Stable Isotope Tests of Evaporative Marine Environments in the Late Silurian Tonoloway Formation of West Virginia

Deborah Fishbeck Advisor: Dr. Alan J. Kaufman Geology 394 4.25.16

II. Table of Contents I. Title Page …………………………………….………..……………………………..1 II. Table of Contents …………………………………………………………………….2 III. Abstract……………………………………………………………………..………...3 IV. Introduction…………………………………………….…………………………….3 V. Hypothesis……………………………………………….……………………..…….5 VI. Geologic Background………………………………….……………………………..5 VII. Methods of Analysis………………………………………….………...... 11 VIII. Results…………………………………………………………………...... 19 IX. Discussion of results………………………………………………………………....27 X. Suggestions for Future work……………………………………………………...….29 XI. Conclusion and Broader Implications…………………………………………..……29 XII. Acknowledgements………………………………………………………………..…30 XIII. Bibliography………………………………………………………………………....31 XIV. Appendix …………………………………………………………………………....34

Figures and Tables Figure 1: Sedimentary Features Found in the Outcrop…………………………………………..3 Figure 2: Silurian and Devonian Lithologic Units of the Appalachian………………………….4 Figure 3: Seawater δ13C Isotopic curve………………………………………………………….4 Figure 4: Percent of Water Evaporated for Evaporite Mineral Formation……………………....5 Figure 5: Framboidal Pyritization of Ostracod fossils ………..…………………………………5 Figure 6: Supratidal, Intertidal, and Subtidal Depositional Zones …………………………..….6 Figure 7: Laminated Micrite………..……………………………………………………………6 Figure 8: Sabkha Tidal Facies…………………………………………………….…..…………7 Figure 9: Intraclastic Brecciation…………………………………………………………..……8 Figure 10: Silurian Seawater Isotopic Compositions of δ13C and δ18O ‰VPDB…………...…..9 Figure 11: Ostracode Shells……………………………………………………………….……11 FigureM1-M16: Instruments and Tools ………………………………………………………..19 Figure 12A-12G: Chemostratigraphic column of Tonoloway Outcrop…………………...……20 Figure 13: Sub-sampling Sites ……………………………………………………………..…..22 Figure 14: δ 13C and δ 18O Values for Sedimentary Textures……………………………….….25 Figure 15: δ 13C and δ 18O Values for Brecciated and Non-Brecciated Dolomicrite………...…25 Figure 16: δ 13C and δ 18O Values for Lithologies…………………………………………...…26 Figure 17: δ 13C and δ 18O Range and Standard Deviation for Lithologies……………………26 Figure 18: Models of Evaporative Dolomitization………………………………………….….27 Figure 19: Weight Percent Organic Carbon versus Weight Percent Pyrite……………..…..….29 Table 1: Carbonate Carbon and Oxygen JTB Standards………………………………….……16 Table 2: Organic Carbon Urea Standards……………………………………………….……...16 Table 3: Pyrite Sulfur NBS-127 and NBS1 standards_4.1.16………………………………….17 Table 4: Pyrite Sulfur NBS-127 and NBS1 standards_4.6.16………………………………….17 Table 5: Subsampling sites; δ13C and δ18O…………………………………………………….22 Table 6: Summary of Chemical Signals by Sedimentary Texture……………………………..24 Table 7: Summary of Chemical Signals by Lithology……………………………….…….…..24

III. Abstract This research project focused on the Late Silurian Tonoloway Formation, which is well- exposed in fresh outcrops along Corridor H in West Virginia. The carbonate-rich succession preserves sedimentary evidence of high degrees of seawater evaporation, in the form of mudcracks, halite-hoppers, and trace gypsum and anhydrite, which conceivably resulted in 18O and 13C enrichments in evaporitic facies relative to open marine environments. To test whether isotopic analyses might provide clues to ancient marine carbonates where sedimentary evidence for evaporation is lacking, I conducted a field and laboratory-based study of the Tonoloway Formation, including the construction of a stratigraphic column and collection of a suite of 43 samples for detailed petrographic and isotopic analysis. Results show that dolomitic facies are enriched in 18O and 13C relative to limestone facies by about 2‰ and 3‰, respectively. This suggests that dolomitization was related to the evaporative concentration of Mg in seawater through the precipitation of Ca-bearing carbonates and evaporites. Anomalous 34S enrichments reflect removal of sulfate from the water through pyrite burial and sulfate evaporate mineral precipitation.

IV. Introduction The Silurian was a period of overall warm climate and high sea levels, which allowed for shallow epeiric seas to form, and through evaporative concentration of seawater for carbonates and salts to accumulate widely. The Late Figure 1A, 1B- Images of sedimentary features Silurian Tonoloway Formation is comprised both marine found in the outcrop. Figure 1A shows vugs, and terrestrial sedimentary rocks, and contains ample with a 250 µm needle for scale. Figure 1B evidence for highly evaporative conditions including halite shows halite hoppers. hoppers, mud cracks, and trace amounts of sulfate evaporite minerals (Figure 1). A 40 meter section of the Tonoloway Formation near Moorefield, West Virginia was recently exposed due to the creation of the highway known as “Corridor H”. Construction of Corridor H began in 2000, and the highway was opened in 20051. The road cuts through Appalachian Paleozoic strata have thus only been exposed for 10-15 years, and subsequently have not undergone extensive weathering. Changes in lithology and sedimentary textures in the Tonoloway Formation provide us with clues about the local depositional setting. Because many ancient deposits do not preserve clear sedimentary evidence for evaporation, I want to investigate whether isotope distributions in the various carbonate facies may provide a tracer for physical, chemical, and biological processes, especially related to the evaporative concentration of seawater. In this study, I provide lithologic and chemostratigraphic data from a 40 meter section of the Tonoloway Formation, including carbonate carbon and oxygen, organic carbon, and pyrite sulfur isotope compositions to evaluate whether chemical and biologic effects are recorded in the shallow marine evaporitic carbonate environment.

1 http://www.wvcorridorh.com/route/map7.html

Figure 2- Silurian and Devonian Lithologic units of the Appalachian.

Figure 3- Seawater isotopic composition of δ13C from Middle Cambrian to Pennsylvanian Period. The age of the Tonoloway Formation is marked in red. As water evaporates, the lighter isotope of 16O preferentially leaves the body of water to 18 16 become gaseous H2O (Urey, 1946). Heavy O and light O are separated through an equilibrium isotope effect, which is the separation of substances due to a change in vibrational energies of the molecules, as represented by liquid water converting to water vapor. This process explains why fresh (or meteoric) water is typically depleted in 18O relative to seawater. Kinetic fractionation also drives the separation of isotopes through rate-limited biological processes. For example, organisms that photosynthesize preferentially use the lighter 12C, which leaves the surrounding environment enriched in 13C. A shallow evaporating body of water where light can reach the bottom water allows for photosynthesis, and a hypersaline evaporating body of

4 water would allow for only hypersaline tolerant organisms to, such as microbial mats. Carbon isotopes enter seawater through continental weathering in the form of bicarbonate ions, and can leave the body of water of water through precipitation of carbonates and as CO2 gas. High rates of 12 evaporation and degassing of CO2 in seawater enriches the remaining water, and associated minerals that form in heavy 13C (Horton, 2016).

In an evaporating body of water (Figure 4), over 90% of H2O has to evaporate out of seawater before halite can precipitate (Sonnenfield, 1984); in contrast, gypsum precipitates after about 80% of the water has evaporated. Trace amounts of gypsum have been found in the Tonoloway (Smosna and Warshauer, 1979) and the vugs (voids) in the Tonoloway rocks were likely once the site of gypsum minerals. Due to the presence of halite hoppers (casts of halite minerals, also called “salt casts”), it is clear that gypsum saturation was reached. Both gypsum precipitation, and burial of pyrite as a byproduct of microbial sulfate reduction (Figure 5) remove sulfur from seawater.

A C

B Figure 4- Percent of water evaporated from seawater for Figure 5a, 5b, 5c- Framboidal pyritization of Ostracod fossils. evaporite minerals to form. Edited figure (Sonnenfield, Needle width of 250 µm. 1984, pg. 103)

V. Hypothesis I hypothesize that strata containing textures indicative of an evaporitic and saline depositional environment will be enriched in 13C and 18O compared to non-evaporative facies, and that 13C and 34S abundances of organic matter and pyrite, which are biologically controlled, may also show anomalous enrichments due to environmental stress. My null hypothesis is that there will be no isotopic enrichments in evaporative strata compared to non-evaporative strata.

VI. Geologic Background Global Silurian The American subdivisions of the Silurian System are made of an Upper, Middle and Lower Silurian Series. The upper Silurian American Series, called the Cayugan series, consists of the Keyseran stage, Tonolowayan stage, and the Salinan stage. The Silurian Period overall was a time of relatively stable warm climate and high sea levels. In contrast, the terminal epoch of the Silurian, the Pridoli (423-419Ma), saw a relative fall in sea level (Johnson et al., 1991).

Glaciation and decreased hydrothermal activity or less rifting, can cause a decrease in sea level. Glaciation or decreased hydrothermal activity (resulting in less ridge volume) could both cause a decrease in global sea level. Two major positive carbon isotope anomalies are recorded in the Upper Silurian. The Ludfordian stage directly prior to the Pridoli Epoch, records a profound positive δ13C excursion to around +5‰, while the Silurian/Devonian boundary is marked by a second event up to +6‰ (Saltzman et al., 2002) (Figure 3). The latter event is believed to be related to either enhanced organic carbon burial or sea level fall and the erosion of 13C enriched carbonate into the oceans (Saltzman et al., 2002). The Pridoli Epoch evaporitic Tonoloway Formation, however, lies in the isotopic calm (with slightly negative δ13C values) between these two positive biogeochemical events. Tonoloway Lithology & Depositional environment Previous studies of Tonoloway lithofacies and depositional environment have been conducted by Bell (1997), Wintermute (1952), Chadwick (1994), Fritz-Miller (1971) and Smosna et al. (1977). While the studies vary slightly in their lithologic descriptions and terminology, they all interpret the depositional environment to be largely intertidal, subtidal and supratidal, (Figure 6) and containing evidence of evaporative environment. Figure 6- Schematic2of supratidal, intertidal, and subtidal depositional zones. Bell (1997) studied the evolution of Tonoloway depositional environments, using a combined facies analysis and sequence stratigraphy. He identified four lithofacies in the Tonoloway; shallow lagoon, open shelf, tempestites and peritidal, which is also called intertidal (Figure 6). The shallow lagoon facies consists of bedded mudstone, peloidal, oolitic, conglomeritic and algal (stromatolitic and thrombolitic) environments all deposited in carbonate mud to carbonate sand flats. The open shelf consists of crinoid rudstones, mixed skeletal, and nodular facies, which Bell interprets were deposited in moderate/high energy carbonate shoal and/or open marine. The tempestites facies consists of carbonate tempestites and was deposited on a storm dominated carbonate ramp. The intertidal lithofacies are characterized by flat to undulose laminites, which were deposited in a carbonate tidal flat. In contrast, dolomite was formed in a supratidal sabkhas. Siliciclastic calcareous or dolomitic sandstone were deposited in sub/intertidal flats and supratidal sabkha respectfully. The laminite lithology (Figure 7) is comprised of laminations which are couplets of thick light calcareous layers overlain by thin dark cryptalgal layer containing “crinkled” laminations, micrite and Figure 7- Laminated micrite, or micron-scale euhedral dolomite. Laminations range from thin to “laminite” in Tonoloway Formation. thick, where the thick laminations measure up to 1cm. Needle width of 250 µm

2 Edited image. Original retrieved from www.beg.utexas.edu

Laminations thin upward from bottom of sets, and dolomite and hexagonal mud cracks seem to increase towards the top of sets. Bell interprets an arid supratidal mud flat, or sabkha, depositional environment, indicated by dolomite containing sedimentary textures of trace anhydrite, vugs, stromatolitic laminae, desiccation cracks and tepee-like buckling, and low faunal diversity. This facies is found immediately above tidal flat laminates. Figure 8 below3 is a schematic of a sabkha, or arid tidal depositional environment, similar to those surrounding the Persian Gulf, as opposed to a humid tidal depositional environment, similar to the marshes of the Chesapeake Bay.

