Skip to main content
Log in

Biodegradability of imidazolium and pyridinium ionic liquids by an activated sludge microbial community

  • Original Paper
  • Published:
Biodegradation Aims and scope Submit manuscript

Abstract

Ionic liquids (ILs) are novel organic salts that have enormous potential for industrial use as green replacements for harmful volatile organic solvents. Varying the cationic components can alter the chemical and physical properties of ILs, including solubility, to suit a variety of industrial processes. However, to complement designer engineering, it is crucial to proactively characterize the biological impacts of new chemicals, in order to fully define them as environmentally friendly. Before introduction of ILs into the environment, we performed an analysis of the biodegradability of six ILs by activated sludge microorganisms collected from the South Bend, Indiana wastewater treatment plant. We examined biodegradability of 1-butyl, 1-hexyl and 1-octyl derivatives of 3-methyl-imidazolium and 3-methyl-pyridinium bromide compounds using the standard Organisation for Economic Cooperation and Development dissolved organic carbon Die-Away Test, changes in total dissolved nitrogen concentrations, and 1H-nuclear magnetic resonance analysis of initial and final chemical structures. Further, we examined microbial community profiles throughout the incubation period using denaturing gradient gel electrophoresis (DNA-PCR-DGGE). Our results suggest that hexyl and octyl substituted pyridinium-based ILs can be fully mineralized, but that imidazolium-based ILs are only partially mineralized. Butyl substituted ILs with either cation, were not biodegradable. Biodegradation rates also increase with longer alkyl chain length, which may be related to enhanced selection of a microbial community. Finally, DGGE analysis suggests that certain microorganisms are enriched by ILs used as a carbon source. Based on these results, we suggest that further IL design and synthesis include pyridinium cations and longer alkyl substitutions for rapid biodegradability.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  • Allen DT, Shonnard DR (2002) Green engineering. Prentice-Hall, Upper Saddle River

    Google Scholar 

  • Bernot RJ, Brueseke MA, Evans-White MA, Lamberti GA (2005a) Acute and chronic toxicity of imidazolium-based ionic liquids on Daphnia magna. Environ Toxicol Chem 24(1):87–92

    Article  CAS  Google Scholar 

  • Bernot RJ, Kennedy EE, Lamberti GA (2005b) Effects of ionic liquids on the survival, movement, and feeding behavior of the freshwater snail, Physa acuta. Environ Toxicol Chem 24(7):1759–1765

    Article  CAS  Google Scholar 

  • Biorad Life Science Group (1996) The Dcode Universal Mutation Detection System. Biorad Life Science Group, Hercules

    Google Scholar 

  • Boethling RS (1996) Designing biodegradable chemicals. Designing safer chemicals: ACS symposium series 640:156–171

    Article  CAS  Google Scholar 

  • Bonhôte P, Dias AP, Papgeorgiou N, Kalyanasundaram K, Gratzel M (1996) Hydrophobic, highly conductive ambient-temperature molten salts. Inorg Chem 35(5):1168–1178

    Article  Google Scholar 

  • Brennecke JF, Maginn EJ (2001) Ionic liquids: innovative fluids for chemical processing. AIChE J 47:2384–2389

    Article  CAS  Google Scholar 

  • Cammarata L, Kazarian SG, Salter PA, Welton T (2001) Molecular states of water in room temperature ionic liquids. Phys Chem Chem Phys 3(23):5192–5200

    Article  CAS  Google Scholar 

  • Docherty KM, Kulpa CF (2005) Toxicity and antimicrobial activity of imidazolium and pyridinium ionic liquids. Green Chem 7:185–189

    Article  CAS  Google Scholar 

  • Docherty KM, Hebbeler SZ, Kulpa CF (2006) An assessment of ionic liquid mutagenicity using the Ames Test. Green Chem 8(6):560–567

    Article  CAS  Google Scholar 

  • Dupont J, deSouza RF, Suarez PAZ (2002) Ionic liquid (molten salt) phase organometallic catalysis. Chem Rev 102:3667–3692

    Article  CAS  Google Scholar 

  • Fredlake CP, Crosthwaite JM, Hert DG, Aki SNVK, Brennecke JF (2004) Thermophysical properties of imidazolium ionic liquids. J Chem Eng Data 49(4):954–964

    Article  CAS  Google Scholar 

  • Gathergood N, Garcia MT, Scammells PJ (2004) Biodegradable ionic liquids: part I. Concept, preliminary targets and evaluation. Green Chem 6:166–175

    Article  CAS  Google Scholar 

  • Gathergood N, Scammells PJ, Garcia MT (2006) Biodegradable ionic liquids: part III. The first readily biodegradable ionic liquids. Green Chem 8:56–160

    Article  CAS  Google Scholar 

  • Gorman-Lewis DJ, Fein JB (2004) Experimental study of the adsorption of an ionic liquid onto bacterial and mineral surfaces. Environ Sci Technol 38:2491–2495

    Article  CAS  Google Scholar 

  • Grabinska-Sota E, Kalka J (2004) An assessment of the toxicity of pyridinium chlorides and their biodegradation intermediates. Environ Int 28:687–690

    Article  CAS  Google Scholar 

  • He J, Robrock KR, Alvarez-Cohen L (2006) Microbial reductive debromination of polybrominated diphenyl ethers (PBDEs). Environ Sci Technol 40:4429–4434

