Journal of Soils and Sediments

, Volume 12, Issue 6, pp 909–920

Characterization and optimization of the preparation procedure for solution P-31 NMR analysis of organic phosphorus in sediments

  • Di Xu
  • Shiming Ding
  • Bin Li
  • Fei Jia
  • Xiang He
  • Chaosheng Zhang
SEDIMENTS, SEC 1 · SEDIMENT QUALITY AND IMPACT ASSESSMENT · RESEARCH ARTICLE
  • 301 Downloads

Abstract

Purpose

The single-step sodium hydroxide–ethylenediaminetetraacetic acid (NaOH–EDTA) extraction is currently the most common preparation technique for the measurement of organic phosphorus (P) composition in sediments using solution 31P nuclear magnetic resonance (NMR). In this study, detailed investigations were conducted to evaluate the performance of this technique, with an objective of finding an optimal procedure for the measurement of sediment organic P.

Materials and methods

A single-step extraction with NaOH–EDTA was investigated on two types of sediment, i.e., Fe/Al-rich sediment and calcareous sediment. The influence of different sediment preparation methods, NaOH–EDTA compositions, solid:solution ratios, extraction time, pre-concentration techniques, and NMR sample frozen storage time on P extraction and solution 31P NMR analysis were investigated.

Results and discussion

Both air- and freeze-drying increased organic P extraction for the calcareous sediment. An extraction time of 16 h was sufficient for quantitative recovery of extracted organic P for both Fe/Al-rich and calcareous sediments. The use of a 1:8 solid:solution ratio achieved stronger NMR signals and greater P diversity than the use of a 1:20 ratio. Extraction of the two sediments with 0.25 NaOH–50 mM EDTA favored 31P NMR detection by reducing the relaxation times required and the risk of organic P degradation compared to the use of stronger NaOH–EDTA solutions. Rotary evaporation was a better technique for pre-concentration of the NaOH–EDTA extracts than freeze drying. The concentrated extracts could be preserved by freezing (−20 °C) for at least 2 months.

Conclusions

An optimized procedure was developed based on these investigations, including freeze-drying of fresh sediments, extraction with 0.25 M NaOH–50 mM EDTA for 16 h using a solid:solution ratio of 1:8, pre-concentration of the extract to the level of ∼10 times of its original concentration using rotary evaporation, and storage of the NMR sample at −20 °C until 31P NMR analysis.

Keywords

Composition Extraction Phosphorus-31 nuclear magnetic resonance Phosphorus speciation NMR Sediment 

Supplementary material

11368_2012_510_MOESM1_ESM.doc (920 kb)
ESM 1(DOC 919 kb)

