The use of Short Time on Stream (STOS) transient kinetics to investigate the role of hydrogen in enhancing NOx reduction over silver catalysts

The role of hydrogen in promoting the reduction by ammonia of NOx on silver catalysts has been investigated using a Short Time on Stream (STOS) technique to allow differentiation between potentially reactive intermediates and relatively inactive spectator species. Under these conditions, we have used DRIFTS to identify surface nitrate species that are formed and removed on a timescale of seconds. This is in contrast to nitrate species observed under normal steady-state conditions which can continue to form over many tens of minutes. Since this timescale of seconds is very similar to the response rate at which the NH3/NOx to N-2 reaction is accelerated when H-2 is added, or decelerated when H-2 is removed, we conclude that this fast-forming and fast disappearing nitrate species is most probably adsorbed on or close to the active Ag sites. The removal of such a blocking nitrate species from the active sites can explain the effect of H-2 in greatly increasing the rate of the overall de-NOx reaction. 

An Integrated Approach to Quantifying Groundwater and Surface Water Contributions of Stream Flow

The management of water resources in Ireland prior to the Water Framework Directive (WFD) has focussed on surface water and groundwater as separate entities. A critical element to the successful implementation of the
WFD is to improve our understanding of the interaction between the two and flow mechanisms by which groundwaters discharge to surface waters. An improved understanding of the contribution of groundwater to surface water is required for the classification of groundwater body status and the determination of groundwater quality thresholds. The results of the study will also have a wider application to many areas of the WFD.
A subcommittee of the WFD Groundwater Working Group (GWWG) has been formed to develop a methodology to estimate the groundwater contribution to Irish Rivers. The group has selected a number of analytical techniques to quantify components of stream flow in an Irish context (Master Recession Curve, Unit Hydrograph, Flood Studies Report methodologies and
hydrogeological analytical modelling). The components of stream flow that can be identified include deep groundwater, intermediate and overland. These analyses have been tested on seven pilot catchments that have a variety of hydrogeological settings and have been used to inform and constrain a mathematical model. The mathematical model used was the NAM (NedbØr-AfstrØmnings-Model) rainfall-runoff model which is a module of DHIs MIKE 11 modelling suite. The results from these pilot catchments have been used to develop a decision model based on catchment descriptors from GIS datasets for the selection of NAM parameters. The datasets used include the mapping of aquifers, vulnerability and subsoils, soils, the Digital Terrain Model, CORINE and lakes. The national coverage of the GIS datasets has allowed the extrapolation of the mathematical model to regional catchments across Ireland.

Dorsal and ventral stream mediated visual processing in genetic subtypes of Prader-Willi syndrome

Previous work has suggested that there are specific deficits in dorsal stream processing in a variety of developmental disorders. Prader-Willi syndrome (PWS) is associated with two main genetic subtypes, deletion and disomy. Relative strengths in visual processing are shown in PWS, although these strengths may be specific to the deletion subtype. We investigated visual processing in PWS using an adapted Simon task which contrasted location (dorsal stream) and shape identity (ventral stream) tasks. Compared to a group of typically developing children, children with PWS deletion showed a greater degree of impairment in the dorsal stream task than in the ventral stream task, a pattern similar to that shown in a group of boys with Fragile-X syndrome. When matched on a measure of non-verbal ability, children with PWS disomy showed the opposite pattern with better performance in the location compared to the shape task, although these task performance asymmetries may have been linked to executive control processes. It is proposed that children with PWS deletion show a relative strength in visual processing in the ventral stream along with a specific deficit in dorsal stream processing. In contrast, children with PWS disomy show neither effect. (C) 2009 Published by Elsevier Ltd.

Use of Short Time-on-Stream Attenuated Total Internal Reflection Infrared Spectroscopy To Probe Changes in Adsorption Geometry for Determination of Selectivity in the Hydrogenation of Citral

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A new experimental procedure based on attenuated total reflection infrared spectroscopy has been developed to investigate surface species under liquid phase reaction conditions. The technique has been tested by investigating the enhanced selectivity in the hydrogenation of α,β-unsaturated aldehyde citral over a 5% Pt/SiO2 catalyst toward unsaturated alcohols geraniol/nerol, which occurs when citronellal is added to the reaction. The change in selectivity is proposed to be the result of a change in the citral adsorption mode in the presence of citronellal. Short time on stream attenuated total internal reflection infrared spectroscopy has allowed identification of the adsorption modes of citral. With no citronellal, citral adsorbs through both the C═C and C═O groups; however, in the presence of citronellal, citral adsorption occurs through the C═O group only, which is proposed to be the cause of the altered reaction selectivity.

