Skip to main content
SpringerLink
Log in

A model for the effects of primary substrates on the kinetics of reductive dehalogenation

  • Articles
  • Published:
Biodegradation Aims and scope Submit manuscript

Abstract

A kinetic model that describes substrate interactions during reductive dehalogenation reactions is developed. This model describes how the concentrations of primary electron-donor and -acceptor substrates affect the rates of reductive dehalogenation reactions. A basic model, which considers only exogenous electron-donor and -acceptor substrates, illustrates the fundamental interactions that affect reductive dehalogenation reaction kinetics. Because this basic model cannot accurately describe important phenomena, such as reductive dehalogenation that occurs in the absence of exogenous electron donors, it is expanded to include an endogenous electron donor and additional electron acceptor reactions. This general model more accurately reflects the behavior that has been observed for reductive dehalogenation reactions. Under most conditions, primary electron-donor substrates stimulate the reductive dehalogenation rate, while primary electron acceptors reduce the reaction rate. The effects of primary substrates are incorporated into the kinetic parameters for a Monod-like rate expression. The apparent maximum rate of reductive dehalogenation (q m, ap ) and the apparent half-saturation concentration (K ap ) increase as the electron donor concentration increases. The electron-acceptor concentration does not affect q m, ap , but K ap is directly proportional to its concentration.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Abbreviations

RX:

halogenated aliphatic substrate

E-Mn :

reduced dehalogenase

E-Mn+2 :

oxidized dehalogenase

[E-Mn]:

steady-state concentration of the reduced dehalogenase (moles of reduced dehalogenase per unit volume)

[E-Mn+2]:

steady-state concentration of the oxidized dehalogenase (moles of reduced dehalogenase per unit volume)

DH2β :

primary exogenous electron-donor substrate

A:

primary exogenous electron-acceptor substrate

A2:

second primary exogenous electron-acceptor substrate

X:

biomass concentration (biomass per unit volume)

f:

fraction of biomass that is comprised of the dehalogenase (moles of dehalogenase per unit biomass)

α:

stoichiometric coefficient for the reductive dehalogenation reaction (moles of dehalogenase oxidized per mole of halogenated substrate reduced)

β:

stoichiometric coefficient for oxidation of the primary electron donor (moles of dehalogenase reduced per mole of donor oxidized)

γ:

stoichiometric coefficient for oxidation of the endogenous electron donor (moles of dehalogenase reduced per unit biomass oxidized)

δ:

stoichiometric coefficient for reduction of the primary electron acceptor (moles of dehalogenase oxidized per mole of acceptor reduced)

κ:

stoichiometric coefficient for reduction of the second electron acceptor (moles of dehalogenase oxidized per mole of acceptor reduced)

r RX :

rate of the reductive dehalogenation reaction (moles of halogenated substrate reduced per unit volume per unit time)

r d1 :

rate of oxidation of the primary exogenous electron donor (moles of donor oxidized per unit volume per unit time)

r d2 :

rate of oxidation of the endogenous electron donor (biomass oxidized per unit volume per unit time)

r a1 :

rate of reduction of the primary exogenous electron acceptor (moles of acceptor reduced per unit volume per unit time)

r a2 :

rate of reduction of the second primary electron acceptor (moles of acceptor reduced per unit volume per unit time)

k RX :

mixed second-order rate coefficient for the reductive dehalogenation reaction (volume per mole dehalogenase per unit time)

k d1 :

mixed-second-order rate coefficient for oxidation of the primary electron donor (volume per mole dehalogenase per unit time)

k d2 :

mixed-second-order rate coefficient for oxidation of the endogenous electron donor (volume per mole dehalogenase per unit time)

b:

first-order biomass decay coefficient (biomass oxidized per unit biomass per unit time)

k a1 :

mixed-second-order rate coefficient for reduction of the primary electron acceptor (volume per mole dehalogenase per unit time)

k a2 :

mixed-second-order rate coefficient for reduction of the second primary electron acceptor (volume per mole dehalogenase per unit time)

q m,ap :

apparent maximum specific rate of reductive dehalogenation (moles of RX per unit biomass per unit time)

K ap :

apparent half-saturation concentration for the halogenated aliphatic substrate (moles of RX per unit volume)

k ap :

apparent pseudo-first-order rate coefficient for reductive dehalogenation (volume per unit biomass per unit time)

