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Enhanced methods for conditioning, storage, and extraction of liquid and solid samples of manure for determination of steroid hormones by solid-phase extraction and gas chromatography–mass spectrometry

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Abstract

Hormones are among the highest-impact endocrine disrupters affecting living organisms in aquatic environments. These molecules have been measured in both wastewater and sewage sludge. Analytical techniques for such matrices are well described in the literature. In contrast, there is little information about the analysis of hormones in animal waste. The objectives of this study were, first, to propose a method for conditioning swine manure samples (addition of formaldehyde, separation of the solid and liquid phases, and duration of storage) in order to determine hormones in the liquid fraction of manure by solid-phase extraction (SPE) coupled with gas chromatography–mass spectrometry (GC–MS). Our results showed that analysis of hormones was affected by matrix changes which occurred during freezing and thawing and after addition of formaldehyde, an additive frequently used to preserve environmental samples. Thus, our results argue for the conditioning of samples without formaldehyde and for separating the solid and liquid fractions of manure before freezing. Second, this study reports on the use of a liquid extraction method coupled with SPE and GC–MS analysis for determination of hormones in the solid fraction of manure. Under the conditions selected, hormone recoveries were between 80 and 100%. Finally, the optimized method was used to quantify hormones in both liquid and solid fractions of swine manure from different breeding units. High levels of estrone and α-estradiol were found in samples whereas β-estradiol was detected in smaller amounts. Estriol and progesterone were mainly found in manure from the gestating sow building whereas testosterone was detected in manure from male breeding buildings.

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References

  1. McLachlan JA (2001) Endocr Rev 22:319–341

    Article  CAS  Google Scholar 

  2. Purdom, CE, Hardiman, PA, Bye, VJ, Eno, NC, Tyler, CR, Sumpter, JP (1994) 8:275–285

  3. Sumpter JP (1995) Toxicol Lett 82–3:737–742

    Article  Google Scholar 

  4. Thorpe KL, Cummings RI, Hutchinson TH, Scholze M, Brighty G, Sumpter JP, Tyler CR (2003) Environ Sci Technol 37:1142–1149

    Article  CAS  Google Scholar 

  5. Desbrow C, Routledge EJ, Brighty GC, Sumpter JP, Waldock M (1998) Environ Sci Technol 32:1549–1558

    Article  CAS  Google Scholar 

  6. Hanselman TA, Graetz DA, Wilkie AC (2003) Environ Sci Technol 37:5471–5478

    Article  CAS  Google Scholar 

  7. Johnson AC, Belfroid A, Di Corcia A (2000) Sci Total Environ 256:163–173

    Article  CAS  Google Scholar 

  8. Johnson AC, Williams RJ (2004) Environ Sci Technol 38:3649–3658

    Article  CAS  Google Scholar 

  9. Sarmah AK, Northcott GL, Leusch FDL, Tremblay LA (2006) Sci Total Environ 355:135–144

    Article  CAS  Google Scholar 

  10. Muller M, Rabenoelina F, Balaguer P, Patureau D, Lemenach K, Budzinski H, Barcelo D, De Alda ML, Kuster M, Delgenes JP, Hernandez-Raquet G (2008) Sci Toxicol Chem 27:1649–1658

    Article  CAS  Google Scholar 

  11. D'Ascenzo G, Di Corcia A, Gentili A, Mancini R, Mastropasqua R, Nazzari M, Samperi R (2003) Sci Total Environ 302:199–209

    Article  Google Scholar 

  12. Belfroid AC, Van der Horst A, Vethaak AD, Schafer AJ, Rijs GBJ, Wegener J, Cofino WP (1999) Sci Total Environ 225:101–108

    Article  CAS  Google Scholar 

  13. Combalbert S, Hernandez-Raquet G (2010) Appl Microbiol Biotechnol 86:1671–1692

    Article  CAS  Google Scholar 

  14. Ternes TA, Stumpf M, Mueller J, Haberer K, Wilken RD, Servos M (1999) Sci Total Environ 225:81–90

    Article  CAS  Google Scholar 

  15. Johnson AC, Aerni HR, Gerritsen A, Gibert M, Giger W, Hylland K, Jurgens M, Nakari T, Pickering A, Suter MJF, Svenson A, Wettstein FE (2005) Water Res 39:47–58

