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| 2. |
- Ahlgren, Joakim, 1972-
(författare)
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Organic Phosphorus Compounds in Aquatic Sediments : Analysis, Abundance and Effects
- 2006
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 3. |
- Ahlgren, Joakim, et al.
(författare)
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Sediment Depth Attenuation of Biogenic Phosphorus Compounds Measured by 31P NMR
- 2005
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Ingår i: Environmental Science and Technology. - Univ Uppsala, Dept Analyt Chem, SE-75124 Uppsala, Sweden. Univ Uppsala, Dept Ecol & Evolut, Uppsala, Sweden. Univ Uppsala, Dept Organ Chem, SE-75124 Uppsala, Sweden. : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 39:3, s. 867-872
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Tidskriftsartikel (refereegranskat)abstract
- Being a major cause of eutrophication and subsequent loss of water quality, the turnover of phosphorus (P) in lake sediments is in need of deeper understanding. A major part of the flux of P to eutrophic lake sediments is organically bound or of biogenic origin. This P is incorporated in a poorly described mixture of autochthonous and allochthonous sediment and forms the primary storage of P available for recycling to the water column, thus regulating lake trophic status. To identify and quantify biogenic sediment P and assess its lability, we analyzed sediment cores from Lake Erken, Sweden, using traditional P fractionation, and in parallel, NaOH extracts were analyzed using 31P NMR. The surface sediments contain orthophosphates (ortho-P) and pyrophosphates (pyro-P), as well as phosphate mono- and diesters. The first group of compounds to disappear with increased sediment depth is pyrophosphate, followed by a steady decline of the different ester compounds. Estimated half-life times of these compound groups are about 10 yr for pyrophosphate and 2 decades for mono- and diesters. Probably, these compounds will be mineralized to ortho-P and is thus potentially available for recycling to the water column, supporting further growth of phytoplankton. In conclusion, 31P NMR is a useful tool to asses the bioavailability of certain P compound groups, and the combination with traditional fractionation techniques makes quantification possible.
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| 4. |
- Ahlgren, Joakim, et al.
(författare)
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Sediment Phosphorus Extractants for Phosphorus-31 Nuclear Magnetic Resonance Analysis : A Quantitative Evaluation
- 2007
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Ingår i: Journal of Environmental Quality. - Uppsala Univ, Dept Phys & Analyt Chem, S-75124 Uppsala, Sweden. Univ So Denmark, Inst Biol, DK-5230 Odense M, Denmark. Uppsala Univ, Dept Biochem & Organ Chem, S-75124 Uppsala, Sweden. Uppsala Univ, Dept Ecol & Evolut, S-75123 Uppsala, Sweden. : Wiley. - 0047-2425 .- 1537-2537. ; 36:3, s. 892-898
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Tidskriftsartikel (refereegranskat)abstract
- The influence of pre-extractant, extractant, and post-extractant on total extracted amounts of P and organic P compound groups measured with 31P nuclear magnetic resonance (31P-NMR) in lacustrine sediment was examined. The main extractants investigated were sodium hydroxide (NaOH) and sodium hydroxide ethylenediaminetetraacetic acid (NaOH-EDTA) with bicarbonate buffered dithionite (BD) or EDTA as pre-extractants. Post extractions were conducted using either NaOH or NaOH-EDTA, depending on the main extractant. Results showed that the most efficient combination of extractants for total P yield was NaOH with EDTA as pre-extractant, yielding almost 50% more than the second best procedure. The P compound groups varying the most between the different extraction procedures were polyphosphates and pyrophosphates. NaOH with BD as pre-extractant was the most efficient combination for these compound groups.
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| 5. |
- De Brabandere, Heidi, 1980-
(författare)
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Organic Phosphorus Compounds in Aquatic Sediments : Towards Molecular Identification with Mass Spectrometry
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 6. |
- De Brabandere, Heidi, et al.
(författare)
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Screening for Organic Phosphorus Compounds in Aquatic Sediments by Liquid Chromatography Coupled to ICP-AES and ESI-MS/MS
- 2008
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Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 80:17, s. 6689-6697
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Tidskriftsartikel (refereegranskat)abstract
- The structures of organic phosphorous (P) compounds in aquatic sediments are to a large extent unknown although these compounds are considered to play an important role in regulating lake trophic status. To enhance identification of these compounds, a liquid chromatography (LC) method for their separation was developed. The stationary phase was porous graphitic carbon (PGC), and the mobile phases used in the gradient elution were compatible with both inductive coupled plasma atomic emission spectroscopy (ICP-AES) and electrospray ionization tandem mass spectrometry (ESI-MS/MS). With LC-ICP-AES, eight different P containing peaks could be observed in the P chromatogram indicating that at least eight different P compounds were separated. With the setup of an information dependent acquisition (IDA) with ESI-MS/MS, the mass over charge (m/z) of compounds containing a phosphate group (H2PO3−, m/z 97) could be measured and further fragmentation experiments gave additional information on the structure of almost 40 separated P compounds, several were verified to be nucleotides. ICP-AES was very suitable in the development of the LC method and allowed screening and quantification of P compounds. The presented LC-ESI-MS/MS technique was able to identify several sediment organic P compounds.
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| 7. |
- De Brabandere, Heidi, et al.