References

  1. Ahlgren J, Tranvik L, Gogoll A, Waldeback M, Markides K, Rydin E (2005) Sediment depth attenuation of biogenic phosphorus compounds measured by P-31 NMR. Environ Sci Technol 39:867–872CrossRefGoogle Scholar
  2. Ahlgren J, Reitzel K, Tranvik L, Gogoll A, Rydin E (2006) Degradation of organic phosphorus compounds in anoxic Baltic Sea sediments: A P-31 nuclear magnetic resonance study. Limnol Oceanogr 51:2341–2348CrossRefGoogle Scholar
  3. Bai XL, Ding SM, Fan CX, Liu T, Shi D, Zhang L (2009) Organic phosphorus species in surface sediments of a large, shallow, eutrophic lake, Lake Taihu, China. Environ Pollut 157:2507–2513CrossRefGoogle Scholar
  4. Bai XL, Zhou YK, Li B, Ding SM (2011) Optimizing chemical extraction of organic phosphorus from sediment using 31P nuclear magnetic resonance spectroscopy. Acta Sci Circumstantiae 31:996–1003Google Scholar
  5. Bowman RA, Moir JO (1993) Basic EDTA as an extractant for soil organic phosphorus. Soil Sci Soc Am J 57:1516–1518CrossRefGoogle Scholar
  6. Brandes JA, Ingall E, Paterson D (2007) Characterization of minerals and organic phosphorus species in marine sediments using soft X-ray fluorescence spectromicroscopy. Mar Chem 103:250–265CrossRefGoogle Scholar
  7. Cade-Menun BJ (2005) Characterizing phosphorus in environmental and agricultural samples by P-31 nuclear magnetic resonance spectroscopy. Talanta 66:359–371CrossRefGoogle Scholar
  8. Cade-Menun BJ, Preston CM (1996) A comparison of soil extraction procedures for P-31 NMR spectroscopy. Soil Sci 161:770–785CrossRefGoogle Scholar
  9. Cade-Menun BJ, Benitez-Nelson CR, Pellechia P, Paytan A (2005) Refining P-31 nuclear magnetic resonance spectroscopy for marine particulate samples: storage conditions and extraction recovery. Mar Chem 97:293–306CrossRefGoogle Scholar
  10. Cade-Menun BJ, Navaratnam JA, Walbridge MR (2006) Characterizing dissolved and particulate phosphorus in water with P-31 nuclear magnetic resonance spectroscopy. Environ Sci Technol 40:7874–7880CrossRefGoogle Scholar
  11. Carman R, Edlund G, Damberg C (2000) Distribution of organic and inorganic phosphorus compounds in marine and lacustrine sediments: a P-31 NMR study. Chem Geol 163:101–114CrossRefGoogle Scholar
  12. Cooper WT, Llewelyn JM, Bennett GL, Salters VJM (2005) Mass spectrometry of natural organic phosphorus. Talanta 66:348–358CrossRefGoogle Scholar
  13. De Brabandere H, Forsgard N, Israelsson L, Petterson J, Rydin E, Waldeback M, Sjoberg PJR (2008) Screening for organic phosphorus compounds in aquatic sediments by liquid chromatography coupled to ICP-AES and ESI-MS/MS. Anal Chem 80:6689–6697CrossRefGoogle Scholar
  14. Ding SM, Bai XL, Fan CX, Zhang L (2010a) Caution needed in pretreatment of sediments for refining phosphorus-31 nuclear magnetic resonance analysis: results from a comprehensive assessment of pretreatment with ethylenediaminetetraacetic acid. J Environ Qual 39:1668–1678CrossRefGoogle Scholar
  15. Ding SM, Xu D, Li B, Fan CX, Zhang CS (2010b) Improvement of P-31 NMR spectral resolution by 8-hydroxyquinoline precipitation of paramagnetic Fe and Mn in environmental samples. Environ Sci Technol 44:2555–2561CrossRefGoogle Scholar
  16. El-Rifai H, Heerboth M, Gedris TE, Newman S, Orem W, Cooper WT (2008) NMR and mass spectrometry of phosphorus in wetlands. Eur J Soil Sci 59:517–525CrossRefGoogle Scholar
  17. He ZQ, Cade-Menun BJ, Toor GS, Fortuna AM, Honeycutt CW, Sims JT (2007) Comparison of phosphorus forms in wet and dried animal manures by solution phosphorus-31 nuclear magnetic resonance spectroscopy and enzymatic hydrolysis. J Environ Qual 36:1086–1095CrossRefGoogle Scholar
