Page 261 - Soil and water contamination, 2nd edition
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248                                                  Soil and Water Contamination

                    Table 13.2  Minimum and maximum biodegradation  rate constants in soil and groundwater (source: EPA, 1999b;
                    Mathess, 1994).
                    Chemical group                  First-order degradation rate constant k
                                                    Minimum             Maximum
                                                    d -1                d -1
                    Benzene*                        0                   0.071
                    Toluene*                        0                   0.186
                    Trichloroethylene*              0.00082             0.04
                    Vinyl chloride*                 0                   0.0582
                    Phenol*                         0                   0.2
                    Halogenated hydrocarbons        0.00016             0.0036
                    Carbamate                       0.0011              0.35
                    Aniline                         0.0022              0.073
                    Urea                            0.00098             0.031
                    Organic phosphorus  compounds   0.0012              0.12
                    Triazine                        0.0018              0.032
                    * anaerobic  groundwater (EPA, 1999b)



                              -1
                    about 0.01 d  – if the concentrations of sediment organic matter or dissolved organic carbon
                    increase and the redox potential  decreases: for example, in polluted  plumes from septic tanks .
                    The denitrification  rate constants may be even larger in organic sediments. Because the
                    aquifer  properties and their accompanying rate constants vary so widely, and information on
                    these parameters is often scarce, the use of first-order kinetics  in regional-scale  groundwater
                    quality modelling  is limited (see Vissers 2006).
                       In surface waters, the first-order constants for nitrification  and denitrification  may also
                    change considerably in space and time. Table 13.3 shows that these constants may vary by
                    over several orders of magnitude for different river systems. As mentioned above, limitation
                    of one of the substrate components or oxidant  may hamper biodegradation . A common
                    expression for the effect of substrate limitation is the Monod equation , also referred to as
                    Michaelis–Menten kinetics :

                             S
                    k            k max                                                (13.17)
                          M    S
                            n
                                                   -3
                    where S = substrate concentration [M L ], k  = maximum rate constant when the substrate
                                                      max
                                   -1
                    is not limiting [T ],  M  = Monod half-saturation concentration  or Michaelis constant
                                        n
                        -3
                    [M L ], which is the substrate concentration for which k = 0.5 ⋅ k . Figure 13.5 shows the
                                                                        max
                    rate constant as function of the substrate concentration. This Equation (13.17) was originally
                    derived by Michaelis–Menten  for modelling uptake kinetics  of organisms growing on a
                    substrate and subsequently applied by Monod to quantify microbial population dynamics
                    in a system.  The equation can also be used to describe substrate or oxidant  limitation in
                    biodegradation  reactions. For example, the effect of oxygen  limitation on nitrification  is
                    described by:
                    dNH        DO
                        4
                                     k  , n  max  NH 4                                (13.18)
                      dt     M    DO
                               n






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