INTRODUCTION
I.2 Geologic Archives of the Ancient Marine Sulfur Cycle
100, 172, 264], outstanding questions regarding the history of the marine sulfur cycle still abound. How faithfully do existing sulfate δ34S records preserve the ac- tual δ34S of primary seawater sulfate? Could temporal changes inδ34Sinandδ34S be responsible for some of the seawater δ34S changes that have traditionally been attributed to changes in the amount of pyrite burial? What other processes (e.g.
hydrothermal circulation) may add important complications to the one input, two output topology depicted in Figure I.1? This thesis attempted to address each of these questions through a combination of new sulfur isotope abundance measurements and mathematical modeling. Temporal variation inδ34S appears to be a particularly significant source of uncertainty that deserves more atten- tion, as changes in both the ε associated with sedimentary sulfur cycling and the role of reactive transport processes (i.e., diffusion, advection, and reaction) in translating ε into aδ34S within a given environment have not been constant in either space or time. This work identifies some of the processes that may be important in forcing temporal change in these parameters. In the following, we have briefly reviewed the geologic archives that are measured as records of sulfur cycle processes. We have also identified the methods that have been de- veloped for making sulfur isotope abundance measurements. Descriptions of the benefits and shortcomings of each archive and measurement method are followed by an outline of the remainder of this thesis.
I.2.1 Sulfate S archives I.2.1.1 Sulfate minerals
Sulfate evaporite minerals are found in the geologic record across much of Earth history (e.g. [33, 72]) and were a target for many of the earliest studies of S isotopic variation among geologic materials [11, 337, 338]. Such minerals — mainly gypsum and anhydrite (CaSO4) — are attractive given their high S con- tent and their deposition with little to no S isotopic fractionation relative to ma- rine SO42− [268]. However, precipitation of evaporite minerals is mostly lim- ited to restricted basins in which evaporation exceeds precipitation. Such basins have not been constant in their abundance throughout geologic time [72, 126]
and may experience δ34S variations reflecting local influences rather than global S cycle changes (e.g. [99]). Evaporite deposits are also often difficult to date due to a lack of diagnostic biostratigraphic markers. These factors have led to tem- poral records that demonstrate substantial (> 20h) Phanerozoic δ34S variability, but with gaps and uncertainties in the timing and global significance of varia- tion.
Barite (BaSO4) is found in recent marine sediments and has also been targeted in studies of marine SO42−δ34S variations [252, 254]. Records generated from this archive [252, 254] are notable for their precision and stratigraphic continuity, but are limited in their temporal extent. Barite begins to dissolve upon quan- titative consumption of SO42− (e.g. [290]) and is only consistently preserved in sediments that have been too organic-poor for complete pore water SO42−
consumption throughout their histories. This dissolution has allowed marine barite δ34S records to be extended from the present only to the mid-Cretaceous [254]. Open questions regarding the microenvironments in which barite forms in seawater [253] and the degree to which these microenvironments are altered from seawater in their fluid composition (e.g. [29]) have also limited detailed evaluation of the accuracy of these records.
I.2.1.2 Minor / trace components of other minerals
In addition to precipitating as sulfate minerals, SO42− ion may substitute for other polyatomic anions (e.g. CO32−,PO43−) in mineral lattices. Calcite (CaCO3), an ubiquitous mineral present in marine rocks throughout geologic
time, has been the most commonly targeted mineral in studies of this substi- tuted SO42−. Early studies demonstrated the presence of sulfate at 1000+ ppm (w/w) abundances in inorganic calcites [53, 330], calcitic and aragonitic skele- tons [318], and bulk ancient carbonates [106]. Pioneering works by Popp (1985) [259] and Burdett, Arthur, and Richardson (1989) [49] also established the po- tential for the δ34S of this carbonate associated sulfate (CAS) to reflect the δ34S of contemporaneous marine SO42–. Stratigraphic continuity and easy biostrati- graphic correlation have enabled δ34S records of impressive temporal resolution and extent (e.g. [172, 279]) to be generated in the several decades since these studies. However, recent works [262, 263, 278] have also demonstrated poten- tial for CAS abundance and δ34S to be altered during burial recrystallization.
