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Degradation rates of organic phosphorus in lake sediment
Institute of Biology, University of Southern Denmark.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
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2007 (English)In: Biogeochemistry, ISSN 0168-2563, E-ISSN 1573-515X, Vol. 82, no 1, 15-28 p.Article in journal (Refereed) Published
Abstract [en]

Phosphorus (P) binding groups were identified in phytoplankton, settling particles, and sediment profiles by 31P NMR spectroscopy from the Swedish mesotrophic Lake Erken. The 31P NMR analysis revealed that polyphosphates and pyrophosphates were abundant in the water column, but rapidly mineralized in the sediment. Orthophosphate monoesters and teichoic acids degraded more slowly than DNA-P, polyphosphates, and P lipids. Humic acids and organic acids from phytoplankton were precipitated from the NaOH extract by acidification and identified by 31P NMR spectroscopy. The precipitated P was significantly more recalcitrant than the P compound groups remaining in solution, but does not constitute a major sink of P as it did not reach a stable concentration with depth, which indicates that it may eventually be degraded. Since P also precipitated from phytoplankton, the origin of humic-P can not be related solely to allochthonous P.

Place, publisher, year, edition, pages
2007. Vol. 82, no 1, 15-28 p.
Keyword [en]
Organic P, 31P NMR, Lake sediment, Degradation rates
National Category
Biological Sciences Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-97627DOI: 10.1007/s10533-006-9049-zISI: 000244070900002OAI: oai:DiVA.org:uu-97627DiVA: diva2:172645
Available from: 2008-10-15 Created: 2008-10-15 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Organic Phosphorus Compounds in Aquatic Sediments: Towards Molecular Identification with Mass Spectrometry
Open this publication in new window or tab >>Organic Phosphorus Compounds in Aquatic Sediments: Towards Molecular Identification with Mass Spectrometry
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Phosphorus (P) regulates trophic status in most aquatic systems. However, only bioavailable P contributes to primary production. In most lakes and shallow seas, mineralisation of sediment P into its bioavailable form and its release to the water column is important for maintaining primary production. Sediment organic P forms a substantial proportion of this P to be mineralised and can originate from different sources on land (farmland, forests, etc.) or from primary production in the lake. These organic P forms can thus be expected to have differing composition, degradability and recyclable P content.

Knowledge of the chemical structure of sediment organic P compounds is scarce, mainly due to lack of appropriate analytical techniques. The commonly used 31P-nuclear magnetic resonance (31P-NMR) technique, only identifies P binding groups, so a mass spectrometric (MS) analysis method was developed that allows individual sediment organic P compounds to be identified.

EDTA as pre-extractant resulted in the highest P yield in subsequent NaOH extraction. Extracted organic P compound groups were identified using 31P-NMR. For identification of specific P compounds with MS, a sample preparation method prior to electrospray tandem mass spectrometry (ESI-MS/MS) analysis was developed. Liquid chromatography (LC) with porous graphitic carbon prior to ESI-MS/MS enhanced sensitivity and selectivity, enabling several of the ions detected to be identified as nucleotides. 31P-NMR analysis showed P monoesters to be the most stabile P compounds throughout a lake sediment profile. The developed LC-ESI-MS/MS analysis method revealed that some monoester-P (nucleotides) were labile, while other P compounds increased in concentration with Baltic Sea sediment depth and were therefore considered stabile. Differences in patterns of P compounds detected were also shown depending on catchment characteristics in relation to Baltic Sea sediment age.

For cost-effective management of eutrophication, knowledge of the sources of degradable organic P forms, contributing to internal loading, is needed. This thesis showed the developed LC-ESI-MS/MS analysis method to be a powerful analytical tool for this purpose.

Place, publisher, year, edition, pages
Uppsala: Universitetsbiblioteket, 2008. 58 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 560
Keyword
electrospray ionisation, mass spectrometry, liquid chromatography, organic phosphorus, aquatic sediment, eutrophication, sample preparation, extraction
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:uu:diva-9319 (URN)978-91-554-7306-8 (ISBN)
Public defence
2008-11-07, B42, BMC, Husargatan 3, Uppsala, Sweden, 10:15
Opponent
Supervisors
Available from: 2008-10-15 Created: 2008-10-15 Last updated: 2010-08-16Bibliographically approved
2. Organic Phosphorus Compounds in Aquatic Sediments: Analysis, Abundance and Effects
Open this publication in new window or tab >>Organic Phosphorus Compounds in Aquatic Sediments: Analysis, Abundance and Effects
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Phosphorus (P) is often the limiting nutrient in lacustrine and brackish eco-systems, and enhanced input of P into an aquatic system might therefore negatively impact the environment. Because modern waste water manage-ment have reduced external P input to surface waters, internal P loading from the sediment has become one of the main P sources to aquatic ecosys-tems, in which relatively unknown organic P compounds seem to be more active in P recycling than previously thought.

This thesis focus is on improving analysis methods for organic P com-pounds in lacustrine and brackish sediments, as well as determining which of these compounds might be degraded, mobilized and subsequently recycled to the water column and on what temporal scale this occur. In both lacustrine and brackish environments, the most labile P compound was pyrophosphate, followed by different phosphate diesters. Phosphate monoesters were the least labile organic P compounds and degraded the slowest with sediment depth. In regulated lakes, it was shown that pyrophosphate and polyphos-phate compound groups were most related to lake trophic status, thus indi-cating their involvement in P cycling. This thesis also indicates faster P turn-over in sediment from the brackish environment compared to sediment from the lacustrine environment.

A comparison of organic P extraction procedures showed that pre-extraction with EDTA, and NaOH as main extractant, was most efficient for total P extraction. Using buffered sodium dithionite (BD) as a pre-extractant and NaOH as main extractant was most efficient for extracting the presuma-bly most labile organic P compound groups, pyrophosphate and polyphos-phate. Furthermore, it was determined that organic P compounds associated with humic substances were more recalcitrant than other P compounds, that the BD step used in traditional P fractionation might extract phosphate monoesters, and that NMR is a statistically valid method for quantification of organic P compounds in sediment extracts.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2006. 57 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 160
Keyword
Environmental chemistry, Organic phosphorus, aquatic sediment, eutrophication, NMR, internal loading, sample preparation, extraction, degradation, Miljökemi
National Category
Environmental Sciences
Identifiers
urn:nbn:se:uu:diva-6701 (URN)91-554-6508-0 (ISBN)
Public defence
2006-04-21, B41, BMC, Husargatan 3, Uppsala, 10:00
Opponent
Supervisors
Available from: 2006-03-31 Created: 2006-03-31 Last updated: 2011-06-10Bibliographically approved

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