Characterizing Pb mobilization from upland soils to streams using (206)Pb/(207)Pb isotopic ratios

Anthropogenically deposited lead (Pb) binds efficiently to soil organic matter, which can be mobilized through hydrologically mediated mechanisms, with implications for ecological and potable quality of receiving waters. Lead isotopic ((206)Pb/(207)Pb) ratios change down peat profiles as a consequence of long-term temporal variation in depositional sources, each with distinctive isotopic signatures. This study characterizes differential Pb transport mechanisms from deposition to streams at two small catchments with contrasting soil types in upland Wales, U.K., by determining Pb concentrations and (206)Pb/(207)Pb ratios from soil core profiles, interstitial pore waters, and stream water. Hydrological characteristics of soils are instrumental in determining the location in soil profiles of exported Pb and hence concentration and (206)Pb/(207)Pb ratios in surface waters. The highest Pb concentrations from near-surface soils are mobilized, concomitant with high dissolved organic carbon (DOC) exports, from hydrologically responsive peat soils with preferential shallow subsurface flows, leading to increased Pb concentrations in stream water and isotopic signatures more closely resembling recently deposited Pb. In more minerogenic soils, percolation of water allows Pb, bound to DOC, to be retained in mineral horizons and combined with other groundwater sources, resulting in Pb being transported from throughout the profile with a more geogenic isotopic signature. This study shows that (206)Pb/(207)Pb ratios can enhance our understanding of the provenances and transport mechanisms of Pb and potentially organic matter within upland soils.

Selenium Characterization in the Global Rice Supply Chain

For up to 1 billion people worldwide, insufficient dietary intake of selenium (Se) is a serious health constraint Cereals are the dominant Se source for those on low protein diets, as typified by the global malnourished population. With crop Se content constrained largely by underlying geology, regional soil Se variations are often mirrored by their locally grown staples. Despite this, the Se concentrations of much of the world's rice, the mainstay of so many, is poorly characterized, for both total Se content and Se speciation. In this study, 1092 samples of market sourced polished rice were obtained. The sampled rice encompassed dominant rice producing and exporting countries. Rice from the U.S. and India were found to be the most enriched, while mean average levels were lowest in Egyptian rice: similar to 32-fold less than their North American equivalents. By weighting country averages by contribution to either global production or export, modeled baseline values for both were produced. Based on a daily rice consumption of 300 g day(-1), around 75% of the grains from the production and export pools would fail to provide 70% of daily recommended Se intakes. Furthermore, Se localization and speciation characterization using X-ray fluorescence (mu-XRF) and X-ray absorption near edge structure (mu-XANES) techniques were investigated in a Se-rich sample. The results revealed that the large majority of Se in the endosperm was present in organic forms.

Arsenic sequestration in iron plaque, its accumulation and speciation in mature rice plants (Oryza sativa L.)

A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order: iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain.

Immunochemical characterization of a polysaccharide antigen of Bacteroides fragilis with an IgM monoclonal antibody

An IgM mouse monoclonal antibody (McAb) Bf4 was produced to a surface polysaccharide of Bacteroides fragilis NCTC 9343. Immunoblotting showed that McAb Bf4 reacted strongly with a high molecular mass structure which was sensitive to oxidation with periodate but resisted protease treatment. An inhibition enzyme-linked immunosorbent assay (ELISA) indicated that McAb Bf4 did not cross react with the sixteen Bacteroides species and strains tested. Cells of B. fragilis NCTC 9343 recovered from the various interfaces of a Percoll discontinuous density gradient were tested in the inhibition ELISA. Bacteria from the 0-20%, 20-40% and 40-60% interfaces inhibited the ELISA; however, cells from the 60-80% interface did not. Electron microscopy with immunogold labelling showed that McAb Bf4 did not react with the extracellular fibrous network on bacteria recovered from the 0-20% interface, or the extracellular electron dense layer on cells from the 60-80% interface; however, it was associated with a surface structure on cells from the 20-40% interface. Growth in vivo did not enrich for bacteria with this structure.

