In situ XAFS investigation of palladium species present during the Heck reaction in room temperature ionic liquids

The Heck reaction, performed in room temperature ionic liquids, has been studied by in situ XAFS, which indicates that palladium clusters of 0.8-1.6 nm diameter are the main species present during reaction.

Evaluation of methodologies to determine vegetable oil species present in oil mixtures: Proposition of an approach to meet the EU legislation demands for correct vegetable oils labelling

Refined vegetable oils are widely used in the food industry as ingredients or components in many processed food products in the form of oil blends. To date, the generic term 'vegetable oil' has been used in the labelling of food containing oil blends. With the introduction of new EU Regulation for Food Information (1169/2011) due to take effect in 2014, the oil species used must be clearly identified on the package and there is a need for development of fit for purpose methodology for industry and regulators alike to verify the oil species present in a product. The available methodologies that may be employed to authenticate the botanical origin of a vegetable oil admixture were reviewed and evaluated. The majority of the sources however, described techniques applied to crude vegetable oils such as olive oil due to the lack of refined vegetable oil focused studies. Nevertheless, DNA based typing methods and stable isotopes procedures were found not suitable for this particular purpose due to several issues. Only a small number of specific chromatographic and spectroscopic fingerprinting methods in either targeted or untargeted mode were found to be applicable in potentially providing a solution to this complex authenticity problem. Applied as a single method in isolation, these techniques would be able to give limited information on the oils identity as signals obtained for various oil types may well be overlapping. Therefore, more complex and combined approaches are likely to be needed to identify the oil species present in oil blends employing a stepwise approach in combination with advanced chemometrics. Options to provide such a methodology are outlined in the current study.

Biodiversity loss and ecosystem functioning: Distinguishing between number and identity of species

Given currently high rates of extinction, it is critical to be able to predict how ecosystems will respond to loss of species and consequent changes in community structure. Much previous research in this area has been based on terrestrial systems, using synthetically assembled communities. There has beer! much less research on inter-trophic effects in different systems, using in situ removal experiments. Problems with the design of early experiments have made it difficult to determine whether reductions in ecosystem functioning in low diversity treatments were due to the number of species present or merely to the reduced likelihood of including particular (

Speciation of Uranium in Sediments before and after In situ Biostimulation

The success of sequestration-based remediation strategies will depend on detailed information, including the predominant U species present as sources before biostimulation and the products produced during and after in situ biostimulation. We used X-ray absorption spectroscopy to determine the valence state and chemical speciation of U in sediment samples collected at a variety of depths through the contaminant plume at the Field Research Center at Oak Ridge, TN, before and after approximately 400 days of in situ biostimulation, as well as in duplicate bioreduced sediments after 363 days of resting conditions. The results indicate that U(VI) in subsurface sediments was partially reduced to 10–40% U(IV) during biostimulation. After biostimulation, U was no longer bound to carbon ligands and was adsorbed to Fe/Mn minerals. Reduction of U(VI) to U(IV) continued in sediment samples stored under anaerobic condition at <4 °C for 12 months, with the fraction of U(IV) in sediments more than doubling and U concentrations in the aqueous phase decreasing from 0.5-0.74 to <0.1 µM. A shift of uranyl species from uranyl bound to phosphorus ligands to uranyl bound to carbon ligands and the formation of nanoparticulate uraninite occurred in the sediment samples during storage.

A PRELIMINARY ASSESSMENT OF THE DISTRIBUTION OF THE SEA LAMPREY (PETROMYZON MARINUS L.), RIVER LAMPREY (LAMPETRA FLUVIATILIS (L.)) AND BROOK LAMPREY (LAMPETRA PLANERI (BLOCH)) IN NORTHERN IRELAND

Lampreys are endangered in Europe, and European states are legally required to take measures to ensure their protection. However, there is currently little information on the distribution of the three species present in Northern Ireland. Anecdotal records of adult lampreys were collated from anglers and other sources, and a systematic electrofishing survey was undertaken to establish the distribution of lamprey ammocoetes. Lampreys were found in seven of the nine Northern Irish river catchments. Brook lampreys (Lampetra planeri (Bloch)) were widely distributed, but the two anadromous species, sea lamprey (Petromyzon marinus L.) and river lamprey (Lampetra fluviatilis (L.)), were more limited in their distribution, possibly due to barriers restricting migration.

