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All DOC is not the same:
DOC classified by functional properties
and their environmental significance


                        Andy Baker
                        University of
                        Birmingham
                        a.baker.2@bham.ac.uk
Battin et al. doi:10.1038/ngeo618
The microbial loop. Fenchel,
doi:10.1016/j.jembe.2008.07.013
(In predominantly natural systems)

Evidence of DOC processing within rivers. DOC becomes increasingly ‘young’ in 14C age
    and hydrophilic with distance from source. Rivers evade CO2. Photodegradation
    and biodegradation occurs, arguably of all DOM fractions.

Seasonal variations in riverine DOM character, typically a hydrophobic / aromatic
   ‘flush’. Differences in DOM character between catchments, depending on soil
   type, land cover and human impact.

Evidence of greater variability in DOC characteristics in headwaters and low order
    streams with ‘fresh’ DOM. Downstream DOC might be 14C ‘young’, but it is more
    homogenous and biogeochemically ‘aged’.

Anthropogenic inputs typically introduce hydrophilic, relatively colourless, DOC.

Clear links between DOC character and function. Aromatic DOC has greater chemical
   and ecological function (metal binding, contaminant binding, UV screening), and is
   easy to treat. Hydrophilic DOC difficult to remove during drinking water treatment.
Peak C fluorescence




                      Time /
                      Processing




                                   Variable and high fluorescence / g C in
                                   bog waters

                                   Less variable and less fluorescent / g C
                                   river waters

                                   IHSS standards have atypically low
                                   fluorescence
Mean and standard deviation colour/DOC
                  CBweir                       10.7 (1.4)
                  Pweir                        10.0 (1.2)
                  PGweir                       8.4 (2.5)
                  ME                           10.8 (3.7)
                  MC                           9.5 (0.8)                                     Different DOC character
                  FE                           12.4 (3.7)
                                                                                             between sub-catchments
                  FC                           11.5 (2.0)

                                                                                                   ‘fresh’ DOC is
                                                                                                   more coloured
                          CB we ir   P we ir       PG we ir   ME     MC       FE        FC
                 1500
Peak Cint/a340




                 1250

                 1000

                 750                                                                                ‘fresh’ DOC is more fluorescent
                 500
                                                                                                    per unit absorbance
                 250
Photodegradation of
lignin over two months



                         Lignin phenol
                         concentration and
                         relationship with
                         optical
                         characteristics
                         through the ‘wet’
Summary

River microbial ecosystem processes DOC. Aromatic bonds in DOC relatively
   easier to break. DOC therefore less aromatic with residence /travel time.
   Easily measured ‘in-situ’ using UV absorbance or fluorescence.
River experience seasonal variations in riverine DOC character. Typically with
   ‘flush’ of relatively fresh (therefore aromatic) DOC. Groundwater rivers
   will have a groundwater hydrophilic DOC source.
Catchment mean DOC character depending on soil type, land cover and
   human impact.
Evidence of greater variability in DOC characteristics in headwaters and low
   order streams with ‘fresh’ DOM; variability decreases downstream as this
   is processed.
Anthropogenic inputs typically introduce relatively hydrophilic, colourless,
   DOC.
Aromatic DOC has greater chemical and ecological function (metal binding,
   contaminant binding, UV screening), and is easy to treat. Hydrophilic DOC
   difficult to remove during drinking water treatment.
2


                                                                                                          13 13
                                                                                                        7 14 14
                                                                                                         1713
                                                                                                            17
                                                                                                   27 32 14
                                                                                                    8 33
                                                                                                       17
                                                                                                    4723
                                                                                                  851821
                                                                                                   3315
                                                                                                      60
                                                                                                    2611
                                                                                                      18
                                                                                                661 61
                                                                                                   30
                                                                                                   32
                                                                                                 11 21
                                                                                                   30
                                                                                                6213 12
                                                                                                  12
                                                                                                 611 23
                                                                                                  11
                                                                                            12 1626 16
                                                                                                  15
                                                                                 29
                                                                                    28       25 21
                                                                                             18
                                                                                             11
                                                                                                18
                                                                                                 10
                                                                                                 12
                                                                                               2310
                                                                                          2130
                                                                                            26
                                                                                          9 32
                                                                                     19 6 2312
                                                                                          33
                                                              38 1 46 46           60 417
                                                                                   24 14 25
                                                                                        864
             10                          46            463831          7
                                                                                   16 63
                                                                                      59
                                                                                  25 62 31
                                        36                                       15 13 50
                                                                                  33 3
                                              37       20 38                     10 52
                                                                              1 19 26
                                                                                 32 55
                                                                              7 18 49
                                              34 41                        64 8 34
                                                                          9 48
                                                                              6
                                                                              1560
                                                                              2
                                                               22 44 48 16 2335 54
                                                                         50 21 30 58
DOC (mg/l)




