(Kalliokoski and Cathles, 1969; Rickard, 1970), and at the
other extreme, totally inorganic, based on their synthesis in
the laboratory and occurrence in igneous rocks and ore
deposits (Berner, 1969; Love and Amstutz, 1969; Farrand,
1970; Sunagawa et al., 1971; Sweeney and Kaplan, 1973;
Ostwald and England, 1979; Graham and Ohmoto, 1994).
Reviews of the different genesis of framboids are presented
by Love and Amstutz (1966), Rickard (1970), Kalliokoski
(1974), and Wilkin and Barnes (1997b), and a recent
review and description of crystallography, structure, and
origin is provided by Ohfuji et al. (2005).
Classifying precipitates as either biomediated mineralization or geological mineralization can be difficult. Often
it is not clear to which category the mineralization
belongs, as is the case for the precipitation of carbonates
and sulfides. The complexities of sulfide precipitations
are highlighted by Machel (2001). In a review of sulfate
reduction mechanisms (which would result in the
formation of pyrite framboids), Machel (2001) concluded
that the association of dissolved sulfate and hydrocarbons is thermodynamically unstable in nearly all
low-temperature environments and that redox reactions
would occur whereby sulfate is reduced by hydrocarbons
either bacterially (bacterial sulfate reduction) or inorganically (thermochemical sulfate reduction). As such, their
geological products are similar. Machel (2001) also concluded that in addition to iron sulfides, both galena
(PbS), and sphalerite [(Zn,Fe)S] can form as by-products
of hydrogen sulfide generation, if the appropriate transition or base metals are present or transported to
a bacterial sulfate reduction site or a thermochemical sulfate reduction site. In this context, generation of metallic
sulfides can be part of the bacterial sulfate reduction process (and be classified as biomediated mineralization) or
produced inorganically in the appropriate estuarine environment (and be classified as geological mineralization).
In addition, once they are precipitated, the sulfide crystals
can be subject to secondary alteration crystallographically
and mineralogically (i.e., diagenesis). The description by
Wilkin and Barnes (1997a) of the precipitation of iron
monosulfides, and various other mineral phases of iron
sulfide and their transformations, for instance, indicates
that the distinction between geological primary mineralization and secondary alteration (diagenesis) of the primary
precipitates can be complicated.
Mineralization in estuaries is manifest at several scales.
At the largest scale, the scale > 1 cm, it is expressed as
biomineralization within the shelly invertebrates and vertebrate fauna and as geological mineralization and diagenesis in the larger crystals, crusts, and nodules that may be
precipitated on tidal flats. At the next scale, the scale
$ 1 mm and less, it is expressed as interstitial precipitates
in geological mineralization and diagenesis and as biomineralization in the exoskeletons, tests, and frustules of
meiofauna, foraminifera, and diatoms. At the finest scale,
the scale of 1–100 mm (or less), it is expressed as pyritic
framboids and as carbonate crystals derived from
disintegrated calcareous algae or from bacterially
mediated mineral precipitates. In this range, though
representing the finest scale of mineralization (in the sense
of precipitation of mineral matter), it is the pyritic
framboids that are the most widespread mineralization
phenomenon in estuaries.
Bibliography
Addadi, L., Joester, D., Nudelman, F., and Weiner, S., 2006.
Mollusk shell formation: a source of new concepts for
understanding biomineralization processes. Chemistry (Weinheim
an der Bergstrasse, Germany), 12(4), 980–987.
Barton, L. L., and Fauque, G. D., 2009. Biochemistry, physiology
and biotechnology of sulfate-reducing bacteria. Advances in
Applied Microbiology, 68, 41–98.
Bates, L., and Jackson, J. A. (eds.), 1987. Glossary of Geology.
Alexandria, VA: American Geological Institute.
Bathurst, R. G. C., 1975. Carbonate Sediments and Their Diagenesis, 2nd edn. Amsterdam: Elsevier.
Berner, R. A., 1969. The synthesis of framboidal pyrite. Economic
Geology, 64, 383–384.
Berner, R. A., 1978. Sulphate reduction and the rate of deposition of
marine sediments. Earth and Planetary Science Letters, 37,
492–498.
Bush, R. T., McGrath, R., and Sullivan, L. A., 2004. Occurrence of
marcasite in an organic-rich Holocene estuarine mud. Soil
Research, 42(6), 617–621.
Campana, S. E., 1999. Chemistry and composition of fish otoliths:
pathways, mechanisms and applications. Marine Ecology Progress Series, 188, 263–297.