    Article  CAS  Google Scholar 

  • Jastorff B, Störmann R, Ranke J, Mölter K, Stock F, Oberheitmann B, Hoffmann W, Hoffmann J, Nüchter M, Ondruschka B, Filser J (2003) How hazardous are ionic liquids? Structure–activity relationships and biological testing as important elements for sustainability evaluation. Green Chem 5:136–142

    Article  CAS  Google Scholar 

  • Kaiser JP, Feng YC, Bollag JM (1996) Microbial metabolism of pyridine, quinoline, acridine, and their derivatives under aerobic and anaerobic conditions. Microbiol Rev 60(3):483–498

    CAS  Google Scholar 

  • Liao Q, Hussey L (1996) Densities, viscosities and conductivities of mixtures of benzene with the Lewis acidic aluminum chloride: 1-methyl-3-ethylimidazolium chloride molten salt. J Chem Eng Data 41:1126–1130

    Article  CAS  Google Scholar 

  • Marsh KN, Deev A, Wu ACT, Tran E, Klamt A (2002) Room temperature ionic liquids as replacements for conventional solvents—a review. Korean J Chem Eng 19(3):357–362

    CAS  Google Scholar 

  • Muyzer G, de Waal EC, Uitterlinden AG (1993) Profiling of complex microbial populations by denaturing gradient gel electrophoresis analysis of polymerase chain reaction-amplified genes coding for 16S rRNA. Appl Environ Microbiol 59:695–700

    CAS  Google Scholar 

  • National Toxicology Program (NTP) and National Institute of Environmental Health Sciences (NIEHS) (2004) Review of toxicological literature for ionic liquids. Prepared by Integrated Laboratory Systems Inc., Research Triangle Park

  • Organisation for Economic Co-operation and Development (OECD) Guideline for Testing of Chemicals 301 A-F. Adopted July 17, 1992

  • Pernak J, Chwala P (2003) Synthesis and anti-microbial activities of choline-like quaternary ammonium chlorides. Eur J Med Chem 38:1035–1042

    Article  CAS  Google Scholar 

  • Pernak J, Rogoza J, Mirska I (2001) Synthesis and antimicrobial activities of new pyridinium and benzimidazolium chlorides. Eur J Med Chem 36:313–320

    Article  CAS  Google Scholar 

  • Pernak J, Goc I, Mirska I (2004) Anti-microbial activities of protic ionic liquids with lactate anion. Green Chem 6:323–329

    Article  CAS  Google Scholar 

  • Pretti C, Chiappe C, Pieraccini D, Gregori M, Abramo F, Monni G, Intorre L (2006) Acute toxicity of ionic liquids to the zebrafish (Danio rerio). Green Chem 8:238–240

    Article  CAS  Google Scholar 

  • Ranke J, Molter K, Stock F, Bottin-Weber U, Poczobutt J, Hoffmann J, Ondruschka B, Filser J, Jastorff B (2004) Biological effects of imidazolium ionic liquids with varying chain lengths in acute Vibrio fischeri and WST-1 cell viability assays. Ecotoxicol Environ Saf 58(3):396–404

    Article  CAS  Google Scholar 

  • Scow KM (2002) Microbial ecology and in situ bioremediation of MTBE-contaminated groundwater. Bioremediation and biodegradation conference paper, Pacific Grove

    Google Scholar 

  • Sheldon RA (2005) Green solvents for sustainable organic synthesis: state of the art. Green Chem 7:267–278

    Article  CAS  Google Scholar 

  • Sigma-Aldrich-Fluka (2001) Green chemistry ChemFiles: ionic liquids, fluorous phase organic synthesis (FPOS). Phase Transfer Catalysis (PTC) 1(7):1–18. (http://www.sigmaaldrich.com/img/assets/15469/chemfiles_v1n7_greenchemistry_small.pdf)

    Google Scholar 

  • Smith AE, Hristova K, Wood I, Mackay DM, Lory E, Lorenzana D, Scow KM (2005) Comparison of biostimulation versus bioaugmentation with bacterial strain PM1 for treatment of groundwater contaminated with methyl tertiary butyl ether (MTBE). Environ Health Perspect 113(3):317–322

    Article  CAS  Google Scholar 

  • Stepnowski P, Storoniak P (2005) Lipophilicity and metabolic route prediction of imidazolium ionic liquids. Environ Sci Pollut Res Int 12(4):199–205

    Article  CAS  Google Scholar 

  • Swatloski RP, Holbrey JD, Memon SB, Caldwell GA, Caldwell KA, Rogers RD (2004) Using Caenorhabditis elegans to probe toxicity of 1-alkyl-3-methylimidazolium chloride based ionic liquids. Chem Commun 6:668–669

    Article  CAS  Google Scholar 

  • United States Geological Survey, National Water Quality Assessment Program (USGS NAWQA) (1995) Occurrence of the gasoline additive MTBE in shallow ground water in urban and agricultural areas. USGS Fact Sheet FS-114–95

Download references

Acknowledgements

We thank J.F. Brenneke for providing ILs and D.M. Costello for assistance in manuscript preparation. Funding provided by the National Oceanic and Atmospheric Administration, the U.S. Department of Education Graduate Assistance in Areas of National Need Fellowship to K.M. Docherty and the Indiana 21st Century Research and Technology Fund is gratefully acknowledged. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship to K.M. Docherty. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Kathryn M. Docherty.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Docherty, K.M., Dixon, J.K. & Kulpa Jr, C.F. Biodegradability of imidazolium and pyridinium ionic liquids by an activated sludge microbial community. Biodegradation 18, 481–493 (2007). https://doi.org/10.1007/s10532-006-9081-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10532-006-9081-7

Keywords

Navigation