References

  • Alvarez-Cohen L & McCarty PL (1991) Effects of toxicity, aeration, and reductant supply on trichloroethylene transformation by a mixed methanotrophic culture. Appl. Environ. Microbiol. 57: 228–235

    Google Scholar 

  • Costello DJ, Greenfield PF & Lee PL (1991) Dynamic modelling of a single-stage high-rate anaerobic reactor—II. Model verification. Water Res. 25: 859–871

    Google Scholar 

  • Criddle CS (1993) The kinetics of cometabolism. Biotech. Bioeng. 41: 1048–1056

    Google Scholar 

  • Criddle CS, DeWitt JT, Grbić-Galić D & McCarty PL (1990a) Transformation of carbon tetrachloride byPseudomonas sp. strain KC under denitrification conditions. Appl. Environ. Microbiol. 56: 3240–3246

    Google Scholar 

  • Criddle CS, DeWitt JT & McCarty PL (1990b) Reductive dehalogenation of carbon tetrachloride byE. coli K-12. Appl. Environ. Microbiol. 56: 3247–3254

    Google Scholar 

  • Dangel W, Schulz H, Diekert G, König H & Fuchs G (1987) Occurrence of corrinoid-containing membrane proteins in anaerobic bacteria. Arch. Microbiol. 148: 52–56

    Google Scholar 

  • DeWeerd KA & Suflita JM (1990) Anaerobic aryl reductive dehalogenation of halobenzoates by cell extracts ofDesulfomonile tiedjei. App. Environ. Microbiol. 56: 2999–3005

    Google Scholar 

  • DeWeerd KA, Concannon F & Suflita JM (1991) Relationship between hydrogen consumption, dehalogenation, and the reduction of sulfur oxyanions byDesulfomonile tiedjei. Appl. Environ. Microbiol. 57: 1929–1934

    Google Scholar 

  • Dolfing J & Tiedje JM (1991a) Acetate as a source of reducing equivalents in the reductive dechlorination of 2,5-dichlorobenzoate. Arch. Microbiol. 156: 356–361

    Google Scholar 

  • —— (1991b) Influence of substituents on reductive dehalogenation of 3-chlorobenzoate analogs. Appl. Environ. Microbiol. 57: 820–824

    Google Scholar 

  • Fathepure BZ & Boyd SA (1988) Dependence of tetrachloro-ethylene dechlorination on methanogenic substrate consumption byMethanosarcina sp. strain DCM. Appl. Environ. Microbiol. 54: 2976–2980

    Google Scholar 

  • Freedman DL & Gossett JM (1989) Biological reductive dechlorination of tetrachloroethylene and trichloroethylene to ethylene under methanogenic conditions. Appl. Environ. Microbiol. 55: 2144–2151

    Google Scholar 

  • Gälli R & McCarty PL (1989) Kinetics of biotransformation of 1,1,1-trichloroethane byClostridium sp. strain TCAIIB. Appl. Environ. Microbiol. 55: 845–851

    Google Scholar 

  • Gantzer CJ & Wackett LP (1991) Reductive dechlorination catalyzed by bacterial transition-metal coenzymes. Environ. Sci. Tech. 25: 715–722

    Google Scholar 

  • Gibson SA & Suflita JM (1990) Anaerobic biodegradation of 2,4,5-trichlorophenoxyacetic acid in samples from a methanogenic aquifer: Stimulation by short-chain organic acids and alcohols. Appl. Environ. Microbiol. 56: 1825–1832

    Google Scholar 

  • —— (1993) Role of electron-donating cosubstrates in the anaerobic biotransformation of chlorophenoxyacetates to chlorophenols by a bacterial consortium enriched on phenoxyacetate. Biodegradation 4: 51–57

    Google Scholar 

  • Gottschalk G (1986) Bacterial Metabolism, Second Edition. Springer-Verlag, New York

    Google Scholar 

  • Henry SM & Grbić-Galić D (1991) Influence of endogenous and exogenous electron donors and trichloroethylene oxidation toxicity on trichloroethylene oxidation by methanotrophic cultures from a groundwater aquifer. Appl. Environ. Microbiol. 57: 236–244