Canfield, D. E., and Raiswell, R., 1999. The evolution of the sulfur
cycle. American Journal of Science, 299, 697–723.
Canfield, D. E., Glazer, A. N., and Falkowski, P. G., 2010. The evolution and future of Earth’s nitrogen cycle. Science, 330,
192–196.
Carlstrom, D., 1957. The crystal structure of a-chitin (N-acetyl-Dglucosamine). Journal of Biophysical and Biochemical Cytology, 3(5), 669–683.
Carriker, M. R., 1961. Comparative functional morphology of boring mechanisms in gastropods. American Zoologist, 1, 263–266.
Castanier, S., Le Metayer-Levrel, G., and Perthusoit, J.-P., 2000.
Bacterial roles in the precipitation of carbonate minerals.
In Riding, R. E., and Awramik, S. M. (eds.), Microbial
Sediments. Berlin: Springer.
Clark, G. R., II, and Lutz, R. A., 1980. Pyritization in the shells of
living bivalves. Geology, 8(6), 268–271.
Cook, P. J., 1973. Supratidal environment and geochemistry of
some recent dolomite concretions, Broad Sound, Queensland,
Australia. Journal of Sedimentary Petrology, 43(4), 998–1011.
Cook, P. J., and Mayo, W., 1980. Geochemistry of a Tropical
Estuary and Its Catchment – Broad Sound Queensland.
Canberra: Australian Government Publishing Service. Bureau
of Mineral Resources, Geology and Geophysics Bulletin,
Vol. 182, p. 211.
Davies, G. R., 1970. Carbonate bank sedimentation, eastern Shark
Bay, Western Australia. In Logan, B. W. (ed.), Carbonate Sedimentation and Environments Shark Bay Western Australia.
Tulsa, Oklahoma: American Association of Petroleum Geologists. American Association of Petroleum Geologists Memoir,
Vol. 13, pp. 85–168.
Dennell, R., 1960. Integument and exoskeleton. In Waterman, T. H.
(ed.), The Physiology of Crustacea. volume 1 – Metabolism and
Growth. New York: Academic Press, pp. 449–472.
Diebel, C. E., Proksch, R., Greenk, C. R., Neilson, P., and Walker,
M. M., 2000. Magnetite defines a vertebrate magnotoreceptor.
Nature, 406, 299–302.
MINERALIZATION
445
other extreme, totally inorganic, based on their synthesis in
the laboratory and occurrence in igneous rocks and ore
deposits (Berner, 1969; Love and Amstutz, 1969; Farrand,
1970; Sunagawa et al., 1971; Sweeney and Kaplan, 1973;
Ostwald and England, 1979; Graham and Ohmoto, 1994).
Reviews of the different genesis of framboids are presented
by Love and Amstutz (1966), Rickard (1970), Kalliokoski
(1974), and Wilkin and Barnes (1997b), and a recent
review and description of crystallography, structure, and
origin is provided by Ohfuji et al. (2005).
Classifying precipitates as either biomediated mineralization or geological mineralization can be difficult. Often
it is not clear to which category the mineralization
belongs, as is the case for the precipitation of carbonates
and sulfides. The complexities of sulfide precipitations
are highlighted by Machel (2001). In a review of sulfate
reduction mechanisms (which would result in the
formation of pyrite framboids), Machel (2001) concluded
that the association of dissolved sulfate and hydrocarbons is thermodynamically unstable in nearly all
low-temperature environments and that redox reactions
would occur whereby sulfate is reduced by hydrocarbons
either bacterially (bacterial sulfate reduction) or inorganically (thermochemical sulfate reduction). As such, their
geological products are similar. Machel (2001) also concluded that in addition to iron sulfides, both galena
(PbS), and sphalerite [(Zn,Fe)S] can form as by-products
of hydrogen sulfide generation, if the appropriate transition or base metals are present or transported to
a bacterial sulfate reduction site or a thermochemical sulfate reduction site. In this context, generation of metallic
sulfides can be part of the bacterial sulfate reduction process (and be classified as biomediated mineralization) or
produced inorganically in the appropriate estuarine environment (and be classified as geological mineralization).
In addition, once they are precipitated, the sulfide crystals
can be subject to secondary alteration crystallographically
and mineralogically (i.e., diagenesis). The description by
Wilkin and Barnes (1997a) of the precipitation of iron
monosulfides, and various other mineral phases of iron
sulfide and their transformations, for instance, indicates
that the distinction between geological primary mineralization and secondary alteration (diagenesis) of the primary
precipitates can be complicated.
Mineralization in estuaries is manifest at several scales.
