The molecular size continuum of soil organic phosphorus and its chemical associations

The chemical nature of most organic P (Porg) in soil remains ‘unresolved’ but is accounted for by a broad signal in the phosphomonoester region of solution 31P nuclear magnetic resonance (NMR) spectra. The molecular size range of this broad NMR signal and its molecular structure remain unclear. The aim of this study was to elucidate the chemical nature of Porg with increasing molecular size in soil extracts combining size exclusion chromatography (SEC) with solution 31P NMR spectroscopy. Gel-filtration SEC was carried out on NaOH-EDTA extracts of four soils (range 238-1135 mg Porg/kgsoil) to collect fractions with molecular sizes of 70 kDa. These were then analysed by NMR spectroscopy. Organic P was detected across the entire molecular size continuum from 70 kDa. Concentrations of Porg in the >10kDa fraction ranged from 107 to 427 mg P/kgsoil and exhibited on average three to four broad signals in the phosphomonoester region of NMR spectra. These broad signals were most prominent in the 10-20 and 20-50 kDa fractions, accounting for on average 77 % and 74 % of total phosphomonoesters, respectively. Our study demonstrates that the broad signal is present in all investigated molecular size fractions and comprises on average three to four components of varying NMR peak line width (20 to 250 Hz). The stereoisomers myo- and scyllo-inositol hexakisphosphates (IP6) were also present across multiple molecular size ranges but were predominant in the 5-10 kDa fraction. The proportion of IP associated with large molecular size fractions >10 kDa was on average 23 % (SD=39 %) of total IP across all soils. These findings suggest that stabilisation of IP in soil includes processes associated with the organic phase

U-Pb zircon dating of the Gruf Complex: disclosing the late Variscan granulitic lower crust of Europe stranded in the Central Alps

Permian granulites associated with noritic intrusions and websterites are a common feature of the post-Variscan European crust. Such granulites are common in the Southern Alps (e.g. Ivrea Zone), but occur only in the Gruf Complex in the Central Alps. To understand the geotectonic significance of these granulites, in particular in the context of Alpine migmatisation, zircons from 15 high-grade samples have been U-Pb dated by SHRIMP II analysis. Oscillatory zoned zircons from charnockite sheets, interpreted as melts generated through granulite facies fluid-absent biotite melting at 920-940°C, yield ages of 282-260Ma. Some of these zircons contain inclusions of opx, unequivocally attributable to the granulite facies, thus confirming a Permian age for the charnockites and associated granulites. Two samples from an enclave-rich orthogneiss sheet yield Cambrian and Ordovician zircon cores. Two deformed leucogranites and six ortho- and augengneisses, which compose two-thirds of the Gruf Complex, give zircon ages of 290-260Ma. Most zircons have milky rims with ages of 34-29Ma. These rims date the Alpine amphibolite facies migmatisation, an interpretation confirmed by directly dating a leucosome pocket from upper amphibolite facies metapelites. The Gruf charnockites associated with metre-scale schlieren and boudins of opx-sapphirine-garnet-granulites, websterites and gabbronorites can thus be identified as part of the post-Variscan European lower crust. A geotectonic reconstruction reveals that this piece of lower crust stranded in the (European) North upon rifting of the Neotethys, such contrasting the widespread granulite units in the Southern Alps. Emplacement of the Gruf lower crust into its present-day position occurred during migmatisation and formation of the Bergell Pluton in the aftermath of the breakoff of the European sla

Phosphorus species in sequentially extracted soil organic matter fractions

The majority of organic P (Porg) in soil is considered to be part of soil organic matter (SOM) associations, but its chemical nature is largely ‘unresolved’. In this study, we investigated the Porg composition in different SOM fractions of a Gleysol soil using the Humeomics sequential chemical fractionation (SCF) procedure combined with nuclear magnetic resonance (NMR) spectroscopy. In summary, SCF procedure with subsequent NaOH-EDTA extraction of the soil residue extracted a total of 1769 mg P/kgsoil compared to 1682 mg P/kgsoil of a single-step NaOH-EDTA extraction. Approximately 38 % of the extracted Porg was present in the form of the unresolved Porg pool, which was represented by one or two underlying broad signals in the phosphomonoester region of solution 31P NMR spectra. The SCF revealed that phosphomonoesters were recovered in each fraction: 47 % of the unresolved phosphomonoesters were associated with the SOM fraction released by breaking ester bonds (40 %) and ether bonds (7 %), whereas about 30 % of this unresolved Porg pool appeared in the SOM fraction closely associated with the soil mineral phase. Furthermore, the extractability of inositol phosphates (IP) was increased from 312 mg P/kgsoil to 534 mg P/kgsoil (factor 1.7) using the SCF procedure compared to a single-step NaOH-EDTA extraction. Previous studies have reported the presence of IP in molecular size fractions greater than 10 kDa. Our findings on the removal of IP with the fractionation of the SOM could explain the presence of IP in these large associations. We demonstrate that major pools of Porg are closely associated with SOM structures, comprising a diverse array of chemical species and bonding types. These results forward our understanding of Porg stabilisation, P transformation, and P cycling in terrestrial ecosystems towards an association point of view