    Google Scholar 

  • Ingvorsen K & Jorgensen BB (1984) Kinetics of sulfate uptake by freshwater and marine species ofDesulfovibrio. Arch. Microbiol. 139: 61–66

    Google Scholar 

  • Ingvorsen K, Zehnder AJB & Jorgensen BB (1984) Kinetics of sulfate and acetate uptake byDesulfobacter postgatei. Appl. Environ. Microbiol. 47: 403–408

    Google Scholar 

  • Jones WJ, Nagle DP Jr & Whitman WB (1987) Methanogens and the diversity of archaebacteria. Microbiological Reviews 51: 135–177

    Google Scholar 

  • Klecka GM & Gonsior SJ (1984) Reductive dechlorination of chlorinated methanes and ethanes by reduced iron (II) porphyrins. Chemosphere 13: 391–402

    Google Scholar 

  • Kochi JK (1978) Organometallic Mechanisms and Catalysis. Academic Press, New York

    Google Scholar 

  • Krone UE, Thauer RK & Hogenkamp HPC (1989a) Reductive dehalogenation of chlorinated C1-hydrocarbons mediated by corrinoids. Biochemistry 28: 4908–4914

    Google Scholar 

  • Krone UE, Laufer K, Thauer RK & Hogenkamp HPC (1989b) Coenzyme F430 as a possible catalyst for the reductive dehalogenation of chlorinated C1 hydrocarbons in methanogenic bacteria. Biochemistry 28: 10,061–10,065

    Google Scholar 

  • Kuhn EP, Townsend GT & Suflita JM (1990) Effect of sulfate and organic carbon supplements on reductive dehalogenation of chloroanilines in anaerobic aquifer slurries. Appl. Environ. Microbiol. 56: 2630–2637

    Google Scholar 

  • McCarty PL (1972) Energetics of organic matter degradation. In: Mitchell R (Ed) Water Pollution Microbiology. (pp 91–118) Wiley-Interscience, New York

    Google Scholar 

  • Mikesell MD & Boyd SA (1990) Dechlorination of chloroform byMethanosarcina strains. Appl. Environ. Microbiol. 56: 1198–1201

    Google Scholar 

  • Nethe-Jaenchen R & Thauer RK (1984) Growth yields and saturation constant ofDesulfovibrio vulgaris in chemostat culture. Arch. Microbiol. 137: 236–240

    Google Scholar 

  • Saéz PB & Rittmann BE (1993) Biodegradation kinetics of a mixture containing a primary substrate (phenol) and an inhibitory cometabolite (4-chlorophenol). Biodegradation 4: 3–21

    Google Scholar 

  • Schauer NL, Brown DP & Ferry JG (1982) Kinetics of formate metabolism inMethanobacterium formicicum andMethanospirillum hungatei. Appl. Environ. Microbiol. 44: 549–554

    Google Scholar 

  • Wade RS & Castro CE (1973a) Oxidation of iron (II) porphyrins by alkyl halides. J. Amer. Chem. Soc. 95: 226–230

    Google Scholar 

  • —— (1973b) Oxidation of heme proteins by alkyl halides. J. Amer. Chem. Soc. 95: 231–234

    Google Scholar 

  • Widdel F (1988) Microbiology and ecology of sulfate- and sulfur-reducing bacteria. In: Zehnder AJB (Ed) Biology of Anaerobic Microorganisms. (pp 468–585) John Wiley and Sons, Inc., New York

    Google Scholar 

  • Wrenn BA & Rittmann BE Experimental evaluation of a model for the effects of primary substrates on reductive dehalogenation kinetics. Submitted to Biodegradation

  • Zeikus JG, Kerby R & Krzycki JA (1985) Single-carbon chemistry of acetogenic and methanogenic bacteria. Science 227: 1167–1173

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Civil and Environmental Engineering, University of Cincinnati, 45221, Cincinnati, OH, USA

    Brian A. Wrenn

  2. Department of Civil Engineering, Northwestern University, 60208-3109, Evanston, IL, USA

    Bruce E. Rittmann

Authors
  1. Brian A. Wrenn
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Bruce E. Rittmann
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Wrenn, B.A., Rittmann, B.E. A model for the effects of primary substrates on the kinetics of reductive dehalogenation. Biodegradation 6, 295–308 (1995). https://doi.org/10.1007/BF00695260

Download citation

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00695260

Key words

Search

Navigation