Figure 8- Sabkha tidal facies3 that consists of subtidal lagoon, algal mat, gypsum and anhydrite facies.

Bell concludes that the Tonoloway parasequences consist of meter scale, upward shallowing depositional packages, capped by intertidal to supratidal facies. Supratidal facies are inferred due to presence of mud-cracked laminites, and dolomitized and sandy terrestrial lithologies respectively. Additionally, thin mudstones and wackestones are the most common lithology in the Tonoloway, and flat to undulose laminites are the second most abundant facies in the Tonoloway Formation, representing open shelf and intertidal facies respectively. Bell concludes that the Tonoloway package records a history of depositional environment change that began as an epeiric seaway, then shifted to a ramp-to-lagoon due to a southwest-northeast transgression that brought increasingly open marine conditions north-eastward into the lagoon from the open shelf at which point water depths reached a peak 40 meters over the ramp and 30 meters over the shelf. Then a regression returned the depositional environment to a shallow, eperic seaway. Wintermute (1952) describes the Tonoloway as 800 feet (~243 meters) of sparsely fossiliferous impure limestone and impure to argillaceous dolomite in which the upper middle strata contain asymmetrical cyclothems of alternating limestone and dolostone. He distinguishes depositional environment of limestone from that of dolomite. He also notes that sedimentary

3 Edited graphic- original retrieved from https://geol.umd.edu/~jmerck/geol342_1501/lectures/15.html

features found in limestone- laminae, bands, ooids and intraformational conglomerates formed in well oxygenated shallow water no more than 10s of feet deep. Rapid accumulation of sediments caused environments to shallow, with a tendency to increase salinity and degree of dolomitization. Some dolostone was clearly exposed subaerially, as shown A B by diagnostic sedimentary features, including mudcracks and vugs, as well as teepees. Chadwick (1994) recognizes the same subtidal, intertidal, and supratidal facies. Subtidal facies are comprised of calcarenites, oolitic limestones, and fossiliferous limestones. Intertidal facies are comprised of cryptalgal limestones which he defines as flat laminated to domal stromatolites. The domal Figure 9A and 9B- Intraclastic Brecciation in stromatolites come from deeper-intertidal, and the flat Tonoloway samples. Needle width of 250 µm. laminites come from shallower-intertidal and contain desiccation cracks. The supratidal facies are recognized by massive, occasionally vuggy, dolomite. Fritz-Miller (1971) conducted a cluster analysis of Tonoloway and Keyser limestone facies based on physical and faunal criteria of supratidal, intertidal and subtidal facies. Samples were scored according to the set of factors, and a dendrogram constructed from the scores that showed eight clusters. Fritz-Miller (1971) infers one of the clusters to be supratidal, one to be subtidal, and the remaining six to be “near-shore” or shallow watered. The lack of environmental change indicated to Fritz-Miller an overall static condition with fluctuating near shore depositional environment. The thickness of the section suggested to these authors that the Tonoloway sediments built up in a subsiding basin with near equal rates of subsidence and accumulation. Smosna et al. (1977) divide the Tonoloway formation into three informal members, a lower, middle and upper member. The middle member is more fossiliferous biopelsparite and biomicrite deposited in subtidal waters. The upper and lower members contain dolomite and anhydrite and are inferred to be deposited in intertidal-supratidal mudflats in a closed evaporite basin affected by periodic influences of seawater. Chemical data from similar Upper Silurian rock Azmy et al. (1998) collected 236 calcitic brachiopod shells from localities worldwide to measure seawater isotopic composition for the entire Silurian. They subsampled the middle prismatic layer of the shells, which was determined to be the best preserved portions, and therefore retained the most primary isotopes signals. For the period, they found that the δ18O values ranged from -2‰ to -6.5‰, and δ13C values ranged from -1‰ to 7.5‰, respectively. They attribute high δ18O and δ13C to cold episodes of low sea level. Low δ18O and δ13C are attributed to warm episodes of high sea level (Azmy et al. 1998).The carbon and oxygen isotope values that Azmy determined was influenced by salinity, paleodepth, stratified oceans, glacial and short term secular changes of seawater isotope compositions. They conclude that slightly higher temperatures of ocean water, as the single controlling factor, cannot explain the low δ18O values. Due to brachiopods being tolerable to a narrow range of salinity, salinity gradients would only be a marginal factor affecting δ18O in brachiopods tested. Paleodepth can only account for

up to 1‰ of variation in isotopic data throughout all samples (Azmy et al, 1998Azmy et al. (1998) collected 236 calcitic brachiopod shells from localities worldwide to measure seawater isotopic composition for the entire Silurian. They subsampled the middle prismatic layer of the shells, which was determined to be the best preserved portions, and therefore retained the most primary isotopes signals. For the period, they found that the δ18O values ranged from -2‰ to - 6.5‰, and δ13C values ranged from - 1‰ to 7.5‰, respectively. They attribute high δ18O and δ13C to cold episodes of low sea level. Low δ18O and δ13C are attributed to warm episodes of high sea level (Azmy et al. 1998).The carbon and oxygen isotope values that Azmy determined was influenced by salinity, paleodepth, stratified oceans, glacial and short term secular changes of seawater isotope compositions. They conclude that slightly higher temperatures of ocean water, as the single controlling factor, cannot explain the low δ18O values. Salinity gradients would only be a marginal factor that Figure 10- Edited graphic from Azmy et al. (1998) of Silurian seawater 18 affects δ O in brachiopods tested, as isotopic compositions of δ13C and δ18O ‰VPDB showing a large they tolerate a narrow range of salinity. carbon excursions in the upper Ludlow. Paleodepth can only account for up to 1‰ of variation in isotopic data throughout all samples (Azmy et al, 1998).

Stratified oceans of warm saline deep water could account for a portion of the isotopic signature, due to evaporative episodes and sea-level high stands that cause dense warm saline δ18O rich water to circulate to lower depths. According to Azmy et al. (1998), glacial and short- term secular changes of seawater cannot explain the overall depletion of δ18O in the Silurian, even though there is a correlation of positive δ18O shifts with glacial episodes. However the authors support the theory of a long term evolution of seawater δ18O, where seawater δ18O decreases with age. The Silurian brachiopods have δ18O values of 4‰+/- 1‰ compared to Holocene brachiopods.

Wigforss-Lange (1999) studied 13C enrichments in marine deposits of terrigenous clastic rocks interlayed by shallow water carbonates from a Ludlow-Pridoli aged formation in Scania. In the formation were oncoid limestones; Oncoids are spherical structures caused by cyanobacterial activity and are indicative of warm waters of depths that sunlight can reach. Due to the presence

of oncoids, the depositional environment of the limestone was constrained to shallow marine waters in the photic zone. 12C preferentially enters the organic matter during periods of high photosynthetic activity, resulting in relatively more 13C to enrich the forming carbonate. While most of the sequence has δ13C values of -1.7 to +2.7 ‰ that corresponds to marine sea water composition, there is a carbon excursion of δ13C between +3.6 to +11.2 ‰ that coincides with a sea level lowstand. There is extreme 13C enrichment in oncoid limestones of δ13C values up to +11.2‰ PDB. Oncoid formation involves cyanobacterial and/or algal coatings of carbonate grains and probable reflects periods of high photosynthetic activity. Oxygen isotope composition ranging from -12.6 to -4.7‰ (PDB) are closer to Silurian sea water values. Wigforss-Lange (1999) finds less negative δ18O and unstable 18O/16O ratio recorded during the δ13C excursion that may be explained by evaporation and restricted water circulation. The low shallow sea levels allow for increased photosynthetic activity which produced oncoids in the limestone. This photosynthetic activity caused high 13C enrichment and less negative 18O depletion. Wigforss-Lange (1999) also suggests that an increase in burial rates of organic matter or primary productivity, leading to larger standing biomass, both result in preferential removal of 12C from the reservoir and subsequent 13C enrichment of the dissolved inorganic carbon. Samtleben et al. (1996) in his study of isotopic changes recorded in Silurian brachiopods of Sweden, found that oxygen isotope ratios reflect changes in palosalinites due to varied freshwater input, as opposed to the oxygen isotope ratios revealing a paleotemperature signal. Samtleben et al. (1996) also concludes that carbon isotope ratios are connected to global changes in burial of organic carbon, where high δ13C would be found in times of black shale deposition in euxinic waters. Paleoecological constraints of Ostracoda Ostracodes are one of the main fossils in the Tonoloway outcrop in this study. Additional fossils of brachiopods, stromatolites, and corals are found in other outcrops of the Tonoloway in the region. The presence of ostracode fossils alone does not constrain the depositional environment as these organisms are found in a diverse range of aquatic habitats from sulfur springs, to streams, to salt marshes. Identification of ostracode genus and species could provide additional constraints on depositional environment however. Species and genera assemblages of particular habitats have been established by the Treatise on Invertebrate Paleontology. These ostracodes are separated into three main environmental categories of freshwater, marine, and brackish-waters. Freshwater ostracodes have relatively smooth unornamented carapaces in comparison to marine ostracodes. Prolific ostracode fauna, and subsequent ostracodal limestones, can be found in slightly alkaline stagnant ponds. Marine ostracodes have complicated ornate carapaces that reflect the marine, largely benthonic habitat that they crawled, burrowed, and swam. Ostracodes first inhabited the marine environment before the terrestrial environment, and therefore the fossil record is the most diverse for marine ostracodes.

Ostracodes are among the few invertebrates that can tolerate brackish waters, and ostracodes are the most abundant microfossils in brackish-water sediments. Pyritized ostracods have been reported from black shales, but they are more likely to be found in transition beds above and below such strata. Most evaporite-bearing strata do not contain ostracodes, although an assemblage interpreted to represent a hypersaline environment has been found in the Devonian of Russia. The genus Cyprideis, a typical brackish water ostracode, inhabits waters of all degrees of salinity from fresh to marine. The carapace (ostracode exterior) ranges from smooth to nodose, and the number of nodose dimorphs increases in proportion A B to the smooth dimorphs as salinity increases (Treatise on Invertebrate Paleontology. (Q) Arthropoda 3). Ostracodes found in the outcrop along Corridor H have smooth carapaces (Figure 11), and if the ostracodes were of the genus Cyprideis, it would likely represent an ostracode that did not tolerate hyper salinity. Curry (1998) determined environmental tolerance indices for 10 common continental ostracodes collected from 341 sites in the United States. He found that the most tolerant species include Cypridopsis vidua, Physocypria globula and Figure 11a and 11b- Smooth ostracodes shells in Tonoloway sample and in P. pustulosa, and float. Needle width of 250 µm. Candona rawsoni. Ostracodes that do not tolerate hydrochemical evolution due to evaporation include Cypria opthalmica and Candona acuta. Abundance of tolerant species of ostracode, and lack of intolerant species of ostracode, are indicative of shallow marine depositional environment, due to the characteristic variability and hydrochemical fluctuation in the shallow marine. Although genus and species identification of ostracode is outside the scope of this thesis project, it can provide constraints on depositional environment of ostracodes with accepted ranges of salinity tolerance.

