Advertisement

Analytical and Bioanalytical Chemistry

, Volume 406, Issue 2, pp 643–655 | Cite as

An assessment of the liquid–gas partitioning behavior of major wastewater odorants using two comparative experimental approaches: liquid sample-based vaporization vs. impinger-based dynamic headspace extraction into sorbent tubes

  • Mohammad Asif Iqbal
  • Ki-Hyun Kim
  • Jan E. Szulejko
  • Jinwoo Cho
Research Paper

Abstract

The gas–liquid partitioning behavior of major odorants (acetic acid, propionic acid, isobutyric acid, n-butyric acid, i-valeric acid, n-valeric acid, hexanoic acid, phenol, p-cresol, indole, skatole, and toluene (as a reference)) commonly found in microbially digested wastewaters was investigated by two experimental approaches. Firstly, a simple vaporization method was applied to measure the target odorants dissolved in liquid samples with the aid of sorbent tube/thermal desorption/gas chromatography/mass spectrometry. As an alternative method, an impinger-based dynamic headspace sampling method was also explored to measure the partitioning of target odorants between the gas and liquid phases with the same detection system. The relative extraction efficiency (in percent) of the odorants by dynamic headspace sampling was estimated against the calibration results derived by the vaporization method. Finally, the concentrations of the major odorants in real digested wastewater samples were also analyzed using both analytical approaches. Through a parallel application of the two experimental methods, we intended to develop an experimental approach to be able to assess the liquid-to-gas phase partitioning behavior of major odorants in a complex wastewater system. The relative sensitivity of the two methods expressed in terms of response factor ratios (RFvap/RFimp) of liquid standard calibration between vaporization and impinger-based calibrations varied widely from 981 (skatole) to 6,022 (acetic acid). Comparison of this relative sensitivity thus highlights the rather low extraction efficiency of the highly soluble and more acidic odorants from wastewater samples in dynamic headspace sampling.

Keywords

Odorants Vaporization Dynamic headspace Impinger system Relative recovery Wastewater 

Notes

Acknowledgments

This work was supported by a grant from the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (no. 2009-0093848).

Supplementary material

216_2013_7489_MOESM1_ESM.pdf (686 kb)
ESM 1 (PDF 685 kb)