Permafrost response to last interglacial warming: field evidence from non-glaciated Yukon and Alaska

We present stratigraphic observations from three sites in eastern Beringia - Ch'ijee's Bluff in northern Yukon and nearby exposures on the Old Crow River, the Palisades on the Yukon River in Alaska, and placer mining exposures at Thistle Creek in west-central Yukon - which provide insight into the response of permafrost to regional warming during the last interglaciation. Chronology is based on the presence of Old Crow tephra, an important regional stratigraphic marker that dates to late Marine Isotope Stage 6, supplemented by paleoecology and non-finite C ages on wood-rich organic silts. Old Crow tephra overlies several relict ice wedges at the Palisades and Thistle Creek, indicating that permafrost at these sites did not thaw completely during the last interglaciation. Prominent deposits of last interglacial wood-rich organic silt are present at multiple sites in eastern Beringia, and probably represent accumulations of reworked forest vegetation due to thaw slumping or deposition into thermokarst ponds or depressions. Consistent stratigraphic relations between these deposits, Old Crow tephra, and ice wedge pseudomorphs at our three study sites, and at least six other sites in eastern Beringia, suggest that thaw of shallow permafrost was widespread during the last interglaciation. Limited stratigraphic evidence suggests that thaw was probably on the order of meters, rather than 10s of meters. The ubiquity of shallow permafrost degradation during the last interglaciation suggests that current ground warming may foreshadow widespread near-surface thaw under even modest future warming scenarios. However, the persistence of relict pre-last interglacial ice wedges highlights the potential for the regional antiquity of discontinuous permafrost, and provides compelling field evidence for the long-term resilience of deep permafrost during sustained periods of warmer-than-present climate.

Asprich Peptides Are Occluded in Calcite and Permanently Disorder Biomineral Crystals

Macromolecules are a minority but important component of the minerals formed by living organisms, or biominerals. The role these macromolecules play at the early stages of biomineral formation, as well as their long-term and long-range effects on the mature biomineral, is poorly understood. A 42-amino acid peptide, asp2, was derived from the Asprich family of proteins. In this study we present X-ray absorption near-edge structure spectroscopy and X-ray photoelectron emission microscopy data from the asp2 peptide, the calcite (CaCO3) crystals, and the peptide + crystal composites. The results clearly show that asp2 is occluded in fully formed biomineral crystals and slightly but permanently disorders the crystal structure at short- and long-range distances.

Antigen-specific IgA and IgG responses in calves inoculated intranasally with ovalbumin encapsulated in poly(DL-lactide-co-glycolide) microspheres

The immunogenicity of proteins encapsulated in poly(DL-lactide-co-glycolide) (PLG) microspheres has not been investigated to any extent in large animal models. In this study, IgG and IgA responses to ovalbumin (OVA), encapsulated in microspheres was investigated following intranasal inoculation into calves. Scanning electron microscopy and flow cytometric analysis demonstrated a uniform microsphere population with a diameter of <2.5 micrometers. Ovalbumin was released steadily from particles stored in PBS almost in a linear fashion, and after 4 weeks many particles showed cracks and fissures in their surface structure. Following intranasal inoculation of calves with different doses of encapsulated antigen, mean levels of ovalbumin-specific IgA were observed to increase steadily but significant differences in IgA levels (from the pre-inoculation level) were only observed following a second intranasal inoculation. With 0.5 and 1.0mg doses of antigen, ovalbumin-specific IgG was also detected in serum. Ovalbumin-specific IgA persisted in nasal secretions for a considerable period of time and were still detectable in four out of seven animals, 6 months after inoculation.

Iron plaque formation, arsenic uptake and speciation in different genotypes of mature rice plants (Oryza sativa L.)

A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order:? iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain. A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order:? iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain.

Coleoptera and microbe biomass in Antarctic Dry Valley paleosols adjacent to the Inland Ice: Implications for Mars

Bulk paleosol samples collected from a Middle to Early Miocene moraine in the New Mountain area of the Dry Valleys, Antarctica, yielded Coleoptera exoskeletons and occasional endoskeletons showing considerable diagenetic effects along with several species of bacteria, all lodged in a dry-frozen but salt-rich horizon at shallow depth to the land surface. The till is at the older end of a chronologic sequence of glacial deposits, thought to have been deposited before the transition from wet-based to cold-based ice (similar to 15 Ma), and hence, entirely weathered in contact with the subaerial atmosphere. It is possible, though not absolutely verifiable, that the skeletons date from this early stage of emplacement having undergone modifications whenever light snowmelt occurred or salt concentrations lowered the freezing temperature to maintain water as liquid. Correlation of the Coleoptera species with cultured bacteria in the sample and the likelihood of co-habitation with Beauveria bassiani found in two adjacent, although younger paleosols, leads to new questions about the antiquity of the Coleoptera and the source of N and glucose from chitinase derived from the insects. The skeletons in the 831 section may date close to the oldest preserved chitin (Oligocene) yet found on Earth. While harsh Martian conditions make it seemingly intolerable for complex, multicellular organisms such as insects to exist in the near-surface and subaerially, life within similar cold, dry paleosol microenvironments (Cryosols) of Antarctica point to life potential for the Red Planet, especially when considering the relatively diverse microbe (bacteria and fungi) population. (C) 2011 Elsevier Ltd. All rights reserved.