VII. Method of Analysis

Outcrop Information The Silurian Tonoloway Formation is exposed in West Virginia, Virginia, Pennsylvania, and Maryland, with the type section in Pinto, Maryland (Smosna et al. 1977). The Tonoloway overlies the Silurian Wills Creek Shale, and underlies the Devonian Keyser Limestone of the Helderberg Group. The Tonoloway Formation was deposited over a period of 1-3Ma, from the Ludlow Epoch to Middle Pridoli Epoch (Bell, 1997). The Tonoloway was deposited in the central Appalachian basin between the Ordovician Taconic and Devonian Acadian orogenies. My stratigraphic column, samples, and subsequent data come from the outcrop exposed along mile marker 97 on Corridor H highway at latitude and longitude of 39° 7’ 47.918” N and 79° 2’ 22.515”, at an altitude of 546.2 meters above sea level. This particular outcrop was selected due to the presence of a variety of facies, including subtidal, intertidal, and supratidal,

11 which represent changes in water depth, and also because it is only gently folded relative to other outcrops of the Tonoloway Formation. Field Methods A datum was established at the lowest stratum exposed at the base of the anticline (Figure M1), and thicknesses of individual beds characterized by distinctive lithologies were measured using a 1.5 meter Jacob staff (Figure M2). Samples were collected in carbonate-rich levels, avoiding highly weathered and shale-rich intervals, at approximately one to two meter intervals, and labeled according to the exact height above the datum. Forty-six hand samples were collected in total and placed into cloth or plastic bags labeled with their height above the datum. Dry Lab Methods Stratigraphic hand samples were cut perpendicular to bedding planes to produce flat slabs, or billets, with a thickness of 0.5 - 1 cm using the MK Tile Saw PRO (model number 155747-101) in CHEM 0234 (Figure M3). Resulting slabs were ground and polished using the Struers LaboPol- 21 rock slab polisher (Figure M4) in CHEM0224 with a progression of increasingly fine-grained silica carbide discs from 80, 220, 320 to 500 grit. Polished slabs were examined for textural variations with the Leica binocular microscope with a digital camera in CHEM 1211. After this examination, specific areas for micro-drilling were identified and marked with a Sharpie pen on the surface of the polished billets. Drilled textures were typically chosen from the finest-grained, most reactive (to 3% HCl), and homogeneous micrite, avoiding shale-rich intervals or those with secondary carbonate veins. Surfaces were cleaned with ethanol and a Kimwipe and then placed on the lab-jack beneath a Servo Products micro-drill model 7170 in CHEM0224 (Figure M5). With a 0.8 mm dental drill bit (model SSWFG-1156), approximately 10 shallow holes were drilled within the marked areas, and the resulting powder were gathered into small labelled vials that were then capped and stored. The drill bit was cleaned with ethyl alcohol between each new sample.

Mass Spectrometric Methods: Carbonate Approximately 100 mg (± 10%) of sample rock powder and calibrated house standard carbonate (JTB) were weighed using the Mettler Toledo AT21 Comparator mass balance in CHEM0227 (Figure M10). The tools used in the process were systematically cleaned between samples with Kimwipes and ethyl alcohol. A millimeter-scale sample cup was placed in the center of the balance using curved tweezers, and the mass of the cup was zeroed prior to introduction of the sample or standard material. The weighed material was then transferred to 3.7mL Labco Exetainer vials, sealed with Labco septa, and transferred to a holding rack. Labeled sample vials were given to the Stable Isotope Co-Laboratory Manager Rebecca Plummer to conduct carbonate analysis using the Multiflow Isoprime Mass Spectrometer in CHEM 1216 (Figure M9). Prior to the analysis, the Isoprime was tested for stability using a reference CO2 gas (Figure M8). Sample vials were placed into loading tray (Figure M6) heated to 65 degrees Celsius where an automated needle pierced each of the vials to flush out the air with 99.999% helium through a hole in the side of the needle. Then ~100 ml of 102% H3PO4 was added to the vials to react with the carbonate for one hour at 60 degrees Celsius and released CO2 into the headspace. The automated needle then pierced the vial to extract an aliquot of the CO2 with a stream of He through a gas chromatograph column and a Nafion water trap to purify the gas prior to its introduction to the Elementar Isoprime stable isotope mass spectrometer fitted with a continuous flow interface (see flow chart in Figure M11). In the ion source the cloud of CO2 molecules were bombarded with electrons boiled off of a W filament, causing electrons to be

12 stripped from the neutral gas and produce positively charged ions. A voltage potential across the flight tube accelerated the positively charged CO2 ions towards the three detectors, but in their flight an electromagnet bent the path of the isotopic CO2 masses (m/z = 44, 45, and 46) into separate paths and abundances for each path were quantified in currents (the typical linear range used for publishable data is between 2 and 14 nA) recorded in the Faraday cups (Figure M7). Data were corrected via automated Matlab scripting on the Vienna PeeDee Belemnite and LSVEC Lithium Carbonate (VPDB-LSVEC) scale using periodic in-run measurement of international reference carbonate materials and/or in-house standard carbonates, from which empirical corrections for signal amplitude, sequential drift, and one or two-point mean corrections were applied. The isotopic results were reported using delta notation shown below: 13C = ((13C/12C) sample / (13C/12C) standard -1)*1000 ‰ 18O = ((18O/16O) sample / (18O/16O) standard -1)*1000 ‰ 𝛿𝛿 Isotopic data were then𝛿𝛿 corrected for instrumental drift, determined by the measurement of standard materials throughout the run, using a computer algorithm. Lab Methods: Wet Stratigraphic hand samples were cut perpendicular to bedding planes to produce thin billets with a thickness of 0.25-0.5 centimeters using the MK Tile Saw PRO (model number 155747-101) in CHEM 0234 (Figure M3). Resulting hand sample billets were crushed into large pieces, and pieces containing shale, carbonate veins, and weathered surfaces were removed with a tweezer. Remaining homogenous micrite and dolomicrite were crushed into a fine powder using a stainless steel mortar and pestle (Figure M16). Mortar, pestle and tweezers were cleaned with ethyl alcohol between samples. Approximately six to seven grams of sample powder was weighed using Mettler Toledo AB104 mass balance in CHEM 0224. Weighed powder was placed into 50 mL CORNING CentriStarTM centrifuge tube (Figure M12). Mass of tube and powder was recorded. To quantitatively remove carbonate from the powdered samples, 3M HCl was added, a few drops at a time, into the centrifuge tube, allowing the calcium carbonate to be consumed by the acid, producing water and carbon dioxide gas, which escaped from the tube. The centrifuge tube was first lightly shaken by hand, and then shaken more vigorously by Vortex Genie 2 (model G560) (Figure 13) to ensure HCl mixed with sample carbonate at the bottom of the tube. After 25- 30 mL of 3M HCl was added and allowed to react completely with the carbonate, the neutralized solution was separated from the residue by centrifugation in the Fisher Centrific centrifuge (Figure 14) in CHEM0224 for five minutes at medium speed (5 on a scale of 1-10). After the solid pellet and liquid supernatant were separated from the centrifuge, the supernatant was poured into HCl waste container, being careful to only pour the supernatant and not any of the sample pellet. Additional HCl was added to the centrifuge tube, and tube shaken, until the addition of HCl did not result in further reaction. Once the sample powder had been sufficiently acidified and the carbonate quantitatively removed from the samples, then the centrifuge tube was placed into the Fisher Centrific centrifuge for five minutes on medium speed. Supernatant poured into HCl waste container. To wash the residue, approximately 30 mL of Milli-Q water added to the centrifuge tube, and shaken to cleanse the sample and tube of remnant HCl. Centrifuge tube was placed in Fisher Centrific centrifuge for 5 minutes on medium speed. Supernatant acidic water poured into HCl waster container. About 10 mL of Milli-Q water added to tube and shaken to mix with the sample pellet. Centrifuge tube was placed into Fisher Centrific centrifuge for 5 minutes on medium speed.

Supernatant water poured into waste container, being careful not to lose any sample. Centrifuge tube was placed into metal rack in VWR Scientific Product Utility Oven (model 1305U) (Figure 15) to dry for two days on low heat. After two days the tube was taken out of the oven, allowed to cool to room temperature, and then weighed on the Mettler Toledo AB104 mass balance. The starting mass of sample was subtracted by post-acidification and drying mass of sample, and divided by original mass to determine percentage of carbonate in sample. Dried powder in the tube was homogenized using a glass stirring rod. Glass stirring rod was cleaned with ethyl alcohol and Kimwipes between samples. Homogenized powder was poured into small labelled vials that were then capped and stored. Mass Spectrometric Methods: Sulfur Approximately 1 mg (± 10%) of sample rock powder, 0.1 mg calibrated house standard

NZS1 and NTS-127, and 1-2 mg of V2O5 were weighed using the Mettler Toledo AT21 Comparator mass balance in CHEM0227 (Figure M10). The tools used in the process were systematically cleaned between samples with Kimwipes and ethyl alcohol. A millimeter-scale tin cup was placed in the center of the balance using curved tweezers, and the mass of the cup was zeroed prior to introduction of the sample or standard material. The tin cup was then folded into a ball. Measured samples and standards were given to the Stable Isotope Co-Laboratory Manager Rebecca Plummer to conduct pyrite sulfur isotope composition analysis. Samples and standards were combusted to SO2 with a Eurovector elemental analyzer in-line with a second Elementar Isoprime isotope ratio mass spectrometer in CHEM 1216. Tin cups were sequentially dropped with a pulsed 12ml O2 purge into a catalytic combustion furnace of 1030 degrees Celsius. Frosted quartz reaction tube was filled with high purity reduced copper wire for quantitative oxidation and O2 resorption.

10 cm Mg(ClO4)2 column removed any water produced in the combustion, and 0.8m PTFE GC column filled with Porapak 50-80 mesh heated to 115 degrees Celsius separated the SO2 gas from the other gases. The effluent was introduced in a flow of He (80-120 mL/min) to the IRMS through a SGE splitter valve that controls the variable open split. SO2 reference gas (Air Products 99.9% purity, ~3nA) were introduced in timed pulses at the beginning of the run using an injector connected to the IRMS with a fixed open ratio split. Isotope ratios of reference and sample peaks were measured by monitoring ion beam intensities relative to background values. Analysis cycles lasted 210 seconds, where the reference gas was injected as a 30 second pulse, starting at 20 seconds. Sample SO2 pulses began at 110 seconds and returned to baseline values between 150-180 seconds. Sulfur isotope ratios were determined by comparing integrated peak areas of m/z 66 and 64 for the reference and sample SO2 pulses, relative to baseline of -11 approximately 1 x 10 A. The left limit of the sample SO2 peak determined the background height. Isotopic results are expressed in delta notation as per mil (‰) deviations from the Vienna Canyon Diablo Troilite (V-CDT) standard.

Pyrite Sulfur Data Correction To correct the SO2 data, standards and samples were run, and an isotope ratio of peak height relative to peak height of SO2 gas was calculated. Peak heights are between 1-10 nA, as that is the linear range of the instrument. Measured 34S was plotted relative to true values of δ34S for standards NBS-127 and NZS1 as a function of position, and a slope and intercept was found from that line. Average position and average measured S were found for both standards that results in a slope that corrects for instrument drift.

Mass Spectrometric methods: Organic Carbon Approximately 1 mg (± 10%) of sample rock powder, 0.1 mg Calibrated House standard Urea were weighed using the Mettler Toledo AT21 Comparator mass balance in CHEM0227 (Fig.###). The tools used in the process were systematically cleaned between samples with Kimwipes and ethyl alcohol. A millimeter-scale tin cup was placed in the center of the balance using curved tweezers, and the mass of the cup was zeroed prior to introduction of the sample or standard material. The tin cup was then folded into a ball. Measured samples and standards were given to the Stable Isotope Co-Laboratory Manager Rebecca Plummer to conduct organic carbon isotope composition analysis. Samples and standards were combusted to CO2 with a Eurovector elemental analyzer in-line with a second Elementar Isoprime isotope ratio mass spectrometer in CHEM 1216 (Fig#). Tin cups were sequentially dropped with a pulsed 12ml O2 purge into a catalytic combustion furnace of 1040 degrees Celsius. Frosted quartz reaction tube was filled with chromium oxide and silvered cobaltous/cobaltic oxide for quantitative reduction of NO2 and N2O and O2 resorption. A 3m stainless steel GC column filled with Porapak-Q heated to 60 degrees Celsius separated the CO2 gas from the other gases. The effluent was introduced in a flow of He (80-120 mL/min) to the IRMS through a SGE splitter valve that controls the variable open split. CO2 reference gas (Airgas 99.9% purity, ~6nA) were introduced in timed pulses at the beginning of the run using an injector connected to the IRMS with a fixed open ratio split. Isotope ratios of reference and sample peaks were measured by monitoring ion beam intensities relative to background values. Analysis cycles lasted 430 seconds, where the reference gas was injected as two 30 second pulses, starting at 15 seconds and 60 seconds. Sample CO2 pulses began at 200 seconds and returned to baseline values around 240 seconds. Carbon isotope ratios were determined by comparing integrated peak areas of m/z 45 and 44 for the reference and sample -11 CO2 pulses, relative to baseline of approximately 2 x 10 A. The left limit of the sample CO2 peak determined the background height. Isotopic results are expressed in delta notation as per mil (‰) deviations from the Vienna Pee Dee Belemnite (V-PDB) standard. Uncertainties The intrinsic error of the height of the stratigraphic column is 5 centimeters, half of the smallest unit of measure on the Jacob staff, which is 10 centimeters. The uncertainty of the mass balance is one microgram. The uncertainty of the isotopic measurements were determined by calculating the average and 1-sigma standard deviations of the standard JTB, NZS1, NBZ analyses using an Excel spreadsheet. Tables 1 to 4 of standard 1-sigma standard deviation show uncertainty for each type of analysis.

