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Carbon-sulfur-iron relationships in sedimentary rocks from southwestern Taiwan: influence of geochemical environment on greigite and pyrrhotite formation

Carbon-sulfur-iron relationships in sedimentary rocks from southwestern Taiwan: influence of geochemical environment on greigite and pyrrhotite formation
Carbon-sulfur-iron relationships in sedimentary rocks from southwestern Taiwan: influence of geochemical environment on greigite and pyrrhotite formation
The importance of the magnetic iron sulfide minerals, greigite (Fe3S4) and pyrrhotite (Fe7S8), is often underappreciated in geochemical studies because they are metastable with respect to pyrite (FeS2). Based on magnetic properties and X-ray diffraction analysis, previous studies have reported widespread occurrences of these magnetic minerals along with magnetite (Fe3O4) in two thick Plio-Pleistocene marine sedimentary sequences from southwestern Taiwan. Different stratigraphic zones were classified according to the dominant magnetic mineral assemblages (greigite-, pyrrhotite-, and magnetite-dominated zones). Greigite and pyrrhotite are intimately associated with fine-grained sediments, whereas magnetite is more abundant in coarse-grained sediments. We measured total organic carbon (TOC), total sulfur (TS), total iron (FeT), 1N HCl extractable iron (FeA), and bulk sediment grain size for different stratigraphic zones in order to understand the factors governing the formation and preservation of the two magnetic iron sulfide minerals. The studied sediments have low TS/FeA weight ratios (0.03-0.2), far below that of pyrite (1.15), which indicates that an excess of reactive iron was available for pyritization. Observed low TS (0.05-0.27%) is attributed to the low organic carbon contents (TOC=0.25-0.55%), which resulted from dilution by rapid terrigenous sedimentation. The fine-grained sediments also have the highest FeT and FeA values. We suggest that under conditions of low organic carbon provision, the high iron activity in the fine-grained sediments may have removed reduced sulfur so effectively that pyritization was arrested or retarded, which, in turn, favored preservation of the intermediate magnetic iron sulfides. The relative abundances of reactive iron and labile organic carbon appear to have controlled the transformation pathway of amorphous FeS into greigite or into pyrrhotite. Compared to pyrrhotite-dominated sediments, greigite-dominated sediments are finer-grained and have higher FeA but lower TS. We suggest that diagenetic environments with higher supply of reactive iron, lower supply of labile organic matter, and, consequently, lower sulfide concentration result in relatively high Eh conditions, which favor formation of greigite relative to pyrrhotite
0009-2541
153-168
Kao, S-J.
abf735a8-c070-4692-8611-70468ac6ace8
Horng, C-S.
2961ce90-a6c3-4b7f-b464-a2a9fb507ea9
Roberts, A.P.
4497b436-ef02-428d-a46e-65a22094ba52
Liu, K-K.
5f15de5e-7202-4311-9788-e2726c4847ce
Kao, S-J.
abf735a8-c070-4692-8611-70468ac6ace8
Horng, C-S.
2961ce90-a6c3-4b7f-b464-a2a9fb507ea9
Roberts, A.P.
4497b436-ef02-428d-a46e-65a22094ba52
Liu, K-K.
5f15de5e-7202-4311-9788-e2726c4847ce

Kao, S-J., Horng, C-S., Roberts, A.P. and Liu, K-K. (2004) Carbon-sulfur-iron relationships in sedimentary rocks from southwestern Taiwan: influence of geochemical environment on greigite and pyrrhotite formation. Chemical Geology, 203 (1-2), 153-168. (doi:10.1016/j.chemgeo.2003.09.007).

Record type: Article

Abstract

The importance of the magnetic iron sulfide minerals, greigite (Fe3S4) and pyrrhotite (Fe7S8), is often underappreciated in geochemical studies because they are metastable with respect to pyrite (FeS2). Based on magnetic properties and X-ray diffraction analysis, previous studies have reported widespread occurrences of these magnetic minerals along with magnetite (Fe3O4) in two thick Plio-Pleistocene marine sedimentary sequences from southwestern Taiwan. Different stratigraphic zones were classified according to the dominant magnetic mineral assemblages (greigite-, pyrrhotite-, and magnetite-dominated zones). Greigite and pyrrhotite are intimately associated with fine-grained sediments, whereas magnetite is more abundant in coarse-grained sediments. We measured total organic carbon (TOC), total sulfur (TS), total iron (FeT), 1N HCl extractable iron (FeA), and bulk sediment grain size for different stratigraphic zones in order to understand the factors governing the formation and preservation of the two magnetic iron sulfide minerals. The studied sediments have low TS/FeA weight ratios (0.03-0.2), far below that of pyrite (1.15), which indicates that an excess of reactive iron was available for pyritization. Observed low TS (0.05-0.27%) is attributed to the low organic carbon contents (TOC=0.25-0.55%), which resulted from dilution by rapid terrigenous sedimentation. The fine-grained sediments also have the highest FeT and FeA values. We suggest that under conditions of low organic carbon provision, the high iron activity in the fine-grained sediments may have removed reduced sulfur so effectively that pyritization was arrested or retarded, which, in turn, favored preservation of the intermediate magnetic iron sulfides. The relative abundances of reactive iron and labile organic carbon appear to have controlled the transformation pathway of amorphous FeS into greigite or into pyrrhotite. Compared to pyrrhotite-dominated sediments, greigite-dominated sediments are finer-grained and have higher FeA but lower TS. We suggest that diagenetic environments with higher supply of reactive iron, lower supply of labile organic matter, and, consequently, lower sulfide concentration result in relatively high Eh conditions, which favor formation of greigite relative to pyrrhotite

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Published date: 2004

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Local EPrints ID: 1253
URI: http://eprints.soton.ac.uk/id/eprint/1253
ISSN: 0009-2541
PURE UUID: 8f257a74-29a3-410b-8436-f3cd200bca5c

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Date deposited: 07 Apr 2004
Last modified: 15 Mar 2024 04:42

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Contributors

Author: S-J. Kao
Author: C-S. Horng
Author: A.P. Roberts
Author: K-K. Liu

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