EMISSION STUDIES OF THE PLUME PRODUCED DURING YBA2CU3O7 FILM PRODUCTION BY LASER-ABLATION

The optical plume emissions produced on excimer laser ablation of a YBa2Cu3O7 target are reported and identified with the various atomic, ionic, and molecular species present. The spatial and temporal distribution of these emissions were studied as a function of the laser fluence and oxygen pressure. At the laser fluences used (4-6 J/cm(2)) some target material is ablated or evaporated directly in molecular form. In addition efficient formation of molecular oxides is observed at the contact front of the expanding plume with the surrounding oxygen atmosphere. The intensity and spatial distribution of oxide emission in the visible plume therefore provides a sensitive diagnostic for optimization of substrate location and deposition conditions.

Arsenic accumulation and phosphorus status in two rice (Oryza sativa L.) cultivars surveyed from fields in South China

The consumption of paddy rice (Oryza sativa L.) is a major inorganic arsenic exposure pathway in S.E. Asia. A multi-location survey was undertaken in Guangdong Province, South China to assess arsenic accumulation and speciation in 2 rice cultivars, one an Indica and the other a hybrid Indica. The results showed that arsenic concentrations in rice tissue increased in the order grain <husk <straw <root. Rice grain arsenic content of 2 rice cultivars was significant different and correlated with phosphorus concentration and molar ratio of P/As in shoot, being higher for the Indica cultivar than for the hybrid Indica, which suggests altering shoot phosphorus status as a promising route for breeding rice cultivars with reduced grain arsenic. Speciation of grain arsenic, performed using HPLC-ICP-MS, identified inorganic arsenic as the dominant arsenic species present in the rice grain.

Can arsenic-phytochelatin complex formation be used as an indicator for toxicity in Helianthus annuus?

The formation of arsenic-phytochelatin (As-PC) complexes is thought to be part of the plant detoxification strategy for arsenic. This work examines (i) the arsenic (As) concentration-dependent formation of As-PC complex formation and (ii) redistribution and metabolism of As after arrested As uptake in Helianthus annuus. HPLC with parallel ICP-MS/ES-MS detection was used to identify and quantify the species present in plant extracts exposed to arsenate (As(V)) (between 0 and 66.7 micromol As l-1 for 24 h). At As concentrations below the EC50 value for root growth (22 micromol As l-1) As uptake is exponential, but it is reduced at concentrations above. Translocation between root and shoot seemed to be limited to the uptake phase of arsenic. No redistribution of As between root and shoot was observed after arresting As exposure. The formation of As-PC complexes was concentration-dependent. The amount and number of As-PC complexes increased exponentially with concentration up to 13.7 micromol As l-1. As(III)-PC3 and GS-As(III)-PC2 complexes were the dominant species in all samples. The ratio of PC-bound As to unbound As increased up to 1.3 micromol As l-1 and decreased at higher concentrations. Methylation of inorganic As was only a minor pathway in H. annuus with about 1% As methylated over a 32 d period. The concentration dependence of As-PC complex formation, amount of unbound reduced and oxidized PC2, and the relative uptake rate showed that As starts to influence the cellular metabolism of H. annuus negatively at As concentrations well below the EC50 value determined by more traditional means. Generally, As-PC complexes and PC-synthesis rate seem to be the more sensitive parameters to be studied when As toxicity values are to be estimated.

Arsenic accumulation and metabolism in rice (Oryza sativa L.)