Table 1- Carbonate Carbon and Oxygen JTB Standards sample_ID date_time position RT amplitude mass c13asdt o18asdt 10292015_JTB_R1.raw 42306.53668 54 134.1 11.004283 0.155 1.75 -8.70 10292015_JTB_R2.raw 42306.54225 55 134 15.859739 0.158 1.81 -8.74 10292015_JTB_R3.raw 42306.5478 56 134 15.446932 0.148 1.76 -8.71 10292015_JTB_R4.raw 42306.55336 57 134.3 11.715112 0.11 1.77 -8.66 10292015_JTB_R5.raw 42306.6144 68 134.3 13.94323 0.124 1.82 -8.67 10292015_JTB_R6.raw 42306.61994 69 134.7 9.411366 0.088 1.80 -8.76 10292015_JTB_R7.raw 42306.65878 76 138.7 6.658236 0.088 1.74 -8.84 10292015_JTB_R8.raw 42306.66432 77 135.6 9.517451 0.1 1.78 -8.61 01292016_REP_Fishbeck_JTB-1_R1.raw 42398.82492 129 125.3 11.943404 0.109 1.82 -8.81 01292016_REP_Fishbeck_JTB-1_R2.raw 42398.83043 130 125.2 10.101091 0.09 1.76 -8.80 01292016_REP_Fishbeck_JTB-1_R3.raw 42398.89144 141 125.5 11.868869 0.115 1.79 -8.65 01292016_REP_Fishbeck_JTB-1_R4.raw 42398.89699 142 125.4 13.207743 0.118 1.79 -8.60 01292016_REP_Fishbeck_JTB-1_R5.raw 42398.95821 153 125.7 11.510017 0.103 1.74 -8.55 01292016_REP_Fishbeck_JTB-1_R6.raw 42398.96376 154 125.5 14.602577 0.141 1.75 -8.78 01292016_REP_Fishbeck_JTB-1_R7.raw 42399.02483 165 125.7 11.005248 0.1 1.78 -8.64 01292016_REP_Fishbeck_JTB-1_R8.raw 42399.03037 166 125.5 14.869233 0.138 1.81 -8.70 01292016_REP_Fishbeck_JTB-1_R9.raw 42399.08589 176 125.7 10.372021 0.095 1.76 -8.69 01292016_REP_Fishbeck_JTB-1_R10.raw 42399.09145 177 125.7 10.129756 0.093 1.81 -8.88

Avg 1.78 -8.71 10/29/2015 std dev 0.0305 0.0682

Avg 1.78 -8.71 1/29/2016 std dev 0.0279 0.1053 Table 2- Organic Carbon Urea Standards

Acquisition Height Weight Elemental d13C_corr Sample Number Name date (nA) (mg) Composition vs. VPDB SampleNo/s DataFileName/s AcquisitionDate/sMaOorHeightnASampleWeight/ R_1EC 31 04052016_Urea_9.raw 5/4/16 12:58 9.08 0.09 20.34 -29.22 32 04052016_Urea_10.raw 5/4/16 13:05 11.15 0.12 18.94 -29.51 43 04052016_Urea_11.raw 5/4/16 14:20 10.46 0.10 20.59 -29.44 44 04052016_Urea_12.raw 5/4/16 14:27 15.76 0.15 20.47 -29.34 55 04052016_Urea_13.raw 5/4/16 15:43 13.41 0.13 19.93 -29.42 56 04052016_Urea_14.raw 5/4/16 15:50 10.05 0.10 19.72 -29.41

avg 20.00 -29.39 stdev 0.61343725 0.102203

Table 3- Pyrite Sulfur NBS-127 and NBS1 standards_4.1.16

peak Elemental Sample mass height Compositi Delta_CD Number Name (mg) (nA) on T (correct) 6 04012016_NBS127_R1.raw 0.20 6.29 14.16 20.97 7 04012016_NBS127_R2.raw 0.21 6.35 14.31 21.19 8 04012016_NBS127_R3.raw 0.24 7.11 14.09 21.11 9 04012016_NBS127_R4.raw 0.18 5.38 14.12 21.13 10 04012016_S1_R1.raw 0.21 5.68 13.21 -0.33 11 04012016_S1_R2.raw 0.19 5.12 13.15 -0.27 22 04012016_NBS127_R5.raw 0.22 5.45 13.69 21.09 23 04012016_NBS127_R6.raw 0.17 4.21 13.19 21.11 24 04012016_S1_R3.raw 0.22 5.11 12.74 -0.31 25 04012016_S1_R4.raw 0.25 5.90 12.93 -0.29 36 04012016_NBS127_R7.raw 0.15 3.38 13.50 21.09 37 04012016_NBS127_R8.raw 0.20 4.26 12.95 21.11 38 04012016_S1_R5.raw 0.21 4.59 12.87 -0.31 39 04012016_S1_R6.raw 0.22 4.69 12.65 -0.29

avg 13.75 21.10 NBS-127 stdev 0.502 0.063 avg 12.93 -0.30 S1 stdev 0.222 0.022 Table 4- Pyrite Sulfur NBS-127 and NBS1 standards_4.6.16

peak Elemental Sample mass height Compositi Delta_CD Number Name (mg) (nA) on T (correct) 6 04062016_NBS-127_1.raw 0.34 10.15 12.88 21.04 7 04062016_NBS-127_2.raw 0.24 7.18 13.12 21.10 8 04062016_NBS-127_3.raw 0.22 6.80 13.01 21.12 9 04062016_NBS-127_4.raw 0.18 5.81 13.07 21.15 10 04062016_S1_1.raw 0.17 0.22 0.62 1.15 11 04062016_S1_2.raw 0.35 10.56 12.47 -0.30 20 04062016_NBS-127_5.raw 0.19 5.88 13.41 21.26 21 04062016_NBS-127_6.raw 0.20 5.68 12.62 20.94 22 04062016_S1_3.raw 0.24 7.95 13.22 -0.30 23 04062016_S1_4.raw 0.37 10.31 29.53 3.75

avg 13.02 21.10 NBS-127 stdev 0.263371 0.109786 avg 12.84 -0.30 S1 stdev 0.52631 1.88E-15

Figure M1-M11. M1: Tonoloway Formation outcrop where red dots mark location of hand sample collection. M2: 1.5m Jacob’s Staff against mud-cracked interval in the Tonoloway Formation. M3: MK Tile Saw PRO. M4: Struers LaboPol-21 rock slab polisher. M5: Servo Products model 7170 micro-drill. M6: Multiflow carbonate inlet device with automated needle. M7: Gas flight tube and electromagnet on the Isoprime gas Mass Spectrometer. M8: Reference gas box for standard gas injections and stability testing. M9: Multiflow Isoprime gas source Mass Spectrometer. M10: Mettler Toledo AT21 Comparator mass balance. M11: Flow chart for gas transfer in the Multiflow inlet device to the Isoprime gas source Mass Spectrometer. M12: Corning CentriStar 50 mL centrifuge tube. M13: Vortex Genie Model No. G560. M14: Fisher Centrific Centrifuge. M15: VWR Scientific Product Utility Oven (model 1305U). M16: Stainless Steel Mortar and Pestle.

VIII. Results Stratigraphic Column, Lithology, and Sedimentary Textures Figure 6A shows the 40 meter stratigraphic column of lithologies and sedimentary textures based on data gathered in the field and from visual observation of cut and polished hand samples. Stratigraphic column was composed from outcrop and hand sample information shown in Table A.1 and A.12. The primary lithologies present are micrite, laminite, grainstone, and dolomicrite and accessory lithologies are shale, siltstone, and sandstone. The sedimentary features are indicated by symbols next to the strata. Sedimentary features include presence of brachiopod, ostracode fragments, whole ostracodes, vugs, mud cracks, and intraclastic breccia. Halite hoppers and syneresis cracks have been found on float at the base of the outcrop, but these likely come from the highly weathered shalely intervals that are light tan to brown in color (see Figure M1), which are likely the dolomitic and highly evaporitic intervals. Micrite samples are largely microcrystalline calcite mud with minor amounts of silt and clay. Laminite samples consist of coupled microcrystalline calcite mud and layers of clay/shale/silt. Dolomicrite is microcrystalline dolomite to calcite mud with minor amounts of silt and clay that does not react or reacts lightly to 3% HCl. Generally speaking, micrites and grainstones were deposited in the subtidal zone, laminites were deposited in the intertidal zone, and siltstones, sandstones, and dolomicrite were deposited in the supratidal zone.

Figure 12A-12G- Chemostratigraphic column of 40 meter section of Tonoloway Formation outcrop. 12A shows the lithologies and sedimentary textures of the outcrop. Lithologies: Micrite is blue, grainstone is pink, dolomicrite is white, laminite is grey stripped, shale is black, siltstone is tan, and sandstone is orange. Sedimentary texture: ostracodes are indicated by black circles, ostracode fragments by curved lines, brachiopods by brachiopod symbol, intraclastic brecciation by rectangular symbol, vugs by cloud-like symbol, and mud-cracks by pentagon. 12B shows the percent carbonate in the sample on a scale of 20-100%. 12C shows carbonate δ13C values in blue and δ18O values in red, on a scale of -10 to 2 ‰ VPDB. Circles represent micrite values, triangles represent laminite values, and squares represent dolomicrite values. 12D shows percent Total Organic Carbon from 0 to 0.6. 12E shows δ13C of Total Organic Carbon on a scale from -32 to -26 δ13C. 12F shows percent total sulfur on a scale of 0 to 4 %. 12G shows δ34S on a scale from -20 to 30 ‰ VCDT.

The first eight meters of the stratigraphic column are mainly laminites capped by thin recessive shale layers about 20 centimeters thick, which indicate subtidal and intertidal depositional environment. Laminite containing desiccation cracks lay directly below the unconformity at 2.3 m above the datum. Directly above that unconformity is a micrite containing carbonate intraclastic brecciation. Laminite is the major lithology from the datum to about 21 meters above the datum, which indicates that these strata were deposited in the intertidal zone. The micrite layer from 21.55-22.3 m is markedly unique, containing ostracod fragments and abundant mm scale vugs, which create a pseudo- vesicular texture. The abundance of vugs in this lithologic section of the outcrop could be due to a weathering feature or other diagenetic alteration. Dolomitic siltstone appears in the section starting at 23.4 m. The increase in siltstones and sandstones in this section represents a greater terrestrial influence on the depositional environment as you go up section. From 21 m to 25 m, there are alternating sets of micrite and dolomicrite. From 24 to 33 m, there are carbonate cemented siltstones and sandstones which

