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86                                                   Soil and Water Contamination

                    However, the decay rates of the various organic compounds may differ considerably and the
                    complete breakdown may be a very slow process taking several decades or – in the case of
                    recalcitrant humic substances  – thousands of years. Because of its complex composition,
                    there is no general chemical formula for organic matter. However, it is possible to write a
                    general simplified equation of the reaction, which only involves the initial reactants and the
                    final products:
                    CH  O +  e. a.  CO +  H  O +  inorganic  N,  P,  S                  (4.2)
                       2               2    2
                    where CH O refers to organic matter and e.a. to the various electron acceptors (oxidants )
                            2
                                                                 -
                                                                                  2-
                    available in the system (e.g. oxygen  (O ), nitrate (NO ), and sulphate (SO )). In well-
                                                    2           3                4
                    aerated soils and surface waters, oxygen is the predominant electron acceptor  :
                    CH  O  + O .    CO  + H  O      HCO   + H  +                        (4.3)
                       2     2         2    2           3
                    In many environments, however, the amount of oxygen  is limited, and the other oxidants
                    are used consecutively. Figure 4.10 shows the sequence of redox reactions  which operate
                    at successively lower redox potential s. Firstly, if oxygen  is depleted, nitrate -reducing
                    microbe species take over the decomposition  of organic matter , using nitrate as oxidant .
                                                -
                    Nitrate is reduced via nitrite (NO ) , nitric oxide (NO ) , and nitrous oxide (N O)  to free
                                               2                x                  2
                    nitrogen  (N ). This process is called denitrification  (see also Section 6.2) and this overall
                             2
                    transformation  can be written as:
                                                 .
                                                0
                           0
                                                                  .
                    CH  O  + 8  NO       HCO   + 4  N  + 4  H  O  + 2  H  +             (4.4)
                                                         .
                                                                 0
                                                        0
                            .
                       2         3           3       2       2
                    Not all nitrate  is transformed into free nitrogen  gas, because both nitric oxide)  and nitrous
                    oxide)  are also gases, which can escape prematurely from the system. If nitrate has been
                    depleted, manganese -reducing bacteria use Mn(IV) as the principal electron acceptor
                    (oxidant ):
                       900
                               O        H O
                                2   2
                                   NO 3-         N
                                          2
                       600
                                          MnO         Mn 2+
                                             2
                       300
                     Eh (mV)
                        0
                                                     Fe(OH)         Fe 2+
                                                          3
                                                                SO 2-         H S
                                                                  4   2
                                                                          CO         CH
                       -300                                                2     4
                                                                                 (H O        H )
                                                                                   2    2
                     6642  6642  6642  -600
                                                   Organic matter consumption

                    Figure 4.10  Evolution of the redox potential  (Eh) as function of organic matter consumption  .









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        Soil and Water.indd   98                                                            10/1/2013   6:44:23 PM
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