The use of arsenic (As) contaminated groundwater for irrigation of crops has resulted in elevated concentrations of arsenic in agricultural soils in Bangladesh, West Bengal (India), and elsewhere. Paddy rice (Oryza sativa L.) is the main agricultural crop grown in the arsenic-affected areas of Bangladesh. There is, therefore, concern regarding accumulation of arsenic in rice grown those soils. A greenhouse study was conducted to examine the effects of arsenic-contaminated irrigation water on the growth of rice and uptake and speciation of arsenic. Treatments of the greenhouse experiment consisted of two phosphate doses and seven different arsenate concentrations ranging from 0 to 8 mg of As L(-1) applied regularly throughout the 170-day post-transplantation growing period until plants were ready for harvesting. Increasing the concentration of arsenate in irrigation water significantly decreased plant height, grain yield, the number of filled grains, grain weight, and root biomass, while the arsenic concentrations in root, straw, and rice husk increased significantly. Concentrations of arsenic in rice grain did not exceed the food hygiene concentration limit (1.0 mg of As kg(-1) dry weight). The concentrations of arsenic in rice straw (up to 91.8 mg kg(-1) for the highest As treatment) were of the same order of magnitude as root arsenic concentrations (up to 107.5 mg kg(-1)), suggesting that arsenic can be readily translocated to the shoot. While not covered by food hygiene regulations, rice straw is used as cattle feed in many countries including Bangladesh. The high arsenic concentrations may have the potential for adverse health effects on the cattle and an increase of arsenic exposure in humans via the plant-animal-human pathway. Arsenic concentrations in rice plant parts except husk were not affected by application of phosphate. As the concentration of arsenic in the rice grain was low, arsenic speciation was performed only on rice straw to predict the risk associated with feeding contaminated straw to the cattle. Speciation of arsenic in tissues (using HPLC-ICP-MS) revealed that the predominant species present in straw was arsenate followed by arsenite and dimethylarsinic acid (DMAA). As DMAA is only present at low concentrations, it is unlikely this will greatly alter the toxicity of arsenic present in rice.

Field observation of sequestration of uranium in iron-rich sediments under sequential reduction-oxidation conditions at the DOE Oak Ridge IFRC

At the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site, the iron content of shallow subsurface materials (i.e. weathered saprolite) is relatively high (up to 5-6% as w/w), and therefore, the forms of the iron species present plays a critical role in the long-term sequestration of uranium. A long term pilot-scale study of the bioreduction and reoxidation of uranium conducted at the ORIFRC area 3 site, adjacent to the former S-3 disposal ponds (source zone), has provided us with the opportunity to study the impact of iron species on the sequestration of U(VI). The aqueous U(VI) concentrations at the site were decreased to below the EPA MCL through the intermittent injection of ethanol as the electron donor. Previous field tests indicated that both oxygen and nitrate could oxidize the bioreduced U(IV) and cause a short-term rebound of aqueous phase uranium concentration after the oxidative agents were delivered directly to the bioreduced zone.

A field test has been conducted to examine the long-term effect of exposure of bioreduced sediments to nitrate in contaminated groundwater for more than 1,380 days at the Area 3 site. Contaminated groundwater was allowed to invade the previously bioreduced zone via the natural groundwater gradient after an extended period in which reducing conditions were maintained and the bioreduced zone was protected from the influx of upgradient contaminated groundwater. The geochemical response to the invasion of contaminated groundwater was dependent on whether the monitoring location is in the middle or the fringe of the previously bioreduced zone. In general, the nitrate concentrations in the previously bioreduced area, increased gradually from near zero to ~50-300 mM within 200 days and then stabilized. The pH declined from bioreduced levels of 6.2-6.7 to below 5.0. Uranium concentrations rebounded in all monitoring wells but at different rates. At most locations U concentrations rebounded, declined and then rebounded again. Methane gas disappeared while a significant level (20,000 to 44,000 ppmv) N2O was found in the groundwater of monitoring wells after three years of reoxidization.