20 signify a greater terrestrial sediment input and shift to supratidal facies. The top 10 meters of the section contain dolomicrites primarily. The overall shift of the 40 meter section from laminite towards the base to dolomicrite at the top indicates an intertidal to supratidal depositional environment shift. The presence of ostracode fossils indicate non-evaporative depositional environment, as ostracodes can tolerate brackish water, but still require aquatic setting. Presence of brachiopods indicate non-evaporative depositional environment, as brachiopods were marine organisms. Presence of vugs in the sample could indicate that there was once something in the void space while the surrounding rock was deposited, likely a sulfur-bearing evaporite mineral. Alternatively, the vugs could be due to diagenetic alteration with groundwater. Intraclastic brecciation indicates that a storm event ripped up pieces of limestone on a carbonate shelf, which deposited as lathes and broken pieces. The presence of mud cracks indicate that the sediments were exposed and dried subaerially, and presence of halite hoppers, or salt casts, indicate that sediments were deposited where 90% or more of marine water had to evaporate. Percent Carbonate Panel 6B shows the percent carbonate in 19 of the samples, which were used for the organic C and pyrite S determinations. There is more carbonate from height 10-35m, and significantly less carbonate from 35-40m, and slightly less carbonate from 0-10m. The depletion of carbonate in the uppermost and lowest section could be from supratidal dolomicrite and intertidal laminites, which have a greater amount of silt and clay respectively than is found in the micrite. δ13C and δ18O in Carbonate Analysis yielded a total of 24 micrite, 10 laminite and 16 dolomicrite δ13C and δ18O compositions δ13C values were plotted in blue, and δ18O in red; micrite is shown as circles, laminate as triangles, and dolomite as squares. The dolomicrite is somewhat enriched in 13C compared to non-dolomicrite lithologies, and is clearly enriched in 18O compared to non- dolomicrite lithologies. Multiple data points at one height represent sub-sampling within a

polished slab due to variations within the sample. Table 5 shows the sub-sampling isotopic variation present in samples, where the bolded values show notable enrichments of either 18O or 13C. Images show sites of sub-sampling, labeled with sample name and site 1, 2 or 3. Sample 22.3_1 was taken from a vug-rich area, while 22.3_2 was taken from a relatively vug-free area. Sample 22.3_1 shows an 18O enrichment of 0.80 ‰, which is consistent with the hypothesis of vug formation being indicative of an evaporative environment. Sample 23.5_2 is almost 3 ‰ enriched in 13C compared to 23.5_1 which is only 18mm away. 23.5_2 is ostracode rich, as compared to 23.5_1 which was an ostracod free interval. Sample 23.6_1, directly above a vuggy interval, is enriched in 13C compared to the other sampling sites. Sample 23.6_2, from an ostracod poor level and in between vuggy layers, shows 18O enrichment of up to 1.45 ‰. A large pile of float that contains halite hoppers appear to have likely come from this interval as well.

7.8_1

7.8_2

7.8_2 22.3_1 7.8_1

21.3_2

32.6_1

23.5_2

23.5_1 32.6_2 Table 5- Subsampling sites; δ13C and δ18O Height DFtop2_1 δ13C δ18O Sample above datum Carbonate Carbonate DFTF_7-8_1 7.8 -1.96 -5.27 DFtop2_1 DFTF_7-8_2 7.8 -2.07 -5.3 DFTF_22-3_1 22.3 -4.97 -8.02 DFTF_22-3_2 22.3 -4.55 -8.82 DFTF_23.5_1 23.5 -5.83 -8.32 DFTF_23.5_2 23.5 -2.97 -8.96 DFtop2_2 DFtop2_2 DFTF_23.6_1 23.6 -4.63 -9.01 DFTF_23.6_3 23.6 -5.45 -7.86 23.6_1 DFTF_23.6_2 23.6 -5.11 -7.56 DFTF_32-6_1 32.6 -3.13 -5.87 DFTF_32-6_2 32.6 -3.17 -5.69

23.6_2 DFTF_34-3_1 34.3 -2.63 -8.85 DFTF_34-3_2 34.3 -2.6 -9.31 DFtop2_1 35 -1.53 -5.88

23.6_3 DFtop2_2 35 -1.47 -5.94

Figure 13- Images of sub-sampling locations in select samples. Corresponding isotopic values for each sub sampling site are in Table 5.

18 3 No feature shows O enrichment except for intraclastic brecciation, which is found primarily in dolomicrite. Table 6 shows the δ13C and δ18O values for all samples with intraclastic brecciation, brecciated dolomite, and non-brecciated dolomite. Although the texture of brecciation, regardless of lithology, shows enrichment in 18O compared to other textures, and dolomicrite show enrichment in 18O compared to other lithologies, non-brecciated dolomicrite is more enriched in 18O than brecciated dolomicrite. Samples containing fossils show depletion, not enrichment, in 18O, which is expected as brachiopods and ostracods are not expected to have lived in evaporitic depositional environment. Samples containing pyrite, in the form of pyritized ostracodes, have enrichment in 13C. The texture of mud-cracks and vugs, which were expected to have enrichment, show no enrichment in either 13C or 18O, and appear to be depleted in 13C.

Table 7 shows values for δ13C and δ18O for the three main lithologies of micrite, laminite and dolomicrite, plotted as blue circles, grey circles, and light grey squares respectfully. Error bars on individual points represent 1 sigma standard deviation about the mean of the carbonate JTB standards (Table 1). Vertical error bars are the standard deviation of the JTB standard δ18O, and the horizontal error bars are the standard deviation of the JTB standard δ13C. Although my two sets of standard runs yielded two sets of standard deviation, I use the greatest standard deviation out of both trials for all samples. The center point of the larger thick lines is the average value for each lithology, and the vertical and horizontal bars are 1 sigma standard deviation about that average. This cross plot visually shows that the laminite and dolomicrite are slightly enriched in 13C, and the dolomicrite is clearly enriched in 18O. Figure 17 shows the range δ13C and δ18O of values for micrite, laminite and dolomicrite, where shaded-in box is +/- 1 standard deviation about the mean. The lines extend from the box to the highest and lowest value in each category. This visually shows that dolomicrite not only has a higher average value of δ18O, but the values of δ18O for dolomicrite are contained within a narrow range. 13 Percent Total Organic Carbon (TOC) and δ Corganic Figure 12D of shows the percent total organic carbon of the samples, at the height at which the sample was retrieved from. These are overall very low values, which could mean that organic carbon has reoxidized or there simply wasn’t a lot of organic carbon to be buried in these strata. These explanations are conducive to a well oxygenated and evaporitic environment. 13 Average and standard deviation of δ COrganic values for all textures and lithologies are in Table 6 and Table 7. Percent Total Sulfur and δ34S 12F shows percent total sulfur on a scale of 0 to 4 % and 12G shows δ34S on a scale from -20 to 30 ‰ VCDT. δ34S values cover a wide range, although most are positive values, approaching 25‰. Average and standard deviation of δ 34S values for all textures and lithologies are in Table 6 and Table 7.

δ13C δ13C δ34S δ18O Carbonate Organic Pyrite Carbonate Intraclastic Average -1.97 -27.95 9.36 -6.49 Brecciation Std Dev 0.67 n/a n/a 1.00 Average -3.28 -28.10 12.76 -8.38 Fossils Std Dev 1.77 0.91 7.35 0.50 Average -4.74 -28.86 17.31 -7.25 Vugs Std Dev 1.45 0.72 5.15 1.32 -4.59 -28.85 18.87 -7.53 Mudcracks Average Std Dev 1.00 0.44 2.31 1.38 Average -1.51 -27.56 11.97 -7.61 Pyrite Std Dev 0.71 0.68 4.51 1.38 Table 6 - Averages and 1-sigma standard deviation of chemical signals in samples containing textures of Intraclastic Brecciation, Fossils, Vugs, Mud cracks, and Pyrite.

δ13C δ13C δ34S δ18O Carbonate Organic Pyrite Carbonate Average -3.55 -28.18 13.59 -7.84 Micrite Std Dev 1.89 0.99 7.32 1.20 Average -2.46 -29.07 9.62 -7.67 Laminite Std Dev 0.73 1.52 14.64 1.36 Average -1.80 -28.08 11.28 -5.77 Dolomicrite Std Dev 1.10 0.92 6.27 0.39 Table 7 - Averages and 1-sigma standard deviation of chemical signals in samples of micrite, laminite, and dolomicrite.

Figure 14- Averages of δ 13C and δ 18O values for sedimentary textures of vugs, mud-cracks, intraclastic brecciation, and fossils. The center point is the average, and the vertical and horizontal bars are 1 sigma standard deviation of the lithology average values of δ 13C and δ 18O.

Figure 15 - Averages of δ 13C and δ 18O values for texture of intraclastic brecciation, brecciated dolomicrite, and non-brecciated dolomite. The center point is the average, and the vertical and horizontal bars are 1 sigma standard deviation of the average values of δ 13C and δ 18O

Figure 16 -Averages of δ 13C and δ 18O values for lithologies respectfully. The center point is the average, and the vertical and horizontal bars are 1 sigma standard deviation of the average values of δ 13C and δ 18O.

δ13C and δ18O statistics

13 -2 δ C δ13C δ13C -4 (‰ VPDB) δ -6 δ18O

18 -8 δ18O δ O

-10 Micrite δ18O Micrite δ13C Laminite δ18O Laminite δ13C Dolomicrite Dolomicrite δ13C δ18O

Figure 17- Range of values for micrite, laminite and dolomicrite, where shaded-in box is +/- 1 standard deviation about the mean.

IX. Discussion of Results

Isotope compositions, when paired with sedimentary features, can provide insight into evaporative or non-evaporative depositional environments. When analyzing carbon and oxygen isotopes to investigate stratigraphic variations, it is important to be aware of the effects of diagenetic and metamorphic alteration. Metamorphized low-high grade dolostones were examined by Melezhik et. al. (2003), and they found that most of the low-grade greenshist facies dolostones from Kola Superdeep Drillhole X, had 18O depletion of 1-2 ‰. Metamorphism can alter the isotopic composition of the rock, and the rocks in my study were gently folded into a syncline and experienced low grade regional metamorphism during the post-depositional Taconic orogeny. To best compensate for any diagenetic alterations of isotope composition I selected areas of purest micrite and dolomicrite in the sampling process. Diagenetic dolostones could be formed by stratigraphic types of replacement of calcium carbonate sediments within beds and along surfaces of stratigraphic discontinuities, including faults and fractures.

An evaporative model of dolomitization can explain the high δ13C and δ18O values (see Figure 10). Figure 10 shows the upward transpiration of sea water through aerially exposed sediments on a supratidal flat. As the water evaporates, the remaining sea water around the sediments are progressively concentrated in heavier isotopes of δ 18O and δ 13C. Enrichment of dolostones in 13C and 18O suggest that it formed in waters enriched in 13C and 18O, and that the enrichment of the original water in 13C and 18O must have resulted from strong evaporative processes with the lighter isotopes preferentially removed with evading CO2. (Sonnenfield, 1984).

Figure 18A- Model of evaporative dolomitization. 18B-E alternative models of dolomitization, Edited from Land (1985)

Whether dolomite formed syngenetically, epigenetically or diagenetically, their origin is due to hypersaline brine, or less commonly due to bacterial processes (Sonnenfield, 1984). In an evaporating brine, the concentrated heavy saline waters sinks down slope. If the return of the brine waters to the sea is blocked by a natural barrier such as a reef or sill, the waters migrate to the lowest possible topographic depressions and seeps to the underlying sediments, which are progressively dolomitized (Sonnenfield, 1984). Assuming a concentrating brine, each bed of

27 dolomicrite does not have to have evidence of subaerial exposure to conclude that high evaporation was taking place- simply being a dolomicrite adjacent to beds of mud cracking and halite precipitation suggests that there was high evaporation.

An evaporating body of seawater would further be an appropriate setting for dolomite precipitation, as the depositional environment resolves the kinetic barriers to dolomitization: an increase in temperature, a freshening of hypersaline waters, and an increase of seawater mg/ca to about 0.8. Evaporating shallow waters are warmer in temperature than cold deeper marine waters. The water can be freshened with the influence of meteoric waters. Lastly, the Mg/Ca ratio of about 0.8 can achieved through removal of calcium in the form of precipitating gypsum and anhydrite (Sonnenfield, 1984). Once the kinetic barriers have been resolved, the dolomite could replace existing calcite or aragonite though this reaction (Berner, 1965, p.1298):

2+ 2+ Mgaq + 2CaCO3 CaMg(CO3)2 + Caaq

Formation of dolomite requires the reduction of gypsum to H2S, iron sulfide, and native sulfur. Reduction of gypsum sulfate by bacterial processes occurs in the zone of brine reflux. When temperatures are high enough to release CO2 as gas, mass precipitation of aragonite takes - 2- 2- place, and there is a drastic decrease in HCO3 , SO4 and oxygen. The SO4 content returns to normal though bacterial reduction of gypsum to H2S, H2S oxidation to sulfate ions at the depth and surface respectively of a concentrating brine (Sonnenfield, 1984). The H2S released causes a blackening of sediments and production of dark laminae. The black sediment grains and laminae in my samples could be caused by bacterial sulfate reduction.