  18. Hill JE, Cade-Menun BJ (2009) Phosphorus-31 nuclear magnetic resonance spectroscopy transect study of poultry operations on the delmarva peninsula. J Environ Qual 38:130–138CrossRefGoogle Scholar
  19. Hupfer M, Gachter R, Rüegger HR (1995) Polyphosphate in lake sediments: P-31 NMR spectroscopy as a tool for its identification. Limnol Oceanogr 40:610–617CrossRefGoogle Scholar
  20. Hupfer M, Rube B, Schmieder P (2004) Origin and diagenesis of polyphosphate in lake sediments: a P-31 NMR study. Limnol Oceanogr 49:1–10CrossRefGoogle Scholar
  21. Liu JY, Wang H, Yang HJ, Ma YJ, Cai OC (2009) Detection of phosphorus species in sediments of artificial landscape lakes in China by fractionation and phosphorus-31 nuclear magnetic resonance spectroscopy. Environ Pollut 157:49–56CrossRefGoogle Scholar
  22. Lukkari K, Hartikainen H, Leivuori M (2007) Fractionation of sediment phosphorus revisited. I: fractionation steps and their biogeochemical basis. Limnol Oceanogr Meth 5:433–444CrossRefGoogle Scholar
  23. McDowell RW (2009) Effect of land use and moisture on phosphorus forms in upland stream beds in South Otago, New Zealand. Mar Freshw Res 60:619–625CrossRefGoogle Scholar
  24. McDowell RW, Stewart I (2005) Phosphorus in fresh and dry dung of grazing dairy cattle, deer, and sheep: sequential fraction and phosphorus-31 nuclear magnetic resonance analyses. J Environ Qual 34:598–607CrossRefGoogle Scholar
  25. McDowell RW, Stewart I, Cade-Menun BJ (2006) An examination of spin–lattice relaxation times for analysis of soil and manure extracts by liquid state phosphorus-31 nuclear magnetic resonance spectroscopy. J Environ Qual 35:293–302CrossRefGoogle Scholar
  26. McDowell RW, Cade-Menun BJ, Stewart I (2007a) Organic phosphorus speciation and pedogenesis: analysis by solution P-31 nuclear magnetic resonance spectroscopy. Eur J Soil Sci 58:1348–1357CrossRefGoogle Scholar
  27. McDowell RW, Scott JT, Stewart I, Condron LM (2007b) Influence of aggregate size on phosphorus changes in a soil cultivated intermittently: analysis by P-31 nuclear magnetic resonance. Biol Fertil Soils 43:409–415CrossRefGoogle Scholar
  28. Monbet P, McKelvie ID, Saefumillah A, Worsfold PJ (2007) A protocol to assess the enzymatic release of dissolved organic phosphorus species in waters under environmentally relevant conditions. Environ Sci Technol 41:7479–7485CrossRefGoogle Scholar
  29. Murphy J, Riley JP (1962) A modified single solution method for determination of phosphate in natural waters. Anal Chim Acta 26:31–36CrossRefGoogle Scholar
  30. Murphy PNC, Bell A, Turner BL (2009) Phosphorus speciation in temperate basaltic grassland soils by solution P-31 NMR spectroscopy. Eur J Soil Sci 60:638–651CrossRefGoogle Scholar
  31. Newman RH, Tate KR (1980) Soil phosphorus characterisation by 31P nuclear magnetic resonance. Communic Soil Sci Plant Anal 11:35–842Google Scholar
  32. Paytan A, Cade-Menun BJ, McLaughlin K, Faul KL (2003) Selective phosphorus regeneration of sinking marine particles: evidence from P-31 NMR. Mar Chem 82:55–70CrossRefGoogle Scholar
  33. Reitzel K, Ahlgren J, Gogoll A, Jensen HS, Rydin E (2006a) Characterization of phosphorus in sequential extracts from lake sediments using P-31 nuclear magnetic resonance spectroscopy. Can J Fish Aquat Sci 63:1686–1699CrossRefGoogle Scholar
  34. Reitzel K, Ahlgren J, Gogoll A, Rydin E (2006b) Effects of aluminum treatment on phosphorus, carbon, and nitrogen distribution in lake sediment: a P-31 NMR study. Water Res 40:647–654CrossRefGoogle Scholar