                                    1 242   46                  63
                               36                                          43         56
                                               40 5 28     36 43 927 20 14 44
                                                                          17
                                                                      48 20 48
                                                                        2740
                                                                         48        61
                                                            4      363349 41
                             3               37 29        43 43 3847 51 57
                                                                      44
                                  19 3628 37
                                   24                       2    6330
                                                                  3710
                        35       29
                                  39               27 20 4444 32 28 64
                                                 38 47 55 4 26
                                                                     25
                                          1      27 50 585616950 43 62
                                                   47
                                                  49     5 34 42 8
                                                          6 22
                                           39            49     45
                                      3937       7         52         22
                        45                  3440 54 41     15 61
                                           4251 28
                                                 35
                                                 40         60
                                  51       47
                                            45
                                             63
                                           51       3
                                     29
                                      3    49 22        50
                                  34
                  57                   25             53 41 62 55
                                                       20
                    2                             41             54
                         3                     10
                                                22             56
                                              40       31
             1               45
                               35
                                     42    5539




                                0.01                                                       0.1
                                 UV Absorbance (410 nm) /cm

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All doc is_not_the_same_abaker

  • 1. All DOC is not the same: DOC classified by functional properties and their environmental significance Andy Baker University of Birmingham a.baker.2@bham.ac.uk
  • 2. Battin et al. doi:10.1038/ngeo618 The microbial loop. Fenchel, doi:10.1016/j.jembe.2008.07.013
  • 3. (In predominantly natural systems) Evidence of DOC processing within rivers. DOC becomes increasingly ‘young’ in 14C age and hydrophilic with distance from source. Rivers evade CO2. Photodegradation and biodegradation occurs, arguably of all DOM fractions. Seasonal variations in riverine DOM character, typically a hydrophobic / aromatic ‘flush’. Differences in DOM character between catchments, depending on soil type, land cover and human impact. Evidence of greater variability in DOC characteristics in headwaters and low order streams with ‘fresh’ DOM. Downstream DOC might be 14C ‘young’, but it is more homogenous and biogeochemically ‘aged’. Anthropogenic inputs typically introduce hydrophilic, relatively colourless, DOC. Clear links between DOC character and function. Aromatic DOC has greater chemical and ecological function (metal binding, contaminant binding, UV screening), and is easy to treat. Hydrophilic DOC difficult to remove during drinking water treatment.
  • 4. Peak C fluorescence Time / Processing Variable and high fluorescence / g C in bog waters Less variable and less fluorescent / g C river waters IHSS standards have atypically low fluorescence
  • 5. Mean and standard deviation colour/DOC CBweir 10.7 (1.4) Pweir 10.0 (1.2) PGweir 8.4 (2.5) ME 10.8 (3.7) MC 9.5 (0.8) Different DOC character FE 12.4 (3.7) between sub-catchments FC 11.5 (2.0) ‘fresh’ DOC is more coloured CB we ir P we ir PG we ir ME MC FE FC 1500 Peak Cint/a340 1250 1000 750 ‘fresh’ DOC is more fluorescent 500 per unit absorbance 250
  • 6. Photodegradation of lignin over two months Lignin phenol concentration and relationship with optical characteristics through the ‘wet’
  • 7.
  • 8.
  • 9. Summary River microbial ecosystem processes DOC. Aromatic bonds in DOC relatively easier to break. DOC therefore less aromatic with residence /travel time. Easily measured ‘in-situ’ using UV absorbance or fluorescence. River experience seasonal variations in riverine DOC character. Typically with ‘flush’ of relatively fresh (therefore aromatic) DOC. Groundwater rivers will have a groundwater hydrophilic DOC source. Catchment mean DOC character depending on soil type, land cover and human impact. Evidence of greater variability in DOC characteristics in headwaters and low order streams with ‘fresh’ DOM; variability decreases downstream as this is processed. Anthropogenic inputs typically introduce relatively hydrophilic, colourless, DOC. Aromatic DOC has greater chemical and ecological function (metal binding, contaminant binding, UV screening), and is easy to treat. Hydrophilic DOC difficult to remove during drinking water treatment.
  • 10. 2 13 13 7 14 14 1713 17 27 32 14 8 33 17 4723 851821 3315 60 2611 18 661 61 30 32 11 21 30 6213 12 12 611 23 11 12 1626 16 15 29 28 25 21 18 11 18 10 12 2310 2130 26 9 32 19 6 2312 33 38 1 46 46 60 417 24 14 25 864 10 46 463831 7 16 63 59 25 62 31 36 15 13 50 33 3 37 20 38 10 52 1 19 26 32 55 7 18 49 34 41 64 8 34 9 48 6 1560 2 22 44 48 16 2335 54 50 21 30 58 DOC (mg/l) 1 242 46 63 36 43 56 40 5 28 36 43 927 20 14 44 17 48 20 48 2740 48 61 4 363349 41 3 37 29 43 43 3847 51 57 44 19 3628 37 24 2 6330 3710 35 29 39 27 20 4444 32 28 64 38 47 55 4 26 25 1 27 50 585616950 43 62 47 49 5 34 42 8 6 22 39 49 45 3937 7 52 22 45 3440 54 41 15 61 4251 28 35 40 60 51 47 45 63 51 3 29 3 49 22 50 34 57 25 53 41 62 55 20 2 41 54 3 10 22 56 40 31 1 45 35 42 5539 0.01 0.1 UV Absorbance (410 nm) /cm