Evaporation and water restriction was hypothesized to cause the less negative 18O values in Upper Silurian marine calcareous rocks in Scania, Sweden. The Whitcliffian Upper Silurian rocks of Scania Sweden exhibit 13C excursions, associated with less negative 18O values, were possibly caused by high rates of photosynthesis and burial of organic matter. The high rates of photosynthesis were seen through oncoid rich limestones, where oncoids are attributed to photosynthesizing cyanobacteria and algae. The enrichment of 18O was believed to have been caused by evaporation and/or variations in water circulation (Wigforss-Lange, 1999). My samples exhibit a wide range of δ13C values, so an enrichment in the rocks is possibly, although not clearly seen in my samples.

Gill (2007) finds that sulfur can track changes in the carbon cycle (with variability through time), and relationship has been linked to the mass-balance between the oxidized and reduced reservoirs of the two elements through the following equation:

4FeS2+8CaCO3+7MgCO3+7SiO2+31H2O  8CaSO42H2O+2Fe2O3+15CH2O+7MgiO3

Sulfur in the oceans is largely from weathering of continental sulfides and sulfates, and also from magmatic sulfur from mid-ocean ridges. Present-day seawater has a sulfur isotope composition near to +21‰. Sulfur is removed from seawater though precipitation of evaporate sulfate minerals and during burial of pyrite. Precipitation of sulfate minerals during evaporation has an associated fractionation of 0-3‰ which does not greatly impact the ocean reservoir, (Gill, 2007) although the effects would be greater in an epeiric shallow marine setting. The other

28 remover of sulfur, pyrite burial, occurs in anoxic sediments with the help of bacterial sulfate reduction to change H2S to FeS2. The bacterial formed pyrite preferential incorporates the lighter 34S, leaving the heavier 34S to be enriched in the sediment.

Where there is pyrite burial in my samples I see a depletion in 34S, and where there is evidence for evaporate precipitation I see an enrichment in 34S. Rapid sedimentation can enrich pyrite in 34S through enhancing the rate of bacterial sulfate reduction and reactive iron availability beneath the sediment surface. Low δ34S values are typical of marine values where bacterial sulfate reduction is not limited by sulfur availability (Mackenzie, 2005). See figure 18 that shows weight percent of organic carbon versus weight percent pyrite S. Where low weight percent of organic carbon and higher weight percent of pyrite sulfur suggest an Figure 19- Weight percent organic carbon versus weight percent pyrite, environment of euxinic marine and environmental factors for high and low combination of values for deposition, and high percent of organic each (Mackenzie, 2005). carbon and also pyrite sulfur suggest a marine or saline lake depositional environment. I would expect a depositional environment of sulfate-limited freshwater to brackish depositional environment found in higher weight percent organic carbon and low weight percent pyrite sulfur.

X. Suggestions for Future Work

Future analysis involves identification of the ostracode genus and species, in order to biostratigraphically constrain the salinity of the facies containing ostracode fossils. Another suggestion for future work is to examine small scale changes in the lithologies with sedimentary features of evaporation present.

XI. Conclusions and Broader Implication In conclusion, textural variations in the Tonoloway Formation preserve evidence of evaporative depositional environment. 18O and 13C enrichments are preserved in some subsampling sites, where textural evidence indicates a more evaporative environment, is enriched compared to the other subsampling site(s) which do not contain those textures. While those changes are preserved on the millimeter scale, on the meter scale there is a general trend of increasing 18O and 13C values as you go up section toward the largely dolomitic uppermost 10

meters of the section. 34S enrichments could be due to sulfate mineral precipitation in an evaporative depositional environment.

XII. Acknowledgements

I would like to thank my advisor Dr. Kaufman for his guidance, instruction and support in my Senior Thesis project. I am especially grateful to my advisor for his donating time, especially traveling over 6 hours on trips to the outcrop with me. I would like to thank Rebecca Plummer for processing my isotopic data and informing me of the Mass Spectrometric instruments and methods. I would like to thank Dr. Candela for leading the Senior Thesis program.

XIV. Bibliography Azmy et al. 1998. Oxygen and carbon isotopic composition of Silurian Brachiopods: Implications for coeval seawater and glaciations. Geological society of America Bulletin. 110(11). Bahniuk, A. et al. 2015. Characterization of environmental conditions during microbial Mg- carbonate precipitation and early diagenetic dolomite crust formation: Brejo do Espinho, Rio de Janeiro, Brazil. Geological Society of London, Special publications. 418. Baumman, N. 2016. [Senior Thesis]. [College Park (MD)]: University of Maryland. Bell, S. 1997. Cyclic lithofacies, sequence stratigraphy, and depositional basin evolution of the Tonoloway Limestone [dissertation]. [Morgantown (WV)]: West Virginia University. Berner, R.A. 1982. Burial of Organic Carbon and Pyrite Sulfur in the Modern Ocean: Its Geochemical and Environmental Significance. American Journal of Science. 282: 451-475. Chadwick, W. 1994. Correlation of milankovitch-band cyclicity in the peritidal carbonates of the Tonoloway Formation, central Pennsylvania and western Maryland [dissertation]. [Philadelphia (PA): Temple University. Coplen, T.B. et al. 2006. New Guidelines for δ13C Measurements. Analytical Chemistry, 78(7):2439-2441. Curry, B. 1998. An environmental tolerance index for ostracods as indicators of physical and chemical factors in aquatic habitats. Palaeogeography, Palaeoclimatology, Palaeoecology. 148:51-63. David, S., Jean, V., and Palmer, D. 1991. Silurian myodocopes pioneer pelagic ostracods and the chronology of an ecological shift. Journal of Micropalaeontology. 10:151-173. Dewey, C. 1987. Palaeoecology of a hypersaline Carboniferous ostracod fauna. Journal of Micropalaeontology. 6(2):29-33. Friedman, G. 1980. Dolomite is an evaporate mineral: Evidence from the rock record and from sea-marginal ponds of the red sea. The Society of Economic Paleontologists and Mineralogists (SEPM). (28):69-80. Chillingar, G., Bissell, H., Fairbridge, R. 1967. Developments in Sedimentology. Chapter 6 Origin and Occurrence of Dolostones. Elsevier publishing company. 9 (A):267-348. Fritz-Miller, M. 1971. Paleoenvironmental analysis of the Tonoloway and lower Keyser Limestone at four localities in Hardy and Pendleton Counties, West Virginia [dissertation]. [Washington (DC)]: George Washington University. Horton, T.W. et al. 2016. Evaporation induced 18O and 13C enrichment in lake systems: A global perspective on hydrologic balance effects. Quaternary Science Reviews. 131(B):365-379. Johnson, M. E., Kaljo, D., and Rong, J.Y. 1991. Silurian eustasy. Special papers in paleontology. 44:145-163. Land, L.S.1985.The origin of massive dolomite. Journal of Geological Education. 33(2):112-125

Mackenzie, F.T. 2005. Sediments, Diagenesis, and Sedimentary Rocks: Treatise on Geochemistry, Second Edition. 7:128-129. Melezhik, V. et al. 2003. Fractionation of carbon and oxygen in 13C-rich Paleoproterozic dolostones in the transition from medium-grade to high-grade greenschist facies: a case study from the Koala Superdeep drillhole. Journal of the geological society. 160:71-82. Saltzman, M., 2002, Carbon isotope (δ13C) stratigraphy across the Silurian–Devonian transition in North America: Evidence for a perturbation of the global carbon cycle. Palaeogeography, Palaeoclimatology, Palaeoecology, 187(1-2): 83-100. Sambtleben, C. et al. 1995. The Silurian of Gotland (Sweden): facies interpretation based on stable isotopes in brachiopod shells. Geol Rundsch. 85:278-292. Schidlowski, M., Matzigkeit, U., Krumbein, W. 1984. Superheavy organic carbon from hypersaline microbial mats. Naturwissenschaften. 71:303-308. Smosna, R., Patchen, D. 1978. Silurian evolution of central Appalachian basin: American Association of Petroleum Geologists Bulletin. 62:2308–2328. Smosna, R., Patchen D.G., Warshauer, S.M., and Perry, W.J., JR. 1977. Relationships between depositional environments, Tonoloway Limestone, and distribution of evaporites in the Salina Formation, West Virginia. American Association of Petroleum Geologists. Studies in Geology: Reefs and Evaporites--Concepts and Depositional Models. 5:125-143. Smosna, R., and Warshauer, S.M. 1979. A scheme for Multivariate Analysis in Carbonate Petrology with an example from the Silurian Tonoloway Limestone. Journal of Sediment Petrology. 49 (1):257-271. Sonnenfield, P. 1984. Brines and Evaporites. Academic Press, Inc. Harcourt Brace Jovanovich, Publishers.13-174. Spotl, C. 2011. Long-term performance of the Gasbench isotope ratio mass spectrometry system for the stable isotope analysis of carbonate microsamples. Rapid communications in Mass Spectrometry. 25(11):1683-1685. Tourek, T. 1970. The depositional environments and sediment accumulation models for the Upper Silurian Wills Creek Shale and the Tonoloway Limestone, Central Applications [dissertation]. [Baltimore (MD)]: John Hopkins University. Treatise on Invertebrate Paleontology. (Q) Arthropoda 3. Geological society of America. University of Kansas Press. Urey, H. 1946. The Thermodynamic Properties of Isotopic Substances. Journal of the Chemical Society (resumed). 0: 562-581. Walker, J., 1986, Global geochemical cycles of carbon, sulfur, and oxygen. Elsevier Science Publishers B.V., Amsterdam, Marine geology, 70, p. 159-174.

Warshauer S. M, Smosna R. 1997. Paleoecologic controls of the ostracode communities in the Tonoloway Limestone (Silurian; Pridoli) of the central Appalachians. Aspects of ecology and zoogeography of recent and fossil Ostracoda. 475–485. Wigforss-Lange, J. 1999. Carbon Isotope 13C enrichment in Upper Silurian (Whitcliffian) marine calcareous rocks in Scania, Sweden. Journal of the Geological Society of Sweden. 121(4):273- 279 Wintermute, T. 1952. Stratigraphy of the Tonoloway and Keyser Limestones near Bedford, Pennsylvania [dissertation]. [State College (PA)]: Pennsylvania State College. Wenzel, B., Joachimski, M. 1996. Carbon and oxygen isotopic composition of Silurian brachiopods: palaeoceanographic implications. Palaeogeography, Palaeoclimatology, Palaeoecology. 122 (1-4) 143-166.