The U(IV) in sediments was mainly reoxidized to U(VI) species. Based on XANES analysis, the predominate uranium in all samples after re-oxidation was similar to a uranyl nitrate form. But the U content in the sediment remained as high as that determined after bioreduction activates were completed, indicating that much of the U is still sequestrated in situ. SEM observations of surged fine sediments revealed that clusters of colloidal-sized (200-500nm) U-containing precipitates appeared to have formed in situ, regardless from sample of FW106 in non-bioactivity control area or of pre-bioreduced FW101-2 and FW102-3. Additionally, SEM-EDS and microprobe analysis, showed that the U-containing precipitates (~1% U) in FW106 are notably higher in Fe, compared to the precipitates (~1-2.5% U) from FW101-2 and FW102-3. However, XRF analysis indicated that the U content was remained as high as 2180 and 1810 mg/kg with U/Fe ratio at 0.077 and 0.055 vs 0.037 g/g, respectively in pre-bioreduced FW101-2 and FW102-3, suggesting more U sequestrated by Fe in pre-bioreduced sediments.

Physicochemical tolerance, habitat use and predation are drivers of patterns of coexistence and exclusion among invasive and resident amphipods

1. Patterns of coexistence and exclusion among resident and invading species in freshwaters may be generated by direct biotic interactions well as by indirect interactions with the broader abiotic and biotic environments. The North American ‘shrimp’ Crangonyx pseudogracilis (Crustacea: Amphipoda) is invasive in Europe where it forms complex patterns of apparent exclusion and coexistence with resident Gammarus spp. amphipods. Using a comprehensive integrated approach, we investigated the potential biotic and interacting abiotic factors driving these distribution patterns.
2. A 2009 of 69 sites revealed that of 56 river sites containing amphipods only 6 contained C. pseudogracilis and these always co-occurred with Gammarus spp.. In contrast, C. pseudogracilis was the only species present in the 12 ponds/reservoirs containing amphipods.
3. Field transplant experiments in ponds and laboratory oxygen tolerance experiments revealed that C. pseudogracilis tolerates physicochemical regimes which Gammarus spp. are incapable of surviving.
4. River microhabitat sampling showed C. pseudogracilis dominating in slower, more pooled and macrophyte-dense patches, while Gammarus spp. were dominant in faster, more riffled areas.
5. Field bioassays indicated that predation of C. pseudogracilis by Gammarus spp. may be frequent in patches of rivers if/when the species meet.
6. River drift sampling revealed that C. pseudogracilis was greatly underrepresented in night/day drift relative to the Gammarus spp.. Laboratory studies showed C. pseudogracilis to be more photophobic and less active than Gammarus spp., both behaviours potentially contributing to low drift prevalence and consequent reduced exposure to shared drift predators.
7. These interacting factors may ultimately contribute to the coexistence, exclusion and relative distributions of C. pseudogracilis and Gammarus spp.. The former is potentially subject to intense predation from the latter if they encounter one another in the same microhabitat. However, with C. pseudogracilis being more physicochemically tolerant and displaying different habitat utilisation patterns than the Gammarus spp. in respect of the benthos and drift, such encounters are probably minimised. Hence C. pseudogracilis can persist in the same sites with the Gammarus spp., albeit in different microhabitats.

Phylogeographical analysis of two cold-tolerant plants with disjunct Lusitanian distributions does not support in situ survival during the last glaciation

Aim: We used a combination of modelling and genetic approaches to investigate whether Pinguicula grandiflora and Saxifraga spathularis, two species that exhibit disjunct Lusitanian distributions, may have persisted through the Last Glacial Maximum (LGM, c. 21 ka) in separate northern and southern refugia.

Location: Northern and eastern Spain and south-western Ireland.

Methods: Palaeodistribution modelling using maxent was used to identify putative refugial areas for both species at the LGM, as well as to estimate their distributions during the Last Interglacial (LIG, c. 120 ka). Phylogeographical analysis of samples from across both species' ranges was carried out using one chloroplast and three nuclear loci for each species.

