70 research outputs found

    Determination of neo- and d-chiro-Inositol Hexakisphosphate in Soils by Solution 31P NMR Spectroscopy

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    The inositol phosphates are an abundant but poorly understood group of organic phosphorus compounds found widely in the environment. Four stereoisomers of inositol hexakisphosphate (IP6) occur, although for three of these (scyllo, flea, and D-chiro) the origins, dynamics, and biological function remain unknown, due in large part to analytical limitations in their measurement in environmental samples. We synthesized authentic neo- and n-chiro-IP6 and used them to identify signals from these compounds in three soils from the Falkland Islands. Both compounds resisted hypobromite oxidation and gave quantifiable P-31 NMR signals at delta = 6.67 ppm (equatorial phosphate groups of the 4-equatorial/2-axial conformer of neo-IP6) and delta = 6.48 ppm (equatorial phosphate groups of the 2-equatorial/4-axial conformer of D-chiro-IP6) in soil extracts. Inositol hexakisphosphate accounted for 46-54% of the soil organic phosphorus, of which the four stereoisomers constituted, on average, 55.9% (myo), 32.8% (scyllo), 6.1% (neo), and 5.2% (n-chiro). Reappraisal of the literature based on the new signal assignments revealed that neo- and D-chiro-IP6 occur widely in both terrestrial and aquatic ecosystems. These results confirm that the inositol phosphates can constitute a considerable fraction of the organic phosphorus in soils and reveal the prevalence of neo- and D-chiro-IP6 in the environment. The hypobromite oxidation and solution P-31 NMR spectroscopy procedure allows the simultaneous quantification of all four IP6 stereoisomers in environmental samples and provides a platform for research into the origins and ecological significance of these enigmatic compounds

    Polyphosphates as a source of enhanced P fluxes in marine sediments overlain by anoxic waters: Evidence from (31)P NMR

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    Sedimentary phosphorus (P) composition was investigated in Effingham Inlet, a fjord located on the west coast of Vancouver Island in Barkley Sound. Solid-state (31)P nuclear magnetic resonance (NMR) spectroscopy was applied to demineralized sediment samples from sites overlain by oxic and anoxic bottom waters. The two sites were similar in terms of key diagenetic parameters, including the mass accumulation rate, integrated sulfate reduction rate, and bulk sediment organic carbon content. In contrast, P benthic fluxes were much higher at the anoxic site. (31)P NMR results show that P esters and phosphonates are the major organic P species present at the surface and at depth in sediments at both sites. Polyphosphates were only found in the surface sediment of the site overlain by oxic waters. The varying stability of polyphosphates in microorganisms under different redox conditions may, in part, explain their distribution as well as differences in P flux between the two sites

    Sediment source fingerprinting: benchmarking recent outputs, remaining challenges and emerging themes

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    Abstract: Purpose: This review of sediment source fingerprinting assesses the current state-of-the-art, remaining challenges and emerging themes. It combines inputs from international scientists either with track records in the approach or with expertise relevant to progressing the science. Methods: Web of Science and Google Scholar were used to review published papers spanning the period 2013–2019, inclusive, to confirm publication trends in quantities of papers by study area country and the types of tracers used. The most recent (2018–2019, inclusive) papers were also benchmarked using a methodological decision-tree published in 2017. Scope: Areas requiring further research and international consensus on methodological detail are reviewed, and these comprise spatial variability in tracers and corresponding sampling implications for end-members, temporal variability in tracers and sampling implications for end-members and target sediment, tracer conservation and knowledge-based pre-selection, the physico-chemical basis for source discrimination and dissemination of fingerprinting results to stakeholders. Emerging themes are also discussed: novel tracers, concentration-dependence for biomarkers, combining sediment fingerprinting and age-dating, applications to sediment-bound pollutants, incorporation of supportive spatial information to augment discrimination and modelling, aeolian sediment source fingerprinting, integration with process-based models and development of open-access software tools for data processing. Conclusions: The popularity of sediment source fingerprinting continues on an upward trend globally, but with this growth comes issues surrounding lack of standardisation and procedural diversity. Nonetheless, the last 2 years have also evidenced growing uptake of critical requirements for robust applications and this review is intended to signpost investigators, both old and new, towards these benchmarks and remaining research challenges for, and emerging options for different applications of, the fingerprinting approach

    The Diversity of Nuclear Magnetic Resonance Spectroscopy

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    Pedological trends and implications for forest productivity in a Holocene soil chronosequence, Calvert Island, British Columbia, Canada.

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    Chronosequence studies of soil formation and ecosystem development provide important insights into the pathways and rates of change occurring on centennial and millennial time scales. In cool or temperate humid environments, Podzols are the predominant soil type formed under coniferous forests in coarse-textured parent material and have been a major focus of chronosequence studies. This study examined the rate and mechanisms of Podzol development and related forest productivity in a sand dune chronosequence in a hypermaritime climate in coastal British Columbia (BC). The sequence spans 10,760 864 years over eight sites and is the first documented chronosequence in coastal BC to span most of the Holocene Epoch. Soil samples from each genetic horizon were analyzed for bulk density, pH and concentrations of total carbon (C), pyrophosphate- and oxalate-extractable aluminum (Al) and iron (Fe), and total elements. Within ~3,500 years a mature Podzol had formed, with cemented horizons (ortstein and placic) present. Organo-metallic complexation appeared to be the dominant mechanism involved in podzolization . Despite a mild, moist climate conducive to chemical weathering, all soils had similarly low values for the Chemical Index of Alteration, suggesting that congruent dissolution of primary minerals may be occurring. Ecosystem retrogression is apparent in the latter stages of the chronosequence – a phenomenon not previously documented in coastal BC. Further research is needed to examine the interactions of nutrient limitation, soil physical barriers, and other possible drivers of ecosystem retrogression.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author
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