XV. Appendix Table A.1 - Field notes for measured sections

Strata upper limit [Thickness of bed] Description of Strata of height above Datum (meters) 34.3 [0.05m] Nice limestone (pure) 34.25 [0.5m] Limestone/ shaley rhythmite/ calcareous shale 33.75 [0.6m] Thick limestone interval 33.15 [0.2m] Brown, recessive shaley interval 32.95 [0.3m] Thick bedded limestone. massive laminated limestone 32.65 [0.15m] Calcareous shale, vuggy 32.5 [0.65m] Laminated and brecciated limey siltstone 31.85 [0.2m] Sandstone 31.65 [1.0m] Shaley limestone/rhythmite 30.65 [0.35m] Vuggy limestone, limey siltstone, weathers brown 30.3 [2.3m] Grey laminite 28 [0.5m]Thin-medium bedded brown limestone 27.5 [0.4m] Dolomitic siltstone 27.1 [0.9m] Rhythmic limey shale 26.2 [0.8m] Calcareous shale 25.4 [0.35m] micrite. more competent layer as evidenced by the veins which show the layer broke rather than deformed(folded) 25.05 [0.15m] Calcareous shale 24.9 [1.5m] dolomitic siltstone with brecciation. Medium bedded shaley dolomite with variegated beds 23.4 [0.6m] Grey massive shale 22.8 [1.3m] Convoluted shaley limestone 22.3 [0.7m] Vuggy, limey, strange limestone. Something dissolved out of it to form vugs. Maybe paleosols within layer. Limey at top, and ostracods. 21.55 [0.4m] Shale, strong cliff-forming beds. 21.15 [1.5m] rhythmite/shaley limestone? Pure Shale? 19.65 [0.05m] limey shale 19.6 limestone with shaley interbeds (*from 18.6-19.6 limestone with shaley limestone interbeds) 19 [1.5m] Rhythmic, shaley limestone, 17.5 [1.0m] Thick recessive shaley limestone, fissile. 16.5 [1.5m] Thick bedded “ostracodish” limestones with thin shale partings; increasing shale upward. Last 40cm of interval convolute shale bedding. 15 [0.2m] microbial laminite; pre-stromatolitic bedding 14.8 [0.2m] recessive shale 14.6 [3.0m] Laminite- increasing dolomitic-ness up section overall 11.6 [1.5m] black medium bedded limestone. Readily effervesces

10.1 [0.7m] Intermixed dolomitic limestone and thin (lime, pure limestone beds, 1-2cm thick) 9.4 [0.8m] Dolomitic limestone, shaley alternating medium-thinly laminated 8.6 [0.5m] Thinly bedded brown recessive limestone 8.1 [0.4m] Massive dolomite, darker 7.7 [3.5m] stringers of pure carbon(ate?) on shaley rhythmic limestone, Becomes more dolomitic as you approach recessive shale 4.25 [0.05m] brown limey shale 4.2 [1.8m]Wavy, nodular, dark colored limestone, folded above intraclastic layer. Stromatolitic. Carbonate nodules, fairly massive. Wavy bedded limestone. 2.4 [0.10m] Intraclastic micrite @2.3 unconformity 2.3 [1.5m] shaley limestone, mud-cracked at top of shaley limestone 0.77 [0.02m] shale 0.75 [0.5m] shaley limestone, increasing carbonate upward 0.25 [0.05m] brown shale 0.2 [0.2m] laminite/rhythmite/shaley limestone 0 Datum

Table A.2 – Pyrite Sulfur Raw Data_4.6.16

Elemental Sample Acquisition Height Weight Compositi Number Name date RT (Sec) (nA) Type (mg) S34 on SampleNo/s DataFileName/s AcquisitionDate/ RetTimeSec MajorHeight ampleType/ Sample Display SMOWCon R_1EC s s nA Weight/s Delta1 verted

6 04062016_NBS-127_1.raw 6/4/16 13:11 133.0 10.15 Elem 0.34 14.47 30.86 12.88 7 04062016_NBS-127_2.raw 6/4/16 13:16 134.7 7.18 Elem 0.24 14.48 30.86 13.12 8 04062016_NBS-127_3.raw 6/4/16 13:22 133.3 6.80 Elem 0.22 14.46 30.86 13.01 9 04062016_NBS-127_4.raw 6/4/16 13:28 133.2 5.81 Elem 0.18 14.46 30.86 13.07 10 04062016_S1_1.raw 6/4/16 13:34 136.5 0.22 Elem 0.17 -5.20 30.86 0.62 11 04062016_S1_2.raw 6/4/16 13:39 132.7 10.56 Elem 0.35 -6.67 30.86 12.47 12 04062016_DFTF25-1.raw 6/4/16 13:45 118.8 0.33 6.61 -25.64 30.86 0.00 133.1 5.68 0.14 30.86 0.35 13 04062016_DFtop6.raw 6/4/16 13:51 134.0 2.06 11.49 15.52 30.86 0.07 14 04062016_DFtop10.raw 6/4/16 13:57 133.0 4.47 11.21 17.75 30.86 0.16 150.8 0.75 3.86 30.86 0.00 151.7 0.65 45.85 30.86 0.00 15 04062016_DFTF32-6.raw 6/4/16 14:03 132.9 6.40 10.54 15.38 30.86 0.25 16 04062016_DFTF22-3.raw 6/4/16 14:08 135.8 1.64 11.02 9.02 30.86 0.06 17 04062016_DFTF28.raw 6/4/16 14:14 134.7 4.22 11.26 -1.46 30.86 0.15 18 04062016_DFTF23-6.raw 6/4/16 14:20 134.8 2.19 12.57 10.73 30.86 0.07 19 04062016_DFTFtop8.raw 6/4/16 14:26 135.3 0.27 12.17 16.84 30.86 0.01 20 04062016_NBS-127_5.raw 6/4/16 14:31 133.9 5.88 Elem 0.19 14.14 30.86 13.41 21 04062016_NBS-127_6.raw 6/4/16 14:37 134.0 5.68 Elem 0.20 13.78 30.86 12.62 22 04062016_S1_3.raw 6/4/16 14:43 132.5 7.95 Elem 0.24 -7.14 30.86 13.22 23 04062016_S1_4.raw 6/4/16 14:49 132.4 10.31 Elem 0.37 -3.20 30.86 29.53

Table A.3 – Pyrite Sulfur Raw Data_4.1.16

Elemental Sample Acquisition Height Weight Compositi Number Name date RT (Sec) (nA) Type (mg) S34 on SampleNo/s DataFileName/s AcquisitionDate/ RetTimeSec MajorHeight SampleTy Sample Display SMOWCon R_1EC s s nA pe/s Weight/s Delta1 verted

6 04012016_NBS127_R1.raw 1/4/16 11:29 136.2 6.29 Elem 0.20 12.77 30.86 14.16 7 04012016_NBS127_R2.raw 1/4/16 11:35 136.2 6.35 Elem 0.21 13.01 30.86 14.31 8 04012016_NBS127_R3.raw 1/4/16 11:41 136.4 7.11 Elem 0.24 12.96 30.86 14.09 9 04012016_NBS127_R4.raw 1/4/16 11:46 136.6 5.38 Elem 0.18 13.00 30.86 14.12 10 04012016_S1_R1.raw 1/4/16 11:52 136.0 5.68 Elem 0.21 -7.95 30.86 13.21 11 04012016_S1_R2.raw 1/4/16 11:58 136.5 5.12 Elem 0.19 -7.87 30.86 13.15 12 04012016_DFTF25-1.raw 1/4/16 12:07 138.8 0.68 0.92 -2.17 30.86 0.39 13 04012016_DFtop6.raw 1/4/16 12:13 139.8 0.18 1.17 9.30 30.86 0.09 14 04012016_DFTF17.raw 1/4/16 12:19 138.7 2.90 1.54 2.34 30.86 1.00 15 04012016_DFtop2.raw 1/4/16 12:25 138.0 1.97 1.10 1.61 30.86 0.90 16 04012016_DFtop10.raw 1/4/16 12:30 139.1 0.41 1.26 15.29 30.86 0.18 17 04012016_DFTF8-6.raw 1/4/16 12:36 139.4 1.80 2.02 14.32 30.86 0.47 18 04012016_DFTF32-6.raw 1/4/16 12:42 139.3 0.42 0.81 12.23 30.86 0.28 19 04012016_DFTF7.raw 1/4/16 12:48 138.5 2.79 1.53 0.00 30.86 0.96 21 04012016_DFTF30-5.raw 1/4/16 13:00 138.2 2.42 0.97 0.32 30.86 1.35 22 04012016_NBS127_R5.raw 1/4/16 13:05 138.1 5.45 Elem 0.22 13.24 30.86 13.69 23 04012016_NBS127_R6.raw 1/4/16 13:11 137.9 4.21 Elem 0.17 13.28 30.86 13.19 24 04012016_S1_R3.raw 1/4/16 13:17 136.9 5.11 Elem 0.22 -7.69 30.86 12.74 25 04012016_S1_R4.raw 1/4/16 13:23 137.0 5.90 Elem 0.25 -7.66 30.86 12.93 26 04012016_DFtop3.raw 1/4/16 13:28 138.0 2.84 0.97 2.24 30.86 1.58 27 04012016_DFTF28.raw 1/4/16 13:34 140.5 0.25 0.89 -1.89 30.86 0.18 28 04012016_DFTF3-6.raw 1/4/16 13:40 137.4 7.55 1.31 -0.50 30.86 3.23 29 04012016_DFTF2-2.raw 1/4/16 13:46 138.3 5.72 2.46 -20.34 30.86 1.33 30 04012016_DFtop4.raw 1/4/16 13:51 137.6 6.02 1.85 9.53 30.86 1.84 31 04012016_DFTF16-1.raw 1/4/16 13:57 138.1 5.41 1.49 -8.21 30.86 2.09 32 04012016_DFtop7.raw 1/4/16 14:03 139.2 3.16 1.32 16.26 30.86 1.44 34 04012016_DFTF11-5.raw 1/4/16 14:14 138.2 4.71 1.56 -1.40 30.86 1.78 36 04012016_NBS127_R7.raw 1/4/16 14:26 138.6 3.38 Elem 0.15 13.44 30.86 13.50 37 04012016_NBS127_R8.raw 1/4/16 14:32 138.6 4.26 Elem 0.20 13.47 30.86 12.95 38 04012016_S1_R5.raw 1/4/16 14:38 137.6 4.59 Elem 0.21 -7.42 30.86 12.87 39 04012016_S1_R6.raw 1/4/16 14:43 137.9 4.69 Elem 0.22 -7.39 30.86 12.65

Table A.4 - Organic Carbon Raw Data

delta18O Elemental d13C_cor Sample Acquisition RT Height Weight w.r.t. Compositi r vs . Number Name date (Sec) (nA) Type (mg) 13C 18O SMOW on VPDB SampleNo/s DataFileName/s AcquisitionDate/sRetTimeSecaOorHeightnampleTypempleWeighsplayDeltDisplayDeltaMOWConvert R_1EC 31 04052016_Urea_9.raw 5/4/16 12:58 239.1 9.08 Elem 0.09 -33.98 -7.47 23.16 20.34 -29.22 32 04052016_Urea_10.raw 5/4/16 13:05 239.0 11.15 Elem 0.12 -34.28 -7.16 23.48 18.94 -29.51 33 04052016_DFtop8.raw 5/4/16 13:12 239.5 0.99 1.05 -32.07 -7.24 23.39 0.19 -27.30 34 04052016_DFTF11-5.raw 5/4/16 13:19 239.2 2.40 0.91 -31.56 -6.68 23.97 0.52 -26.79 35 04052016_DFTF23-6.raw 5/4/16 13:26 239.4 1.97 1.26 -33.40 -6.77 23.88 0.31 -28.63 36 04052016_DFtop7.raw 5/4/16 13:32 239.1 5.18 1.04 -34.11 -6.45 24.21 0.98 -29.35 37 04052016_DFTF16-1.raw 5/4/16 13:39 239.5 2.36 1.16 -33.15 -6.66 23.99 0.40 -28.38 38 04052016_DFtop4.raw 5/4/16 13:46 239.4 2.43 1.75 -31.55 -6.57 24.09 0.27 -26.78 39 04052016_DFTF2-2.raw 5/4/16 13:53 239.3 1.04 0.81 -31.62 -6.12 24.55 0.26 -26.85 40 04052016_DFTF3-6.raw 5/4/16 14:00 239.1 6.15 0.97 -35.73 -6.43 24.23 1.24 -30.96 41 04052016_DFTF32-6.raw 5/4/16 14:07 239.1 2.73 1.09 -34.28 -6.67 23.98 0.50 -29.51 42 04052016_DFTF7-8.raw 5/4/16 14:14 239.3 1.17 1.26 -32.46 -6.40 24.26 0.19 -27.69 43 04052016_Urea_11.raw 5/4/16 14:20 238.8 10.46 Elem 0.10 -34.21 -6.38 24.28 20.59 -29.44 44 04052016_Urea_12.raw 5/4/16 14:27 238.8 15.76 Elem 0.15 -34.11 -6.19 24.48 20.47 -29.34 45 04052016_DFTF25-1.raw 5/4/16 14:34 239.2 1.49 1.03 -34.86 -6.10 24.57 0.28 -30.09 46 04052016_DFTF28.raw 5/4/16 14:41 239.1 1.79 0.91 -32.81 -5.83 24.85 0.39 -28.04 47 04052016_DFtop3.raw 5/4/16 14:48 239.1 2.46 1.49 -33.27 -5.71 24.97 0.32 -28.50 48 04052016_DFTF30-5.raw 5/4/16 14:55 239.0 4.21 0.99 -34.75 -5.63 25.06 0.84 -29.98 49 04052016_DFTF22-3.raw 5/4/16 15:02 239.0 1.83 1.21 -33.53 -5.97 24.71 0.30 -28.76 50 04052016_DFTF8-6.raw 5/4/16 15:08 239.5 1.84 1.38 -31.57 -5.61 25.08 0.27 -26.80 51 04052016_DFtop10.raw 5/4/16 15:15 239.2 1.38 1.14 -31.98 -5.79 24.89 0.24 -27.22 52 04052016_DFtop2.raw 5/4/16 15:22 239.0 1.18 1.39 -32.72 -5.67 25.02 0.17 -27.95 53 04052016_DFTF17-0.raw 5/4/16 15:29 239.2 3.05 1.22 -32.52 -5.55 25.14 0.49 -27.75 54 04052016_DFtop6.raw 5/4/16 15:36 239.3 1.06 1.10 -32.73 -5.84 24.84 0.19 -27.96 55 04052016_Urea_13.raw 5/4/16 15:43 238.6 13.41 Elem 0.13 -34.19 -5.74 24.94 19.93 -29.42 56 04052016_Urea_14.raw 5/4/16 15:50 238.7 10.05 Elem 0.10 -34.17 -6.02 24.66 19.72 -29.41