At the largest scale, the scale > 1 cm, it is expressed as
biomineralization within the shelly invertebrates and vertebrate fauna and as geological mineralization and diagenesis in the larger crystals, crusts, and nodules that may be
precipitated on tidal flats. At the next scale, the scale
$ 1 mm and less, it is expressed as interstitial precipitates
in geological mineralization and diagenesis and as biomineralization in the exoskeletons, tests, and frustules of
meiofauna, foraminifera, and diatoms. At the finest scale,
the scale of 1–100 mm (or less), it is expressed as pyritic
framboids and as carbonate crystals derived from
disintegrated calcareous algae or from bacterially
mediated mineral precipitates. In this range, though
representing the finest scale of mineralization (in the sense
of precipitation of mineral matter), it is the pyritic
framboids that are the most widespread mineralization
phenomenon in estuaries.
Bibliography
Addadi, L., Joester, D., Nudelman, F., and Weiner, S., 2006.
Mollusk shell formation: a source of new concepts for
understanding biomineralization processes. Chemistry (Weinheim
an der Bergstrasse, Germany), 12(4), 980–987.
Barton, L. L., and Fauque, G. D., 2009. Biochemistry, physiology
and biotechnology of sulfate-reducing bacteria. Advances in
Applied Microbiology, 68, 41–98.
Bates, L., and Jackson, J. A. (eds.), 1987. Glossary of Geology.
Alexandria, VA: American Geological Institute.
Bathurst, R. G. C., 1975. Carbonate Sediments and Their Diagenesis, 2nd edn. Amsterdam: Elsevier.
Berner, R. A., 1969. The synthesis of framboidal pyrite. Economic
Geology, 64, 383–384.
Berner, R. A., 1978. Sulphate reduction and the rate of deposition of
marine sediments. Earth and Planetary Science Letters, 37,
492–498.
Bush, R. T., McGrath, R., and Sullivan, L. A., 2004. Occurrence of
marcasite in an organic-rich Holocene estuarine mud. Soil
Research, 42(6), 617–621.
Campana, S. E., 1999. Chemistry and composition of fish otoliths:
pathways, mechanisms and applications. Marine Ecology Progress Series, 188, 263–297.
Canfield, D. E., and Raiswell, R., 1999. The evolution of the sulfur
cycle. American Journal of Science, 299, 697–723.
Canfield, D. E., Glazer, A. N., and Falkowski, P. G., 2010. The evolution and future of Earth’s nitrogen cycle. Science, 330,
192–196.
Carlstrom, D., 1957. The crystal structure of a-chitin (N-acetyl-Dglucosamine). Journal of Biophysical and Biochemical Cytology, 3(5), 669–683.
Carriker, M. R., 1961. Comparative functional morphology of boring mechanisms in gastropods. American Zoologist, 1, 263–266.
Castanier, S., Le Metayer-Levrel, G., and Perthusoit, J.-P., 2000.
Bacterial roles in the precipitation of carbonate minerals.
In Riding, R. E., and Awramik, S. M. (eds.), Microbial
Sediments. Berlin: Springer.
Clark, G. R., II, and Lutz, R. A., 1980. Pyritization in the shells of
living bivalves. Geology, 8(6), 268–271.
Cook, P. J., 1973. Supratidal environment and geochemistry of
some recent dolomite concretions, Broad Sound, Queensland,
Australia. Journal of Sedimentary Petrology, 43(4), 998–1011.
Cook, P. J., and Mayo, W., 1980. Geochemistry of a Tropical
Estuary and Its Catchment – Broad Sound Queensland.
Canberra: Australian Government Publishing Service. Bureau
of Mineral Resources, Geology and Geophysics Bulletin,
Vol. 182, p. 211.
Davies, G. R., 1970. Carbonate bank sedimentation, eastern Shark
Bay, Western Australia. In Logan, B. W. (ed.), Carbonate Sedimentation and Environments Shark Bay Western Australia.
Tulsa, Oklahoma: American Association of Petroleum Geologists. American Association of Petroleum Geologists Memoir,
Vol. 13, pp. 85–168.
Dennell, R., 1960. Integument and exoskeleton. In Waterman, T. H.
(ed.), The Physiology of Crustacea. volume 1 – Metabolism and
Growth. New York: Academic Press, pp. 449–472.
Diebel, C. E., Proksch, R., Greenk, C. R., Neilson, P., and Walker,
M. M., 2000. Magnetite defines a vertebrate magnotoreceptor.
Nature, 406, 299–302.
MINERALIZATION
445