Arsenic Speciation and Localization in Horticultural Produce Grown in a Historically Impacted Mining Region

A field and market basket study (similar to 1300 samples) of locally grown fruits and vegetables from historically mined regions of southwest (SW) England (Cornwall and Devon), and as reference, a market basket study of similarly locally grown produce from the northeast (NE) of Scotland (Aberdeenshire) was conducted to determine the concentration of total and inorganic arsenic present in produce from these two geogenically different areas of the U.K. On average 98.5% of the total arsenic found was present in the inorganic form. For both the market basket and the field survey, the highest total arsenic was present in open leaf structure produce (i.e., kale, chard, lettuce, greens, and spinach) being most likely to soil/dust contamination of the open leaf structure. The concentration of total arsenic in potatoes, swedes, and carrots was lower in peeled produce compared to unpeeled produce. For baked potatoes, the concentration of total arsenic in the skin was higher compared to the total arsenic concentration of the potato flesh, this difference in localization being confirmed by laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS). For all above ground produce (e.g., apples), peeling did not have a significant effect on the concentration of total arsenic present.

Vertex Clustering of Augmented Graph Streams

In this paper we propose a graph stream clustering algorithm with a unied similarity measure on both structural and attribute properties of vertices, with each attribute being treated as a vertex. Unlike others, our approach does not require an input parameter for the number of clusters, instead, it dynamically creates new sketch-based clusters and periodically merges existing similar clusters. Experiments on two publicly available datasets reveal the advantages of our approach in detecting vertex clusters in the graph stream. We provide a detailed investigation into how parameters affect the algorithm performance. We also provide a quantitative evaluation and comparison with a well-known offline community detection algorithm which shows that our streaming algorithm can achieve comparable or better average cluster purity.

In silico mining identifies IGFBP3 as a novel target of methylation in prostate cancer

Promoter hypermethylation is central in deregulating gene expression in cancer. Identification of novel methylation targets in specific cancers provides a basis for their use as biomarkers of disease occurrence and progression. We developed an in silico strategy to globally identify potential targets of promoter hypermethylation in prostate cancer by screening for 5' CpG islands in 631 genes that were reported as downregulated in prostate cancer. A virtual archive of 338 potential targets of methylation was produced. One candidate, IGFBP3, was selected for investigation, along with glutathione-S-transferase pi (GSTP1), a well-known methylation target in prostate cancer. Methylation of IGFBP3 was detected by quantitative methylation-specific PCR in 49/79 primary prostate adenocarcinoma and 7/14 adjacent preinvasive high-grade prostatic intraepithelial neoplasia, but in only 5/37 benign prostatic hyperplasia (P < 0.0001) and in 0/39 histologically normal adjacent prostate tissue, which implies that methylation of IGFBP3 may be involved in the early stages of prostate cancer development. Hypermethylation of IGFBP3 was only detected in samples that also demonstrated methylation of GSTP1 and was also correlated with Gleason score > or =7 (P=0.01), indicating that it has potential as a prognostic marker. In addition, pharmacological demethylation induced strong expression of IGFBP3 in LNCaP prostate cancer cells. Our concept of a methylation candidate gene bank was successful in identifying a novel target of frequent hypermethylation in early-stage prostate cancer. Evaluation of further relevant genes could contribute towards a methylation signature of this disease.

Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y^-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. their use potential as organic carbon (C) and nitrogen (N) sources. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of ¹³C:¹⁵N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of ¹³C:¹⁵N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and streamwater sampled from the Oberer Seebach stream (Austria), tracing assimilation and mineralization of ¹³C and ¹⁵N labels from mineral-sorbed and dissolved amino acids.Here we present data on the effects of organo-mineral sorption upon amino acid mineralization and its C:N stoichiometry. Organo-mineral sorption had a significant effect upon microbial activity, restricting C and N mineralization by both the biofilm and streamwater treatments. Distinct differences in community response were observed, with both dissolved and mineral-stabilized amino acids playing an enhanced role in the metabolism of the streamwater microbial community. Mineral-sorption of amino acids differentially affected C & N mineralization and reduced the C:N ratio of the dissolved amino acid pool. The present study demonstrates that organo-mineral complexes restrict microbial degradation of OM and may, consequently, alter the carbon and nitrogen cycling dynamics within aquatic ecosystems.