Characterization of physio-chemical processes and hydration kinetics in concretes containing supplementary cementitious materials using electrical property measurements

The current study monitors both the short- and long-term hydration characteristics of concrete using discretized conductivity measurements from initial gauging, through setting and hardening, the latter comprising both the curing and post-curing periods. In particular, attention is directed to the near-surface concrete as it is this zone which protects the steel from the external environment and has a major influence on durability, performance and service-life. A wide range of concrete mixes is studied comprising both plain Portland cement concretes and concretes containing fly-ash and ground granulated blast furnace slag. The parameter normalised conductivity was used to identify four distinct stages in the hydration process and highlight the influence of supplementary cementitious materials (SCM) on hydration and hydration kinetics. A relationship has been presented to account for the temporal decrease in conductivity, post 10-days hydration. The testing procedure and methodology presented lend itself to in-situ monitoring of reinforced concrete structures. (c) 2013 Elsevier Ltd. All rights reserved.

Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir

In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO₂ selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO₂ selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using first principles method. It is found that CH₃CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO₂ selectivity and only Rh is able to increase the selectivity of CO₂ in DEFCs.

Assessing Climate Effects on Railway Earthworks Using MASW

Many parts of the UK’s rail network were constructed in the mid-19th century long before the advent of modern construction standards. Historic levels of low investment, poor maintenance strategies and the deleterious effects of climate change have resulted in critical elements of the rail network being at significant risk of failure. The majority of failures which have occurred over recent years have been triggered by extreme weather events. Advance assessment and remediation of earthworks is, however, significantly less costly than dealing with failures reactively. It is therefore crucial that appropriate approaches for assessment of the stability of earthworks are developed, so that repair work can be better targeted and failures avoided wherever possible. This extended abstract briefly discusses some preliminary results from an ongoing geophysical research project being carried out in order to study the impact of climate or seasonal weather variations on the stability of a century old railway embankment on the Gloucestershire Warwickshire steam railway line in Southern England.

Ecology of testate amoebae in an Amazonian peatland and development of a transfer function for palaeohydrological reconstruction

Tropical peatlands represent globally important carbon sinks with a unique biodiversity and are currently threatened by climate change and human activities. It is now imperative that proxy methods are developed to understand the ecohydrological dynamics of these systems and for testing peatland development models. Testate amoebae have been used as environmental indicators in ecological and palaeoecological studies of peatlands, primarily in ombrotrophic Sphagnum-dominated peatlands in the mid- and high-latitudes. We present the first ecological analysis of testate amoebae in a tropical peatland, a nutrient-poor domed bog in western (Peruvian) Amazonia. Litter samples were collected from different hydrological microforms (hummock to pool) along a transect from the edge to the interior of the peatland. We recorded 47 taxa from 21 genera. The most common taxa are Cryptodifflugia oviformis, Euglypha rotunda type, Phryganella acropodia, Pseudodifflugia fulva type and Trinema lineare. One species found only in the southern hemisphere, Argynnia spicata, is present. Arcella spp., Centropyxis aculeata and Lesqueresia spiralis are indicators of pools containing standing water. Canonical correspondence analysis and non-metric multidimensional scaling illustrate that water table depth is a significant control on the distribution of testate amoebae, similar to the results from mid- and high-latitude peatlands. A transfer function model for water table based on weighted averaging partial least-squares (WAPLS) regression is presented and performs well under cross-validation (r 2apparent=0.76,RMSE=4.29;r2jack=0.68,RMSEP=5.18. The transfer function was applied to a 1-m peat core, and sample-specific reconstruction errors were generated using bootstrapping. The reconstruction generally suggests near-surface water tables over the last 3,000 years, with a shift to drier conditions at c. cal. 1218-1273 AD