linear polyethylene alone. However, in addition, it was found that when crystallized in the presence of an oriented morphology, the branched polymer also formed anisotropic structures. We have termed the process templating, in which the crystallization behaviour of the bulk of the system (similar to 90% branched material) is completely altered (spherulitic to oriented lamellar) by mapping it onto a pre-existing minority structure (similar to 10% linear polymer). (c) 2006 Elsevier Ltd. All rights reserved.

Composition and cure temperature: The influence on properties of final flexible PU cold cure foam parts

Foams are cellular structures, produced by gas bubbles formed during the polyurethane polymerization mixture. Flexible PU foams meet the following two criteria: have a limited resistance to an applied load, being both permeable to air and reversibly deformable. There are two main types of flexible foams, hot and cold cure foams differing in composition and processing temperatures. The hot cure foams are widely applied and represent the main composition of actual foams, while cold cure foams present several processing and property advantages, e.g, faster demoulding time, better humid aging properties and more versatility, as hardness variation with index changes are greater than with hot cure foams. The processing of cold cure foams also is attractive due to the low energy consumption (mould temperature from 30 degrees to 65 degrees C) comparatively to hot cure foams (mould temperature from 30 degrees to 250 degrees C). Another advantage is the high variety of soft materials for low temperature processing moulds. Cold cure foams are diphenylmethane diisocyanate (MDI) based while hot cure foams are toluene diisocyanate (TDI) based. This study is concerned with Viscoelastic flexible foams MDI based for medical applications. Differential Scanning Calorimetry (DSC) was used to characterize the cure kinetics and Dynamical Mechanical Analisys to collect mechanical data. The data obtained from these two experimental procedures were analyzed and associated to establish processing/properties/operation conditions relationships. These maps for the selection of optimized processing/properties/operation conditions are important to achieve better final part properties at lower costs and lead times.

The chlorine isotope composition of Earth's mantle

Chlorine stable isotope compositions ( delta Cl-37) of 22 mid- ocean ridge basalts ( MORBs) correlate with Cl content. The high-delta Cl-37, Cl- rich basalts are highly contaminated by Cl- rich materials ( seawater, brines, or altered rocks). The low-delta(37) Cl, Cl- poor basalts approach the composition of uncontaminated, mantle- derived magmas. Thus, most or all oceanic lavas are contaminated to some extent during their emplacement. MORB- source mantle has delta(37) Cl <= -1.6 per mil (%), which is significantly lower than that of surface reservoirs (similar to 0 parts per thousand not equal). This isotopic difference between the surface and deep Earth results from net Cl isotopic fractionation ( associated with removal of Cl from the mantle and its return by subduction over Earth history) and/ or the addition ( to external reservoirs) of a late volatile supply that is Cl-37- enriched.

Seasonal trends in the stable isotopic composition of snow and meltwater runoff in a subarctic catchment at Okstindan, Norway

Seasonal variations in the stable isotopic composition of snow and meltwater were investigated in a sub-arctic, mountainous, but non-glacial, catchment at Okstindan in northern Norway based on analyses of delta(18)O and deltaD. Samples were collected during four field periods (August 1998; April 1999; June 1999 and August 1999) at three sites lying on an altitudinal transect (740-970 m a.s.l.). Snowpack data display an increase in the mean values of delta(18)O (increasing from a mean value of - 13.51 to - 11.49% between April and August), as well as a decrease in variability through the melt period. Comparison with a regional meteoric water line indicates that the slope of the delta(18)O - deltaD line for the snowpacks decreases over the same period, dropping from 7.49 to approximately 6.2. This change points to the role of evaporation in snowpack ablation and is confirmed by the vertical profile of deuterium excess. Snowpack seepage data, although limited, also suggest reduced values of deltaD, as might be associated with local evaporation during meltwater generation. In general, meltwaters were depleted in delta(18)O relative to the source snowpack at the peak of the melt (June), but later in the year (August) the difference between the two was not statistically significant. The diurnal pattern of isotopic composition indicates that the most depleted meltwaters coincide with the peak in temperature and, hence, meltwater production.