Results: The palaeodistribution models identified very limited suitable habitat for either species during the LIG, followed by expansion during the LGM. A single, large refugium across northern Spain and southern France was postulated for P. grandiflora. Two suitable regions were identified for S. spathularis: one in northern Spain, corresponding to the eastern part of the species' present-day distribution in Iberia, and the other on the continental shelf off the west coast of Brittany, south of the limit of the British–Irish ice sheet. Phylogeographical analyses indicated extremely reduced levels of genetic diversity in Irish populations of P. grandiflora relative to those in mainland Europe, but comparable levels of diversity between Irish and mainland European populations of S. spathularis, including the occurrence of private hapotypes in both regions.

Main conclusions: Modelling and phylogeographical analyses indicate that P. grandiflora persisted through the LGM in a southern refugium, and achieved its current Irish distribution via northward dispersal after the retreat of the ice sheets. Although the results for S. spathularis are more equivocal, a similar recolonization scenario also seems the most likely explanation for the species' current distribution.

On the analysis of inhomogeneous magnetic field spectrometer for laser-driven ion acceleration

We present a detailed study of the use of a non-parallel, inhomogeneous magnetic field spectrometer for the investigation of laser-accelerated ion beams. Employing a wedged yoke design, we demonstrate the feasibility of an in-situ self-calibration technique of the non-uniform magnetic field and show that high-precision measurements of ion energies are possible in a wide-angle configuration. We also discuss the implications of a stacked detector system for unambiguous identification of different ion species present in the ion beam and explore the feasibility of detection of high energy particles beyond 100 MeV/amu in radiation harsh environments.

Wide-ranging alterations in the brain fatty acid complement of subjects with late Alzheimer’s disease as detected by GC-MS

Disturbed lipid metabolism is a well-established feature of human Alzheimer’s disease (AD). The present study used gas chromatography-mass spectrometry (GC-MS) analysis of fatty acid methyl esters (FAMES) to profile all detectable fatty acid (FA) species present in post-mortem neocortical tissue (Brodmann 7 region). Quantitative targeted analysis was undertaken from 29 subjects (n=15 age-matched controls; n=14 late-stage AD). GC-MS analysis of FAMES detected a total of 24 FAs and of these, 20 were fully quantifiable. The results showed significant and wide ranging elevations in AD brain FA concentrations. A total of 9 FAs were elevated in AD with cis-13,16-docosenoic acid increased most (170%; P=0.033). Intriguingly, docosahexanoic acid (DHA; C22:6) concentrations were elevated (47%; P=0.018) which conflicts with the findings of others (unaltered or decreased) in some brain regions after the onset of AD. Furthermore, our results appear to indicate that subject gender influences brain FA levels in AD subjects (but not in age-matched control subjects). Among AD subjects 7 FA species were significantly higher in males than in females. These preliminary findings pinpoint FA disturbances as potentially important in the pathology of AD. Further work is required to determine if such changes are influenced by disease severity or different types of dementia.

Wide-ranging alterations in the brain fatty acid complement of subjects with late Alzheimer's disease as detected by GC-MS

Disturbed lipid metabolism is a well-established feature of human Alzheimer's disease (AD). The present study used gas chromatography-mass spectrometry (GC-MS) analysis of fatty acid methyl esters (FAMES) to profile all detectable fatty acid (FA) species present in post-mortem neocortical tissue (Brodmann 7 region). Quantitative targeted analysis was undertaken from 29 subjects (n=15 age-matched controls; n=14 late-stage AD). GC-MS analysis of FAMES detected a total of 24 FAs and of these, 20 were fully quantifiable. The results showed significant and wide ranging elevations in AD brain FA concentrations. A total of 9 FAs were elevated in AD with cis-13,16-docosenoic acid increased most (170%; P=0.033). Intriguingly, docosahexanoic acid (DHA; C22:6) concentrations were elevated (47%; P=0.018) which conflicts with the findings of others (unaltered or decreased) in some brain regions after the onset of AD. Furthermore, our results appear to indicate that subject gender influences brain FA levels in AD subjects (but not in age-matched control subjects). Among AD subjects 7 FA species were significantly higher in males than in females. These preliminary findings pinpoint FA disturbances as potentially important in the pathology of AD. Further work is required to determine if such changes are influenced by disease severity or different types of dementia.