Great care must be taken to identify and sample phases thought to contain CAS derived from unaltered seawater to ensure the accuracy of such records (e.g.
[262, 263]). Offsets in δ34S related to equilibrium and kinetic fractionations [15, 243, 244] may add further complications.
Sulfate present as a minor component in the calcium phosphate mineral apatite (Ca5(PO4)3(OH,F,Cl)) has also been targeted as a potential archive of marine SO42−δ34S [16, 34, 74, 114, 216, 235, 258, 307, 368]. Sedimentary apatite is pre- cipitated by biomineralizing organisms to form bones, teeth, and skeletons (e.g.
[113]) and may additionally precipitate authigenically during early diagenesis, sometimes in large quantities (e.g. phosphorites; [216]). Although sulfate is present at significant concentrations (up to several wt%) in phosphorites [16, 34, 74, 114, 216, 235, 258], isotopic studies have shown that the δ34S of phosphate associated sulfate (PAS) is frequently enriched in34S relative to seawater SO42−
due to incorporation of pore water SO42−in sulfate-reducing environments [16, 74, 216, 235, 258]. Lower sulfate abundances (typically < 1 wt%) have limited S isotopic studies of biogenic apatites [113]. Studies targeting such samples [113, 368] are too few in number to draw robust conclusions, but have been at least moderately successful in producing PAS δ34S measurements close to the δ34S of coeval biogenic CAS [368].
I.2.2 Sulfide S archives
I.2.2.1 Sulfide and disulfide minerals
S cycling in marine sediments produces solid phases that are extremely variable in their δ34S across modern environments (e.g. [59]). Consequently, the infor- mation gathered from the δ34S of solid phases at a given site is typically local in its relevance, though compilations of data from many environments [56, 57, 58, 100] may facilitate an understanding of global trends (e.g. [195, 369]).
Pyrite is the most common H2S-derived phase targeted for δ34S measurements and often constitutes the majority of the solid phase S present in marine sedi- ments (e.g. [149, 311, 336]). This mineral is formed via the authigenic precipita- tion of iron monosulfide (FeS) from dissolved Fe2+and H2S, plus a subsequent reaction of FeS with another S species (e.g. S0) to form pyrite [217, 285]. Pyrite is ubiquitous in sedimentary rocks and is typically extracted from sediments us- ing strong reducing agents to form H2S that can be collected in a chemical trap (e.g. [61]), though strong oxidizing agents may also be used if quantitative ex- traction is not crucial (e.g. [274]). Temporal pyrite δ34S records are generated with ease, but again, high pyrite δ34S variability exists at spatial scales ranging from individual grains (e.g. [46]) to different depositional environments (e.g.
[59]). This, combined with the potential for late diagenetic and/or metamorphic pyrite formation (e.g. [193]) generally limits the utility of data from a given site to understanding local processes.
I.2.2.2 Organic S
Organic S is an understudied component of the marine S cycle. Though studies of its concentration and isotopic composition date back to some of the earliest S isotopic studies (e.g. [336]), only recently have concentrated efforts started to unravel the controls on its composition [273, 274, 303, 354, 355, 356]. The rela- tive dearth of studies is surprising given the significance of organic S as a solid phase S output in sediments that are particularly organic-rich and/or Fe-poor (e.g. [275, 303]). Existing studies suggest that organic S is typically enriched in 34S relative to codepositional pyrite [149, 274, 275] and may reflect longer- term sulfurization reactions between organic matter and pore water H2S during burial (e.g. [272]). More work is required to understand the quantitative im-
portance of this flux throughout Earth history and its potential effects on the marine S cycle (esp. the δ34S of seawater).