    Article  CAS  Google Scholar 

  16. Andersen H, Siegrist H, Halling-Sorensen B, Ternes TA (2003) Environ Sci Technol 37:4021–4026

    Article  CAS  Google Scholar 

  17. Johnson AC, Williams RJ, Matthiessen P (2006) Sci Total Environ 362:166–178

    Article  CAS  Google Scholar 

  18. Lange, IG, Daxenberger, A, Schiffer, B, Witters, H, Ibarreta, D, Meyer, HHD (2002) 473:27–37

  19. Burnison, BK, Hartmann, A, Lister, A, Servos, MR, Ternes, T, Van der Kraak, G (2003) 22:2243–2250

  20. Fine DD, Breidenbach GP, Price TL, Hutchins SR (2003) J Chromatogr A 1017:167–185

    Article  CAS  Google Scholar 

  21. Hutchins SR, White MV, Hudson FM, Fine DD (2007) Environ Sci Technol 41:738–744

    Article  CAS  Google Scholar 

  22. Kolodziej EP, Harter T, Sedlak DL (2004) Environ Sci Technol 38:6377–6384

    Article  CAS  Google Scholar 

  23. Kjaer, J, Olsen, P, Bach, K, Barlebo, HC, Ingerslev, F, Hansen, M, Sorensen, BH (2007) 41:3911–3917

  24. Busheé, EL, Edwards, DR, Moore, PA (1998) 41:1035–1041

  25. Bromberg, L, Temchenko, M (1999) 15:8627–8632

  26. Lai KM, Johnson KL, Scrimshaw MD, Lester JN (2000) Environ Sci Technol 34:3890–3894

    Article  CAS  Google Scholar 

  27. Lee, LS, Strock, TJ, Sarmah, AK, Rao, PSC (2003) 37:4098–4105

  28. Hanselman TA, Graetz DA, Wilkie AC (2004) J Environ Qual 33:1919–1923

    Article  CAS  Google Scholar 

  29. Hanselman TA, Graetz DA, Wilkie AC, Szabo NJ, Diaz CS (2006) J Environ Qual 35:695–700

    Article  CAS  Google Scholar 

  30. Raman, DR, Layton, AC, Moody, LB, Easter, JP, Sayler, GS, Burns, RT, Mullen, MD (2001) 44:1881–1888

  31. Shore, LS, Harel-Markowitz, E, Gurevich, M, Shemesh, M (1993) 28:1737–1749

  32. Zheng W, Yates SR, Bradford SA (2008) Environ Sci Technol 42:530–535

    Article  CAS  Google Scholar 

  33. Finlay-Moore O, Hartel PG, Cabrera ML (2000) J Environ Qual 29:1604–1611

    Article  CAS  Google Scholar 

  34. Furuichi T, Kannan K, Suzuki K, Tanaka S, Giesy JP, Masunaga S (2006) Environ Sci Technol 40:7896–7902

    Article  CAS  Google Scholar 

  35. Lorenzen A, Hendel JG, Conn KL, Bittman S, Kwabiah AB, Lazarovitz G, Masse D, McAllister TA, Topp E (2004) Environ Toxicol 19:216–225

    Article  CAS  Google Scholar 

  36. Yang W, Cicek N (2008) Desalination 231:200–208

    Article  CAS  Google Scholar 

  37. Zhao ZY, Fang Y, Love NG, Knowlton KF (2009) Chemosphere 74:551–555

    Article  CAS  Google Scholar 

  38. Shappell NW, Billey LO, Forbes D, Matheny TA, Poach ME, Reddy GB, Hunt PG (2007) Environ Sci Technol 41:444–450

    Article  CAS  Google Scholar 

  39. Labadie P, Budzinski H (2005) Anal Bioanal Chem 381:1199–1205

    Article  CAS  Google Scholar 

  40. Khan, SJ, Roser, DJ, Davies, CM, Peters, GM, Stuetz, RM, Tucker, R, Ashbolt, NJ (2008) 34:839–859

  41. Cespedes R, Petrovic M, Raldua D, Saura U, Pina B, Lacorte S, Viana P, Barcelo D (2004) Anal Bioanal Chem 378:697–708