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH I experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost similar to 9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >similar to 2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction. (C) 2008 Elsevier Ltd. All rights reserved.

Neolithic woodland composition and exploitation in the Southern Levant: a comparison between archaeobotanical remains from WF16 and present day woodland at Hammam Adethni

Excavations at the Pre-Pottery Neolithic site of WF16 in the Southern Levant produced an archaeobotanical assemblage constituted by plant macro-fossils and wood charcoal. As with all such assemblages, its species composition will most likely provide a biased reflection of those within the Neolithic woodland that had been exploited owing to cultural selection and differential preservation. As a means of facilitating its interpretation, a survey was undertaken of a relatively undisturbed patch of gallery woodland associated with a permanent water course at Hammam Adethni, approximately four kilometres south-east of WF16. The substantial overlap of the species within this woodland and those in the archaeobotanical assemblage suggests that this present-day woodland provides an analogue for that of the Neolithic and may therefore indicate what other plant resources the inhabitants of WF16 may have exploited, but which have left no archaeological trace. The interpretation of the results is supported by a comparative study of wood charcoal from present-day Bedouin hearths in Wadi Faynan.

Environmental factors and vegetation composition, Lefka Ori Massif, Crete, S. Aegean

Aim The aim of this study was to explore the environmental factors that determine the spatial distribution of oro-mediterranean and alti-mediterranean plant communities in Crete. Location The paper provides a quantitative analysis of vegetation-environment relationships for two study areas within the Lefka Ori massif Crete, a proposed Natura 2000 site. Methods Eleven environmental variables were recorded: altitude, slope, aspect, percentage of bare rock, percentage of unvegetated ground, soil depth, pH, organic matter content and percentages of sand, silt and clay content. Classification of the vegetation was based on twinspan, while detrended correspondence analysis (DCA) and canonical correspondence analysis (CCA) were used to identify environmental gradients linked to community distribution. Results One hundred and twenty-five species were recorded from 120 plots located within the two study areas. Forty-seven of the recorded species are endemic, belonging to 35 families. Hemicryptophytes and chamaephytes were the most frequent, suggesting a typical oro-mediterranean life form spectrum. The samples were classified into five main community types and one transitional. The main gradients, identified by CCA, were altitude and surface cover type in the North-west site, while in the Central site the gradients were soil formation-development and surface cover type. Main conclusions The use of classification in combination with ordination techniques resulted in a good discrimination between plant communities and a greater understanding of controlling environmental factors. The methodology adopted can be employed for improving baseline information on plant community ecology and distribution in Mediterranean mountain zones.

Analysis of Phytochemical Composition and Chemoprotective Capacity of Rocket (Eruca sativa and Diplotaxis tenuifolia) Leafy Salad Following Cultivation in Different Environments

Consumption of green leafy vegetables is associated with reduced risk of several types of cancer and cardiovascular disease. These beneficial effects are attributed to a range of phytochemicals including flavonoids and glucosinolates, both of which are found in high levels in Brassicaceous crops. Rocket is the general name attributed to cultivars of Eruca sativa and Diplotaxis tenufolia, known as salad rocket and wild rocket, respectively. We have shown that different light levels during the cultivation period of these crops have a significant impact on the levels of flavonoids present in the crop at harvest, with over 15-fold increase achieved in quercetin, isorhamnetin, and cyanidin in high light conditions. Postharvest storage further affects the levels of both flavonoids and glucosinolates, with cyanidin increasing during shelf life and some glucosinolates, such as glucoiberverin, being reduced over the same storage period. In vitro assays using human colon cell lines demonstrate that glucosinolate-rich extracts of Eruca sativa cv. Sky, but not Diplotaxis tenufolia cv. Voyager, confer significant resistance to oxidative stress on the cells, which is indicative of the chemoprotective properties of the leaves from this species. Our findings indicate that both pre and postharvest environment and genotypic selection, when developing new lines of Brassicaceous vegetables, are important considerations with the goal of improving human nutrition and health.

