Brandes,J.A., Ingall,E. and Paterson,D.(2007): Characterization of minerals and organic phosphorus species in marine sediments using soft X-ray fluorescence spectromicroscopy. Marine Geology, 103, 250-265.

『軟X線蛍光分光顕微鏡法を用いた海洋堆積物中の鉱物と有機リンの特長づけ』


Abstract
 Phosphorus Near Edge X-ray Fluorescence Spectroscopy (P-NEXFS) data were collected on phosphorus containing phases including organic and inorganic compounds and minerals. Although phases containing P in the plus five oxidation state P(V) in a tetrahedral PO4 structure have similar primary fluorescence peak positions, the size, shape, and positions of secondary spectral features are diagnostic for different compounds and minerals. In particular, calcium phosphates exhibited a notable post-peak shoulder at 2154.5 eV, while oxidized iron phosphates had a distinctive pre-peak feature at 2148 eV. Polyphosphates have a broad secondary peak located approximately 2 eV higher in energy than a similar feature in phosphate esters and diesters. Compounds containing P(V) in structures other than PO4 tetrahedral such as phosphonates have a primary peak shifted about 1 eV lower than corresponding organo-phosphates. Organo-phosphates with P in the plus three oxidation state P(III) such as phosphines had primary fluorescence peaks shifted still further down in energy (2-3 eV). The substitution of aromatic carbon groups in close proximity to P structures in organic compounds generated both pre- and post-peak features as well as a number of secondary peaks. In addition, X-ray fluorescence mapping of P, Si, Al,Mg, and Na was conducted on a marine sediment sample with sub-micron spatial resolution. Phosphorus was heterogeneously distributed in the sample and not correlated on a broad scale with any other element examined. Much of the P present in the sample was located in small, 0.6-8μm size, P-rich domains. Several P-rich regions were examined with P-NEXFS using a focused beam with 60 nm resolution and were found to consist of either calcium phosphate or polyphosphate phases. The presence of significant polyphosphate-dominated regions in a marine sediment sample supports the present observations that such phases can play an important role in marine P cycling. The combination of fluorescence mapping and P-NEXFS data collection on fine particles provides a powerful new tool for environmental phosphorus studies.

Keywords: Phosphorus; X-ray microscopy; Spectroscopy; Apatite; Polyphosphate; Phosphonate; Marine sediments』

1. Introduction
2. Methods
3. Results
 3.1. Minerals
 3.2. Inorganic compounds
 3.3. Organic compounds
 3.4. Effingham Inlet surface sediment
4. Discussion
5. Conclusions
Acknowledgements
Appendix A. Supplementary data
References


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