    Article  CAS  Google Scholar 

  42. Raman, DR, Williams, EL, Layton, AC, Burns, RT, Easter, JP, Daugherty, AS, Mullen, MD, Sayler, GS (2004) 38:3567–3573

  43. Lee HB, Liu D (2002) Water Air Soil Pollut 134:353–368

    Article  CAS  Google Scholar 

  44. de Alda MJL, Barcelo D (2001) Fresenius J. Anal Chem 371:437–447

    Article  Google Scholar 

  45. Ligon AP, Zuehlke S, Spiteller M (2008) J Sep Sci 31:143–150

    Article  CAS  Google Scholar 

  46. Aerni HR, Kobler B, Rutishauser BV, Wettstein FE, Fischer R, Giger W, Hungerbuhler A, Marazuela MD, Peter A, Schonenberger R, Vogeli AC, Suter MJF, Eggen RIL (2004) Anal Bioanal Chem 378:688–696

    Article  CAS  Google Scholar 

  47. Carballa M, Fink G, Omil F, Lema JM, Ternes T (2008) Water Res 42:287–295

    Article  CAS  Google Scholar 

  48. Casey FXM, Simunek J, Lee J, Larsen GL, Hakk H (2005) J Environ Qual 34:1372–1379

    Article  CAS  Google Scholar 

  49. Vedrennes, F (2007), pp. 182, ENSA, Rennes

  50. Martinez-Suller L, Azzellino A, Provolo G (2008) Biosyst Eng 99:540–552

    Article  Google Scholar 

  51. Holbrook RD, Love NG, Novak JT (2004) Environ Sci Technol 38:3322–3329

    Article  CAS  Google Scholar 

  52. Zhou JL, Liu R, Wilding A, Hibberd A (2007) Environ Sci Technol 41:206–213

    Article  CAS  Google Scholar 

  53. Terqui M (1971) Ann Biol Anim Biochem Biophys 11:569–580

    Article  CAS  Google Scholar 

  54. Robertson HA, King GJ (1974) cid 40:133–141

    CAS  Google Scholar 

  55. Czajka CP, Londry KL (2006) Sci Total Environ 367:932–941

    Article  CAS  Google Scholar 

  56. Draca S (2006) Int J Biomed Sci 2:305

    CAS  Google Scholar 

  57. Choi HS, Kiesenhofer E, Gantner H, Hois J, Bamberg E (1987) Anim Reprod Sci 15:209–216

    Article  CAS  Google Scholar 

  58. Vos, EA Theriog. 46:211–231

  59. Bredeck, HE, Mayer, DT (1958) Estrogenic steroids in swine pregnancy urine., Reproduction and Infertility, Illrd Symposium. Ed. F. X. Gassner

  60. Velle W (1976) Environ Qual Saf Suppl 5:159

    CAS  Google Scholar 

  61. Yang, Y, Borch, T, Young, RB, Goodridge, LD, Davis, JG (2010) J. Environ. Qual. 39

Download references

Acknowledgements

The authors wish to thank the French National Research Agency (ANR) and the French Environment and Energy Management Agency (ADEME) which funded the study. The authors also wish to thank Patrick Dabert of the Research Institute of Agricultural and Environmental Engineering (CEMAGREF) for field sampling and sample conditioning, and for raw dry matter data.

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Authors and Affiliations

  1. INRA- UR050 Laboratoire de Biotechnologie de l’Environnement- Avenue des étangs, 11100, Narbonne, France

    Sarah Combalbert, Marie-Laure Pype, Nicolas Bernet & Guillermina Hernandez-Raquet

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  1. Sarah Combalbert
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  2. Marie-Laure Pype
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  3. Nicolas Bernet
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  4. Guillermina Hernandez-Raquet
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Correspondence to Guillermina Hernandez-Raquet.

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Combalbert, S., Pype, ML., Bernet, N. et al. Enhanced methods for conditioning, storage, and extraction of liquid and solid samples of manure for determination of steroid hormones by solid-phase extraction and gas chromatography–mass spectrometry. Anal Bioanal Chem 398, 973–984 (2010). https://doi.org/10.1007/s00216-010-3954-7

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