Growth and alteration of uranium-rich microlite

Uranium-rich microlite, a pyrochlore-group mineral, occurs in 440 Ma old lithium pegmatites of the Mozambique Belt in East Africa. Microlite exhibits a pronounced growth zoning, with a U-free core surrounded by a U-rich rim (UO{sub 2} up to 17 wt.%). The core exhibits conjugate sets of straight cracks (cleavage planes) which provided pathways for a late-stage U-enriched pegmatitic fluid which interacted with the U-free microlite to produce a distinct U enrichment along the cracks and led to the formation of the U-rich rim. Following the stage of U incorporation into microlite, a second generation of hydrothermal fluids deposited mica along the cleavage planes. Subsequent to these two hydrothermal stages, the host rock was uplifted and subjected to intense low-temperature alteration during which Na, Ca and F were leached from the microlite crystals. This alteration also led to a hydration of microlite, but there is no evidence of U loss. These low-temperature alteration effects were only observed in the U-rich rim which is characterized by a large number of irregular cracks which are most probably the result of metamictization, as indicated by electron diffraction images and powder X-ray patterns. The pyrochlore-group minerals provide excellent natural analogues for pyrochlore-based nuclear waste forms, because samples of variable age and with high actinide contents are available

Charge conservation and time-varying speed of light

It has been recently claimed that cosmologies with time dependent speed of light might solve some of the problems of the standard cosmological scenario, as well as inflationary scenarios. In this letter we show that most of these models, when analyzed in a consistent way, lead to large violations of charge conservation. Thus, they are severly constrained by experiment, including those where $c$ is a power of the scale factor and those whose source term is the trace of the energy-momentum tensor. In addition, early Universe scenarios with a sudden change of $c$ related to baryogenesis are discarded.Comment: 4 page

New constraints on WIMPs from the Canfranc IGEX dark matter search

The IGEX Collaboration enriched 76Ge double-beta decay detectors are currently operating in the Canfranc Underground Laboratory with an overburden of 2450 m.w.e. A recent upgrade has made it possible to use them in a search for WIMPs. A new exclusion plot has been derived for WIMP-nucleon spin-independent interaction. To obtain this result, 30 days of data from one IGEX detector, which has an energy threshold of ~4 keV, have been considered. These data improve the exclusion limits derived from other germanium diode experiments in the ~50 GeV DAMA region, and show that with a moderate improvement of the background below 10 keV, the DAMA region may be tested with an additional 1 kg-year of exposure.Comment: 7 pages, 2 figures, submitted to Physics Letter

New limits on dark--matter WIMPs from the Heidelberg--Moscow experiment

New results after 0.69 kg yr of measurement with an enriched 76Ge detector of the Heidelberg--Moscow experiment with an active mass of 2.758 kg are presented. An energy threshold of 9 keV and a background level of 0.042 counts/(kg d keV) in the energy region between 15 keV and 40 keV was reached.The derived limits on the WIMP--nucleon cross section are the most stringent limits on spin--independent interactions obtained to date by using essentially raw data without background subtraction.Comment: 8 pages (latex) including 5 postscript figures and 2 tables. To appear in Phys. Rev. D, 15. December 199

Particle Dark Matter Physics: An Update

This write--up gives a rather elementary introduction into particle physics aspects of the cosmological Dark Matter puzzle. A fairly comprehensive list of possible candidates is given; in each case the production mechanism and possible ways to detect them (if any) are described. I then describe detection of the in my view most promising candidates, weakly interacting massive particles or WIMPs, in slightly more detail. The main emphasis will be on recent developments.Comment: Invited talk at the 5th Workshop on Particle Physics Phenomenology, Pune, India, January 1998; 21 pages, LaTeX with equation.st

Search for an annual modulation of dark-matter signals with a germanium spectrometer at the Sierra Grande Laboratory

Data collected during three years with a germanium spectrometer at the Sierra Grande underground laboratory have been analyzed for distinctive features of annual modulation of the signal induced by WIMP dark matter candidates. The main motivation for this analysis was the recent suggestion by the DAMA/NaI Collaboration that a yearly modulation signal could not be rejected at the 90% confidence level when analyzing data obtained with a high-mass low-background scintillator detector. We performed two different analyses of the data: First, the statistical distribution of modulation-significance variables (expected from an experiment running under the conditions of Sierra Grande) was compared with the same variables obtained from the data. Second, the data were analyzed in energy bins as an independent check of the first result and to allow for the possibility of a crossover in the expected signal. In both cases no statistically significant deviation from the null result was found, which could support the hypothesis that the data contain a modulated component. A plot is also presented to enable the comparison of these results to those of the DAMA collaboration.Comment: New version accepted by Astroparticle Physics. Changes suggested by the referee about the theoretical prediction of rates are included. Conclusions remain unaffected. 14 pages, LaTeX, 7 figures. Uses epsfig macr