(författare)
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Sediment extraction and clean-up for organic phosphorus analysis by electrospray ionization tandem mass spectrometry
- 2008
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Ingår i: Talanta. - : Elsevier BV. - 0039-9140 .- 1873-3573. ; 74:5, s. 1175-1183
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Tidskriftsartikel (refereegranskat)abstract
- A method to prepare NaOH sediment extracts for organic P compound analysis with electrospray ionization tandem mass spectrometry (ESI-MS-MS) was developed on natural samples. Ion exchange, rotary evaporation and mass cut-off filtering proved to be suitable for sample preparation. Samples were analyzed with ESI-MS-MS, and reproducibility and repeatability of the method was calculated. In addition, 31P-nuclear magnetic resonance spectroscopy (31P NMR) was used to measure recovery of different P compound groups such as orthophosphate (Ortho-P), orthophosphate monoesters (Monoester-P), orthophosphate diesters (Diester-P) and pyrophosphates (Pyro-P). The developed sample preparation method resulted in an easy-to-spray liquid for the ESI-MS-MS instrumentation. The overall P recovery was 65% and 31P NMR showed that Diester-P, possibly in the form of DNA, was apparently lost through the filtering step most likely due to their size. Variances in the total intensities of the MS scans (relative standard deviation (R.S.D.) 35–54%) were for about 50% due to repeated MS runs. Covariances of the peaks in the MS spectra were calculated to be for about 30% due to the sample preparation procedure. Finally, with the ESI-MS-MS approach, 11 peaks in the mass spectra were found likely to represent phosphate containing compounds.
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| 8. |
- Isaac, Giorgis, 1974-
(författare)
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Development of Enhanced Analytical Methodology for Lipid Analysis from Sampling to Detection : A Targeted Lipidomics Approach
- 2005
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis covers a wide range of analytical method development for lipid analysis in complex biological samples; from sample preparation using pressurized fluid extraction (PFE) and separation with reversed phase capillary liquid chromatography (RP-LC) to detection by electrospray ionization mass spectrometry (ESI/MS) and tandem MS.The requirements for fast, reliable and selective extraction methods with minimal usage of solvents have accelerated the development of new extraction techniques. PFE is one of the new automated, fast and efficient liquid extraction techniques which use elevated temperature and pressure with standard liquid solvents. In this thesis the reliability and efficiency of the PFE technique was investigated for the extraction of total lipid content from cod, herring muscle and human brain tissue as well as for pesticides from fatty foodstuffs. Improved or comparable efficiencies were achieved with reduced time and solvent consumption as compared to traditional methods. A RP-LC coupled online to ESI/MS for the analysis of phosphatidylcholine (PC) and sphingomyelin (SM) molecular species was developed and used for the analysis of brain lipids from eight groups of mice treated with vehicle and various neuroleptics. The effect of postnatal iron administration in lipid composition and behavior was investigated. Whether or not these effects could be altered by subchronic administration of the neuroleptics (clozapine and haloperidol) were examined. The results support the hypothesis that an association between psychiatric disorders, behavior abnormalities and lipid membrane constitution in the brain exists.Finally, a tandem MS precursor ion scan was used to analyze the developmental profile of brain sulfatide accumulation in arylsulfatase A (ASA) deficient (ASA -/-) as compared to wild type control (ASA +/+) mice. The ASA -/- mice were developed as a model of the monogenic disease metachromatic leukodystrophy with an established deficiency of the lysosomal enzyme ASA. The results showed that an alteration in the composition of sulfatide molecular species was observed between the ASA -/- and ASA +/+ mice.This thesis shows that modern analytical methods can provide new insights in the extraction and analysis of lipids from complex biological samples.
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| 9. |
- Isaac, Giorgis, et al.
(författare)
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Total Lipid Extraction of Homogenized and Intact Lean Fish Muscles Using Pressurized Fluid Extraction and Batch Extraction Technique
- 2005
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Ingår i: Journal of Agricultural and Food Chemistry. - : American Chemical Society (ACS). - 0021-8561 .- 1520-5118. ; 53:14, s. 5506-5512
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Tidskriftsartikel (refereegranskat)abstract
- The reliability and efficiency of pressurized fluid extraction (PFE) technique for the extraction of total lipid content from cod and the effect of sample treatment on the extraction efficiency have been evaluated. The results were compared with two liquid-liquid extraction methods, traditional and modified methods according to Jensen. Optimum conditions were found to be with 2-propanol/n-hexane (65:35, v/v) as a first and n-hexane/diethyl ether (90:10, v/v) as a second solvent, 115 oC, and 10 min of static time. PFE extracts were cleaned up using the same procedure as in the methods according to Jensen. When total lipid yields obtained from homogenized cod muscle using PFE were compared yields obtained with original and modified Jensen methods, PFE gave significantly higher yields, ~10% higher (t test, P < 0.05). Infrared and NMR spectroscopy suggested that the additional material that inflates the gravimetric results is rather homogeneus and is primarily consists of phospholipid with headgroups of inositidic and/or glycosidic nature. The comparative study demonstrated that PFE is an alternative suitable technique to extract total lipid content from homogenized cod (lean fish) and herring (fat fish) muscle showing a precision comparable to that obtained with the traditional and modified Jensen methods. Despite the necessary cleanup step, PFE showed important advantages in the solvent consumption was cut by ~50% and automated extraction was possible.
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| 10. |
- Reitzel, Kasper, et al.
(författare)
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Degradation rates of organic phosphorus in lake sediment
- 2007
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Ingår i: Biogeochemistry. - Univ So Denmark, Inst Biol, DK-5230 Odense M, Denmark. Uppsala Univ, Dept Analyt Chem, S-75124 Uppsala, Sweden. Uppsala Univ, Dept Organ Chem, S-75124 Uppsala, Sweden. Uppsala Univ, Dept Limnol, S-75236 Uppsala, Sweden. : Springer Science and Business Media LLC. - 0168-2563 .- 1573-515X. ; 82:1, s. 15-28
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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