122
Fig. 4.29. Comparison of the
rates of oxidation of H2S by
Mn(IV) and Fe(III) (hydr)oxides in the Framvaren Fjord
and laboratory measurements
(Yao and Millero 1995a,b, 1996)
F. J. Millero
6.0 r - - - - - - - - - - - - - - - - - ,
_
Framvaren waters
5.0
c=::::J Gulf Stream (diluted toS= 21)
'i
4.0
c
·E
i 3.0
"' "
l 2.0
1.0
0.0
Fe(OH)3 (s)
aFeOOH
the oxic/anoxic interface and probably affects the distribution of products in the field.
The products (S20~-, SO;- and SO~-) formed during the oxidation in the Framvaren
Fjord and Cariaco Trench also have been examined and used to determine k!, k2 and
k 3 • The measured results are compared in Fig. 4.28 with the estimated values at the
same level of Fe. The agreement is quite good.
Yao and Millero (199sa,b) have examined how Fe 3 + (FeOOH) and Mn 4+ (Mn02) that
occur above the anoxic-oxic interface can oxidize hydrogen sulfide and complete the
redox cycle of these metals in anoxic waters. These reactions are much more complicated since the reactions occur on the surfaces of the oxide minerals. The rates of oxidation of H2S by Mn(IV) and Fe(I1I) (hydr)oxides in the water near the oxic/anoxic
interface were determined and compared with the values obtained in the surface waters of the Gulf Stream (Fig. 4.29) in the laboratory. The agreement is quite good. The
slightly higher oxidation rates observed in the field might be related to the microbiological activities near the interface.
References
Andersson LG, Dyrssen D and Hall POJ (1988) On the sulfur chemistry of a super-anoxic fjord,
Framvaren, South Norway. Mar Chern 23:283
Dyrssen D (1988) Sulfide complexation in surface seawater. Mar Chern 24:143-153
Fanning KA, Pilson MEQ (1972) A model for the anoxic zone of the Cariaco Trench. Deep-Sea Res
19:847-86
Grasshoff K (1975) The hydrochemistry of landlocked basins and fjords. In: Riley JP, Skirrow G (eds)
Chemical oceanography, 2nd edn, vol II. Academic Press, New York, pp 456-597
Haraldsson C, Westerlund S (1988) Trace metals in the water columns of the Black Sea and Framvaren
Fjord. Mar Chern 23:417-424
Jacobs L, Emerson S, Skei J (1985) Partitioning and transport of metals across the O/H.S interface in
a permanently anoxic basin: Framvaren Fjord, Norway. Geochim. Cosmochim. Acta 49:14331444
Millero FJ (1986) The thermodynamics and kinetics of the hydrogen sulfide system in natural waters. Mar Chern 18:121-147
Millero FJ (1991a) The oxidation of H2S in Black Sea waters. Deep-Sea Res 38(S2):S1139-S1150
Millero FJ (1991b) The oxidation of H2S in Framvaren Fjord. Limnol Oceanogr 36(5):1007-1014
Millero FJ (1991C) The oxidation of H2S in Chesapeake Bay, Estuarine. Coastal Shelf Sci 33:21-527
Millero FJ (1996) Chemical oceanography. CRC press, Boca Raton
Fig. 4.29. Comparison of the
rates of oxidation of H2S by
Mn(IV) and Fe(III) (hydr)oxides in the Framvaren Fjord
and laboratory measurements
(Yao and Millero 1995a,b, 1996)
F. J. Millero
6.0 r - - - - - - - - - - - - - - - - - ,
_
Framvaren waters
5.0
c=::::J Gulf Stream (diluted toS= 21)
'i
4.0
c
·E
i 3.0
"' "
l 2.0
1.0
0.0
Fe(OH)3 (s)
aFeOOH
the oxic/anoxic interface and probably affects the distribution of products in the field.
The products (S20~-, SO;- and SO~-) formed during the oxidation in the Framvaren
Fjord and Cariaco Trench also have been examined and used to determine k!, k2 and
k 3 • The measured results are compared in Fig. 4.28 with the estimated values at the
same level of Fe. The agreement is quite good.
Yao and Millero (199sa,b) have examined how Fe 3 + (FeOOH) and Mn 4+ (Mn02) that
occur above the anoxic-oxic interface can oxidize hydrogen sulfide and complete the
redox cycle of these metals in anoxic waters. These reactions are much more complicated since the reactions occur on the surfaces of the oxide minerals. The rates of oxidation of H2S by Mn(IV) and Fe(I1I) (hydr)oxides in the water near the oxic/anoxic
interface were determined and compared with the values obtained in the surface waters of the Gulf Stream (Fig. 4.29) in the laboratory. The agreement is quite good. The
slightly higher oxidation rates observed in the field might be related to the microbiological activities near the interface.
References
Andersson LG, Dyrssen D and Hall POJ (1988) On the sulfur chemistry of a super-anoxic fjord,
Framvaren, South Norway. Mar Chern 23:283
Dyrssen D (1988) Sulfide complexation in surface seawater. Mar Chern 24:143-153
Fanning KA, Pilson MEQ (1972) A model for the anoxic zone of the Cariaco Trench. Deep-Sea Res
19:847-86
Grasshoff K (1975) The hydrochemistry of landlocked basins and fjords. In: Riley JP, Skirrow G (eds)
Chemical oceanography, 2nd edn, vol II. Academic Press, New York, pp 456-597
Haraldsson C, Westerlund S (1988) Trace metals in the water columns of the Black Sea and Framvaren
Fjord. Mar Chern 23:417-424
Jacobs L, Emerson S, Skei J (1985) Partitioning and transport of metals across the O/H.S interface in
a permanently anoxic basin: Framvaren Fjord, Norway. Geochim. Cosmochim. Acta 49:14331444
Millero FJ (1986) The thermodynamics and kinetics of the hydrogen sulfide system in natural waters. Mar Chern 18:121-147
Millero FJ (1991a) The oxidation of H2S in Black Sea waters. Deep-Sea Res 38(S2):S1139-S1150
Millero FJ (1991b) The oxidation of H2S in Framvaren Fjord. Limnol Oceanogr 36(5):1007-1014
Millero FJ (1991C) The oxidation of H2S in Chesapeake Bay, Estuarine. Coastal Shelf Sci 33:21-527
Millero FJ (1996) Chemical oceanography. CRC press, Boca Raton