Mining Money: the generative capacities of scientific and legal knowledge practices in the making of resource economies

In 1997 a scandal associated with Bre-X, a junior mining firm, and its prospecting activities in Indonesia, exposed to public scrutiny the ways in which mineral exploration firms acquire, assess and report on scientific claims about the natural environment. At stake here was not just how investors understood the provisional nature of scientific knowledge, but also evidence of fraud. Contemporaneous mining scandals not only included the salting of cores, but also unreliable proprietary sample preparation and assay methods, mis-representations of visual field estimates as drilling results and ‘overly optimistic’ geological reports. This paper reports on initiatives taken in the wake of these scandals and prompted by the Mining Standards Task Force (TSE/OSC 1999). For regulators, mandated to increase investor confidence in Canada’s leading role within the global mining industry, efforts focused first and foremost upon identifying and removing sources of error and wilfulness within the production and circulation of scientific knowledge claims. A common goal cross-cutting these initiatives was ‘a faithful representation of nature’ (Daston and Galison 2010), however, as the paper argues, this was manifest in an assemblage of practices governed by distinct and rival regulative visions of science and the making of markets in claims about ‘nature’. These ‘practices of fidelity’, it is argued, can be consequential in shaping the spatial and temporal dynamics of the marketization of nature.

Using microbiological tracers to assess the impact of winter land use restrictions on the quality of stream headwaters in a small catchment.

Diverse land use activities can elevate risk of microbiological contamination entering stream headwaters. Spatially distributed water quality monitoring carried out across a 17km(2) agricultural catchment aimed to characterize microbiological contamination reaching surface water and investigate whether winter agricultural land use restrictions proved effective in addressing water quality degradation. Combined flow and concentration data revealed no significant difference in fecal indicator organism (FIO) fluxes in base flow samples collected during the open and prohibited periods for spreading organic fertilizer, while relative concentrations of Escherichia coli, fecal streptococci and sulfite reducing bacteria indicated consistently fresh fecal pollution reached aquatic receptors during both periods. Microbial source tracking, employing Bacteroides 16S rRNA gene markers, demonstrated a dominance of bovine fecal waste in river water samples upstream of a wastewater treatment plant discharge during open periods. This contrasted with responses during prohibited periods where human-derived signatures dominated. Differences in microbiological signature, when viewed with hydrological data, suggested that increasing groundwater levels restricted vertical infiltration of effluent from on-site wastewater treatment systems and diverted it to drains and surface water. Study results reflect seasonality of contaminant inputs, while suggesting winter land use restrictions can be effective in limiting impacts of agricultural wastes to base flow water quality.

Spatial and temporal influences of in-stream factors on the chemistry and epilithic biomasses of upland stream metal deposits

The density and composition of stream bed metal deposits are affected by physical, chemical and biological processes. In this paper we investigate the importance of these processes and their relation to algal and non-photosynthetic detrital (NPD) biomass in a set of upland streams in Northern Ireland. Deposit density and Fe, Mn, Al and P concentrations varied with stream pH across sites but not seasonally. No effects of stream bed erosion or photoreduction were detected on deposit densities. Seasonal variation in stream water metal concentrations was correlated with rainfall. NPD biomass was a significant predictor of both spatial and seasonal variation in deposit concentrations. There were strong, non-linear, relations between NPD biomass and deposit metal concentrations, with Fe and Mn becoming relatively more important and algal biomass declining above threshold deposit/NPD densities. The results suggest that NPD biomass influences deposit density and reduces the biomass of photosynthetic autotrophs above a threshold deposit density.

Catchment and in-stream influences on metal concentration and ochre deposit density in upland streams, Northern Ireland

Metal concentrations from stream waters in two geological blocks in Northern Ireland were compared to determine the contributions of catchment characteristics and in-stream conditions. One block is composed of metamorphosed schist and unconsolidated glacial drift with peat or peaty podzol (mainly humic) soils, while the other block consists of tertiary basalt with brown earth and gley soils. Water samples were collected from 52 stream sites and analysed for Fe, Mn and Al as well as a range of other chemical determinands known to affect metal solubility. Densities of metal-rich ochre deposit were determined for stream bed stone samples. Higher conductivities and concentrations of bicarbonate, alkalinity, Ca and Mg occurred on basalt than on schist. Despite higher Fe and Mn oxide concentrations in basalt-derived non-humic soils, stream water concentrations were much lower and ochre deposit densities only one third of those on schist overlain by humic soils. Neither rock nor soil type predicted Al concentrations, but pH and dissolved oxygen did. Peat-generated acidity and the limited acid neutralising capacity of base-poor metamorphosed schist have resulted in elevated concentrations of metals and ochre deposit in surface waters.