  35. Reitzel K, Jensen HS, Flindt M, Andersen FO (2009) Identification of dissolved nonreactive phosphorus in freshwater by precipitation with aluminum and subsequent P-31 NMR analysis. Environ Sci Technol 43:5391–5397CrossRefGoogle Scholar
  36. Ruban V, Lopez-Sanchez JF, Pardo P, Rauret G, Muntau H, Quevauviller P (1999) Selection and evaluation of sequential extraction procedures for the determination of phosphorus forms in lake sediment. J Environ Monit 1:51–56CrossRefGoogle Scholar
  37. Ruttenberg KC, Ogawa NO, Tamburini F, Briggs RA, Colasacco ND, Joyce E (2009) Improved, high-throughput approach for phosphorus speciation in natural sediments via the SEDEX sequential extraction method. Limnol Oceanogr Meth 7:319–333CrossRefGoogle Scholar
  38. Rydin E (2000) Potentially mobile phosphorus in Lake Erken sediment. Water Res 34:2037–2042CrossRefGoogle Scholar
  39. Sparling GP, Whale KN, Ramsay AJ (1985) Quantifying the contribution from the soil microbial biomass to the extractable P levels of fresh and air-dried soils. Aust J Soil Res 23:613–621CrossRefGoogle Scholar
  40. Sundareshwar PV, Morris JT, Pellechia PJ, Cohen HJ, Porter DE, Jones BC (2001) Occurrence and ecological implications of pyrophosphate in estuaries. Limnol Oceanogr 46:1570–1577CrossRefGoogle Scholar
  41. Turner BL (2004) Optimizing phosphorus characterization in animal manures by solution phosphorus-31 nuclear magnetic resonance spectroscopy. J Environ Qual 33:757–766CrossRefGoogle Scholar
  42. Turner BL (2008) Soil organic phosphorus in tropical forests: an assessment of the NaOH-EDTA extraction procedure for quantitative analysis by solution P-31 NMR spectroscopy. Eur J Soil Sci 59:453–466CrossRefGoogle Scholar
  43. Turner BL, Leytem AB (2004) Phosphorus compounds in sequential extracts of animal manures: chemical speciation and a novel fractionation procedure. Environ Sci Technol 38:6101–6108CrossRefGoogle Scholar
  44. Turner BL, Weckström K (2009) Phytate as a novel phosphorus-specific paleo-indicator in aquatic sediments. J Paleolimnol 42:391–400CrossRefGoogle Scholar
  45. Turner BL, Mahieu N, Condron LM (2003) Phosphorus-31 nuclear magnetic resonance spectral assignments of phosphorus compounds in soil NaOH–EDTA extracts. Soil Sci Soc Am J 67:497–510CrossRefGoogle Scholar
  46. Turner BL, Cade-Menun BJ, Condron LM, Newman S (2005) Extraction of soil organic phosphorus. Talanta 66:294–306CrossRefGoogle Scholar
  47. Turner BL, Newman S, Cheesman AW, Reddy KR (2007) Sample pretreatment and phosphorus speciation in wetland soils. Soil Sci Soc Am J 71:1538–1546CrossRefGoogle Scholar
  48. Zhang RY, Wu FC, He ZQ, Zheng JA, Song BA, Jin LH (2009) Phosphorus composition in sediments from seven different trophic lakes, China: a phosphorus-31 NMR study. J Environ Qual 38:353–359CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  • Di Xu
    • 1
  • Shiming Ding
    • 1
  • Bin Li
    • 2
  • Fei Jia
    • 3
  • Xiang He
    • 1
  • Chaosheng Zhang
    • 4
  1. 1.State Key Laboratory of Lake Science and EnvironmentNanjing Institute of Geography and Limnology, Chinese Academy of SciencesNanjingPeople’s Republic of China
  2. 2.College of Forest Resources and EnvironmentNanjing Forestry UniversityNanjingPeople’s Republic of China
  3. 3.College of Environmental Science and EngineeringHohai UniversityNanjingChina
  4. 4.GIS Centre, Ryan Institute and School of Geography and ArchaeologyNational University of IrelandGalwayIreland

Personalised recommendations