References

  1. 1.
    Hobbs P, Misselbrook T, Cumby T (1999) Production and emission of odours and gases from ageing pig waste. J Agric Eng Res 72(3):291–298CrossRefGoogle Scholar
  2. 2.
    Klibanov AM, Alberti B, Morris E, Felshin L (1980) Enzymatic removal of toxic phenols and anilines from waste waters. J Appl Biochem 2(5):414–421Google Scholar
  3. 3.
    Lupton F, Zupancic DM (1991) Removal of phenols from waste water by a fixed bed reactor. Google PatentsGoogle Scholar
  4. 4.
    Schaefer J (1977) Sampling, characterization and analysis of malodours. Agric Environ 3(2–3):121–127CrossRefGoogle Scholar
  5. 5.
    Cruwys JA, Dinsdale RM, Hawkes FR, Hawkes DL (2002) Development of a static headspace gas chromatographic procedure for the routine analysis of volatile fatty acids in wastewaters. J Chromatogr A 945(1–2):195–209CrossRefGoogle Scholar
  6. 6.
    Abalos M, Bayona J, Pawliszyn J (2000) Development of a headspace solid-phase microextraction procedure for the determination of free volatile fatty acids in waste waters. J Chromatogr A 873(1):107–115CrossRefGoogle Scholar
  7. 7.
    Elefsiniotis P, Wareham D, Smith M (2004) Use of volatile fatty acids from an acid-phase digester for denitrification. J Biotechnol 114(3):289–297CrossRefGoogle Scholar
  8. 8.
    Boe K, Batstone DJ, Angelidaki I (2007) An innovative online VFA monitoring system for the anaerobic process, based on headspace gas chromatography. Biotechnol Bioeng 96(4):712–721CrossRefGoogle Scholar
  9. 9.
    Manni G, Caron F (1995) Calibration and determination of volatile fatty-acids in waste leachates by gas-chromatography. J Chromatogr A 690(2):237–242CrossRefGoogle Scholar
  10. 10.
    Narkis N, Henfeldfurie S (1978) Direct analytical procedure for determination of volatile organic-acids in raw municipal wastewater. Water Res 12(7):437–446CrossRefGoogle Scholar
  11. 11.
    Abalos M, Bayona J (2000) Application of gas chromatography coupled to chemical ionisation mass spectrometry following headspace solid-phase microextraction for the determination of free volatile fatty acids in aqueous samples. J Chromatogr A 891(2):287–294CrossRefGoogle Scholar
  12. 12.
    Banel A, Jakimska A, Wasielewska M, Wolska L, Zygmunt B (2012) Determination of SCFAs in water using GC-FID. Selection of the separation system. Anal Chim Acta 716:24–27CrossRefGoogle Scholar
  13. 13.
    Gostelow P, Parsons SA (2000) Sewage treatment works odour measurement. Water Sci Technol 41(6):33–40Google Scholar
  14. 14.
    Koe LC, Shen W (1997) High resolution GC-MS analysis of VOCs in wastewater and sludge. Environ Monit Assess 44(1–3):549–561CrossRefGoogle Scholar
  15. 15.
    Wu B-Z, Feng T-Z, Sree U, Chiu K-H, Lo J-G (2006) Sampling and analysis of volatile organics emitted from wastewater treatment plant and drain system of an industrial science park. Anal Chim Acta 576(1):100–111CrossRefGoogle Scholar
  16. 16.
    Yo S-P (1999) Analysis of volatile fatty acids in wastewater collected from a pig farm by a solid phase microextraction method. Chemosphere 38(4):823–834CrossRefGoogle Scholar
  17. 17.
    Zuriguel V, Causse E, Bounery JD, Nouadje G, Simeon N, Nertz M, Salvayre R, Couderc F (1997) Short chain fatty acids analysis by capillary electrophoresis and indirect UV detection or laser-induced fluorescence. J Chromatogr A 781(1–2):233–238CrossRefGoogle Scholar
  18. 18.
    Guerrant G, Lambert M, Moss CW (1982) Analysis of short-chain acids from anaerobic bacteria by high-performance liquid chromatography. J Clin Microbiol 16(2):355–360Google Scholar
  19. 19.
    Peu P, Béline F, Martinez J (2004) Volatile fatty acids analysis from pig slurry using high-performance liquid chromatography. Int J Environ Chem 84(13):1017–1022CrossRefGoogle Scholar
  20. 20.
    Caron F, Elchuk S, Walker ZH (1996) High-performance liquid chromatographic characterization of dissolved organic matter from low-level radioactive waste leachates. J Chromatogr A 739(1–2):281–294CrossRefGoogle Scholar
  21. 21.
    Kim H, Nochetto C, McConnell LL (2002) Gas-phase analysis of trimethylamine, propionic and butyric acids, and sulfur compounds using solid-phase microextraction. Anal Chem 74(5):1054–1060CrossRefGoogle Scholar
  22. 22.
    Kim Y-H, Kim K-H (2012) Novel approach to test the relative recovery of liquid-phase standard in sorbent-tube analysis of gaseous volatile organic compounds. Anal Chem 84(9):4126–4139CrossRefGoogle Scholar
  23. 23.
    Kim Y-H, Kim K-H (2013) The extent of sample loss on the sampling device and the resulting experimental biases when collecting volatile fatty acids (VFAs) in air using sorbent tube. Anal Chem 85:7818–7825CrossRefGoogle Scholar
  24. 24.
    US EPA (1986) Definition and procedure for the determination of the method detection limit-Revision 1.11, Code of Federal Regulations, Title 40, Part 136, Appendix B, 1984. Fed. Regist., 51, 23703Google Scholar
  25. 25.
    Szulejko JE, Kim Y-H, Kim K-H (2013) Method to predict gas chromatographic response factors for the trace-level analysis of volatile organic compounds based on the effective carbon number concept. J Sep Sci. doi: 10.1002/jssc.201300543 Google Scholar
  26. 26.
    Gilman JB, Vaida V (2006) Permeability of acetic acid through organic films at the air-aqueous interface. J Phys Chem 110(24):7581–7587CrossRefGoogle Scholar
  27. 27.
    Nathanson GM, Davidovits P, Worsnop DR, Kolb CE (1996) Dynamics and kinetics at the gas–liquid interface. J Phys Chem 100(31):13007–13020CrossRefGoogle Scholar
  28. 28.
    Khan I, Brimblecombe P (1992) Henry’s law constants of low molecular weight (<130) organic acids. J Aerosol Sci 23:897–900CrossRefGoogle Scholar
  29. 29.
    Khan I, Brimblecombe P, Clegg SL (1995) Solubilities of pyruvic-acid and the lower (C-1-C-6) carboxylic-acids—experimental-determination of equilibrium vapor-pressures above pure aqueous and salt-solutions. J Atmos Chem 22(3):285–302CrossRefGoogle Scholar
  30. 30.
    NIST Chemistry WebBook (2013) http://webbook.nist.gov/chemistry. Accessed August/October 2013
  31. 31.
    SRC Database (2013) http://www.syrres.com/what-we-do/databaseforms.aspx?id=386. Accessed August/October 2013
  32. 32.
    Kim K-H, Szulejko JE (2013) A theoretical consideration on the unfeasibility of an analytical method recommended for volatile fatty acids (VFA) by the offensive odor prevention law (in Korean with abstract in English). J Korean Soc Odor Res Eng 12:1–7CrossRefGoogle Scholar
  33. 33.
    Lou D-W, Lee X, Pawliszyn J (2008) Extraction of formic and acetic acids from aqueous solution by dynamic headspace-needle trap extraction: temperature and pH optimization. J Chromatogr A 1201(2):228–234CrossRefGoogle Scholar
  34. 34.
    Burns DC, Ellis DA, Webster E, McMurdo CJ (2009) Response to comment on “experimental pKa determination for perfluorooctanoic acid (PFOA) and the potential impact of pKa concentration dependence on laboratory-measured partitioning phenomena and environmental modeling”. Environ Sci Technol 43(13):5152–5154CrossRefGoogle Scholar
  35. 35.
    Barber WP, Stuckey DC (1999) The use of the anaerobic baffled reactor (ABR) for wastewater treatment: a review. Water Res 33(7):1559–1578CrossRefGoogle Scholar
  36. 36.
    Tchobanoglous G, Burton FL (1991) Wastewater engineering treatment, disposal and reuse (3rd ed). McGraw-Hill, New York, pp 126–128Google Scholar
  37. 37.
    Higashikawa FS, Cayuela ML, Roig A, Silva CA, Sánchez-Monedero MA (2013) Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples. Chemosphere, 93(10):2311-2318Google Scholar
  38. 38.
    Saha CK, Feilberg A, Zhang G, Adamsen APS (2011) Effects of airflow on odorants’ emissions in a model pig house—a laboratory study using proton-transfer-reaction mass spectrometry (PTR-MS). Sci Total Environ 410:161–171CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Mohammad Asif Iqbal
    • 1
  • Ki-Hyun Kim
    • 1
  • Jan E. Szulejko
    • 1
  • Jinwoo Cho
    • 1
  1. 1.Department of Environment and EnergySejong UniversitySeoulRepublic of Korea

Personalised recommendations