Influences of space, soil, nematodes and plants on microbial community composition of chalk grassland soils

Microbial communities respond to a variety of environmental factors related to resources (e.g. plant and soil organic matter), habitat (e.g. soil characteristics) and predation (e.g. nematodes, protozoa and viruses). However, the relative contribution of these factors on microbial community composition is poorly understood. Here, we sampled soils from 30 chalk grassland fields located in three different chalk hill ridges of Southern England, using a spatially explicit sampling scheme. We assessed microbial communities via phospholipid fatty acid (PLFA) analyses and PCR-denaturing gradient gel electrophoresis (DGGE) and measured soil characteristics, as well as nematode and plant community composition. The relative influences of space, soil, vegetation and nematodes on soil microorganisms were contrasted using variation partitioning and path analysis. Results indicate that soil characteristics and plant community composition, representing habitat and resources, shape soil microbial community composition, whereas the influence of nematodes, a potential predation factor, appears to be relatively small. Spatial variation in microbial community structure was detected at broad (between fields) and fine (within fields) scales, suggesting that microbial communities exhibit biogeographic patterns at different scales. Although our analysis included several relevant explanatory data sets, a large part of the variation in microbial communities remained unexplained (up to 92% in some analyses). However, in several analyses, significant parts of the variation in microbial community structure could be explained. The results of this study contribute to our understanding of the relative importance of different environmental and spatial factors in driving the composition of soil-borne microbial communities.

Airborne measurements of the spatial distribution of aerosol chemical composition across Europe and evolution of the organic fraction

The spatial distribution of aerosol chemical composition and the evolution of the Organic Aerosol (OA) fraction is investigated based upon airborne measurements of aerosol chemical composition in the planetary boundary layer across Europe. Sub-micron aerosol chemical composition was measured using a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS). A range of sampling conditions were evaluated, including relatively clean background conditions, polluted conditions in North-Western Europe and the near-field to far-field outflow from such conditions. Ammonium nitrate and OA were found to be the dominant chemical components of the sub-micron aerosol burden, with mass fractions ranging from 20--50% each. Ammonium nitrate was found to dominate in North-Western Europe during episodes of high pollution, reflecting the enhanced NO_x and ammonia sources in this region. OA was ubiquitous across Europe and concentrations generally exceeded sulphate by 30--160%. A factor analysis of the OA burden was performed in order to probe the evolution across this large range of spatial and temporal scales. Two separate Oxygenated Organic Aerosol (OOA) components were identified; one representing an aged-OOA, termed Low Volatility-OOA and another representing fresher-OOA, termed Semi Volatile-OOA on the basis of their mass spectral similarity to previous studies. The factors derived from different flights were not chemically the same but rather reflect the range of OA composition sampled during a particular flight. Significant chemical processing of the OA was observed downwind of major sources in North-Western Europe, with the LV-OOA component becoming increasingly dominant as the distance from source and photochemical processing increased. The measurements suggest that the aging of OA can be viewed as a continuum, with a progression from a less oxidised, semi-volatile component to a highly oxidised, less-volatile component. Substantial amounts of pollution were observed far downwind of continental Europe, with OA and ammonium nitrate being the major constituents of the sub-micron aerosol burden. Such anthropogenically perturbed air masses can significantly perturb regional climate far downwind of major source regions.

Atmospheric composition of West Africa: highlights from the AMMA program

The atmospheric composition of West Africa reflects the interaction of various dynamical and chemical systems (i.e. biogenic, urban, convective and long-range transport) with signatures from local to continental scales. Recent measurements performed during the African Monsoon Multidisciplinary Analyses (AMMA) observational periods in 2005 and 2006 provide new data which has allowed new insight into the processes within these systems that control the distribution of ozone and its precursors. Using these new data and recently published results, we provide an overview of these systems with a particular emphasis on ozone distributions over West Africa during the wet season.