Table A.5 - Carbonate Carbon and Oxygen Raw Data_10.29.15

Table A.6 - Carbonate Carbon and Oxygen Raw Data_1.29.15

amplit c13aco o18acor o18asp c13asd o18asd sample_ID position RT ude mass c13 o18 rr r c13aspl l t t 01292016_REP_Fishbeck_JTB-1_R1.raw 129 125.3 11.943 0.109 -4.612 5.20057 1.89914 -8.81886 1.82407 -8.7816 1.82042 -8.8119 01292016_REP_Fishbeck_JTB-1_R2.raw 130 125.2 10.101 0.09 -4.68 5.21284 1.83123 -8.80658 1.75923 -8.774 1.75575 -8.8035 01292016_REP_Fishbeck_DFTF_0-0.raw 131 125.2 0.3931 0.096 -10.65 5.13887 01292016_REP_Fishbeck_DFTF_1-5.raw 132 125.3 6.275 0.105 -9.056 7.43045 -2.5455 -6.58897 -2.61139 -6.5657 -2.6145 -6.5934 01292016_REP_Fishbeck_DFTF_2-4.raw 133 125.4 6.0861 0.1 -9.567 5.5817 -3.056 -8.43772 -3.1188 -8.419 -3.1218 -8.4459 01292016_REP_Fishbeck_DFTF_3-6.raw 134 125.3 14.619 0.139 -9.918 4.49319 -3.4067 -9.52624 -3.46646 -9.512 -3.4693 -9.538 01292016_REP_Fishbeck_DFTF_5-0.raw 135 125.6 7.6832 0.103 -11.72 4.8721 -5.2097 -9.14732 -5.26637 -9.1375 -5.269 -9.1626 01292016_REP_Fishbeck_DFTF_7-8_1.raw 136 125.6 6.2183 0.116 -8.411 8.76708 -1.8997 -5.25234 -1.95333 -5.2467 -1.9558 -5.271 01292016_REP_Fishbeck_DFTF_7-8_2.raw 137 125.3 11.776 0.145 -8.528 8.73963 -2.017 -5.27979 -2.06755 -5.2782 -2.0698 -5.3016 01292016_REP_Fishbeck_DFTF_8-6.raw 138 125.4 12.22 0.138 -9.072 8.49089 -2.5613 -5.52853 -2.60873 -5.5308 -2.6108 -5.5533 01292016_REP_Fishbeck_DFTF_10-3.raw 139 125.4 12.1 0.138 -8.796 5.97461 -2.2849 -8.04481 -2.32929 -8.0507 -2.3312 -8.0723 01292016_REP_Fishbeck_DFTF_11-5.raw 140 125.5 10.67 0.148 -8.188 5.65414 -1.6772 -8.36528 -1.71856 -8.3745 -1.7203 -8.3953 01292016_REP_Fishbeck_JTB-1_R3.raw 141 125.5 11.869 0.115 -4.679 5.40291 1.83166 -8.61651 1.79342 -8.6288 1.79182 -8.6487 01292016_REP_Fishbeck_JTB-1_R4.raw 142 125.4 13.208 0.118 -4.688 5.45524 1.82292 -8.56419 1.78775 -8.5793 1.78631 -8.5983 01292016_REP_Fishbeck_DFTF_13-9.raw 143 125.6 10.875 0.121 -8.266 5.30478 -1.7555 -8.71464 -1.78759 -8.7321 -1.7889 -8.7503 01292016_REP_Fishbeck_DFTF_16-1.raw 144 125.5 10.211 0.11 -10.11 4.98136 -3.6015 -9.03806 -3.63055 -9.0576 -3.6316 -9.0749 01292016_REP_Fishbeck_DFTF_17.raw 145 125.5 13.915 0.143 -13.28 7.27228 -6.7675 -6.74714 -6.79351 -6.7685 -6.7944 -6.7849 01292016_REP_Fishbeck_DFTF_21-5.raw 146 125.7 3.4264 0.126 -9.895 8.29043 -3.3837 -5.72899 -3.40659 -5.7518 -3.4074 -5.7673 01292016_REP_Fishbeck_DFTF_22-3_1.raw 147 125.6 10.627 0.138 -11.46 6.04284 -4.9482 -7.97658 -4.96801 -8.0005 -4.9686 -8.0151 01292016_REP_Fishbeck_DFTF_22-3_2.raw 148 125.6 8.135 0.103 -11.04 5.23725 -4.5296 -8.78217 -4.54631 -8.8069 -4.5467 -8.8206 01292016_REP_Fishbeck_DFTF_23-2.raw 149 125.7 2.4945 0.103 -6.792 7.90109 -0.2807 -6.11833 -0.29442 -6.1435 -0.2947 -6.1564 01292016_REP_Fishbeck_DFTF_25-1.raw 150 125.7 8.7122 0.095 -9.155 8.51082 -2.6438 -5.5086 -2.65437 -5.534 -2.6545 -5.546 01292016_REP_Fishbeck_DFTF_27-5.raw 151 125.7 6.8636 0.144 -6.415 7.79898 0.09551 -6.22045 0.08797 -6.2457 0.08806 -6.2568 01292016_REP_Fishbeck_DFTF_14-8.raw 152 125.7 7.5691 0.117 -9.133 6.32843 -2.6221 -7.691 -2.62656 -7.7158 -2.6263 -7.7261 01292016_REP_Fishbeck_JTB-1_R5.raw 153 125.7 11.51 0.103 -4.773 5.49974 1.73793 -8.51969 1.73652 -8.5438 1.73696 -8.5532 01292016_REP_Fishbeck_JTB-1_R6.raw 154 125.5 14.603 0.141 -4.765 5.2726 1.7461 -8.74682 1.74777 -8.77 1.74837 -8.7785 01292016_REP_Fishbeck_DFTF_28.raw 155 125.7 10.994 0.1 -13.66 7.27018 -7.1509 -6.74924 -7.14616 -6.7711 -7.1454 -6.7788 01292016_REP_Fishbeck_DFTF_30-5.raw 156 125.7 9.4358 0.102 -8.676 7.70912 -2.1647 -6.31031 -2.15689 -6.3307 -2.1559 -6.3375 01292016_REP_Fishbeck_DFTF_32-6_1.raw 157 125.5 11.526 0.133 -9.651 8.17789 -3.14 -5.84154 -3.12918 -5.8602 -3.1281 -5.8661 01292016_REP_Fishbeck_DFTF_32-6_2.raw 158 125.8 8.7826 0.1 -9.699 8.34899 -3.1884 -5.67043 -3.1745 -5.6872 -3.1732 -5.6922 01292016_REP_Fishbeck_DFTF_32-9.raw 159 125.7 9.255 0.11 -9.217 8.40449 -2.7063 -5.61493 -2.68927 -5.6296 -2.6878 -5.6337 01292016_REP_Fishbeck_DFTF_34-3_1.raw 160 125.7 6.5437 0.1 -9.158 5.1863 -2.6474 -8.83312 -2.62728 -8.8454 -2.6257 -8.8487 01292016_REP_Fishbeck_DFTF_34-3_2.raw 161 125.7 8.7212 0.116 -9.135 4.72577 -2.6241 -9.29365 -2.60098 -9.3034 -2.5992 -9.3058 01292016_REP_Fishbeck_DFtop1.raw 162 125.7 8.6762 0.117 -8.178 8.15721 -1.6672 -5.86221 -1.64102 -5.8693 -1.6391 -5.8708 01292016_REP_Fishbeck_DFtop2_1.raw 163 125.8 9.9613 0.119 -8.074 8.14902 -1.5632 -5.87041 -1.53389 -5.8746 -1.5318 -5.8753 01292016_REP_Fishbeck_DFtop2_2.raw 164 125.7 7.2957 0.098 -8.012 8.07673 -1.5012 -5.94269 -1.46889 -5.9439 -1.4666 -5.9437 01292016_REP_Fishbeck_JTB-1_R7.raw 165 125.7 11.005 0.1 -4.765 5.37902 1.74598 -8.6404 1.7814 -8.6385 1.78388 -8.6374 01292016_REP_Fishbeck_JTB-1_R8.raw 166 125.5 14.869 0.138 -4.746 5.31002 1.76471 -8.70941 1.8032 -8.7042 1.80585 -8.7022 01292016_REP_Fishbeck_DFtop3.raw 167 125.7 8.2595 0.098 -8.452 7.26425 -1.9413 -6.75518 -1.89978 -6.7465 -1.897 -6.7437 01292016_REP_Fishbeck_DFtop4.raw 168 125.6 9.1061 0.103 -6.959 5.34451 -0.4483 -8.67491 -0.40366 -8.6628 -0.4007 -8.6591 01292016_REP_Fishbeck_DFtop5.raw 169 125.7 10.721 0.106 -8.498 5.6741 -1.9875 -8.34532 -1.93982 -8.3296 -1.9367 -8.325 01292016_REP_Fishbeck_DFtop6.raw 170 125.7 8.5866 0.132 -6.942 8.56161 -0.4311 -5.45781 -0.38034 -5.4384 -0.377 -5.433 01292016_REP_Fishbeck_DFtop7.raw 171 125.7 9.8302 0.107 -7.492 7.66842 -0.9814 -6.351 -0.92755 -6.3279 -0.9241 -6.3215 01292016_REP_Fishbeck_DFtop8.raw 172 125.9 5.9187 0.137 -9.454 8.50428 -2.9432 -5.51515 -2.88628 -5.4882 -2.8826 -5.481 01292016_REP_Fishbeck_DFtop9.raw 173 125.7 11.219 0.13 -7.978 8.72775 -1.4674 -5.29168 -1.40744 -5.2609 -1.4036 -5.2528 01292016_REP_Fishbeck_DFtop10.raw 174 125.8 5.4422 0.093 -6.677 8.23108 -0.1664 -5.78834 -0.10339 -5.7537 -0.0994 -5.7447 01292016_REP_Fishbeck_DFtop11.raw 175 125.7 8.6358 0.101 -6.527 6.16762 -0.0158 -7.8518 0.05035 -7.8132 0.05453 -7.8034 01292016_REP_Fishbeck_JTB-1_R9.raw 176 125.7 10.372 0.095 -4.821 5.28085 1.68943 -8.73858 1.75862 -8.696 1.76297 -8.6854 01292016_REP_Fishbeck_JTB-1_R10.raw 177 125.7 10.13 0.093 -4.78 5.08045 1.7309 -8.93897 1.80316 -8.8925 1.80768 -8.8809 01292016_blank_R4.raw 178 125.9 0.0713 0 -22.71 -0.7763

Table A.7 – Percent TIC, percent TOC, %TS

Carbon Elemen Sulfur Eleme Wt of Wt of Elemen tal Eleme ntal Sample Wt of Wt after remainin % tal compo ntal compo % Wt of in Tube sample( acidificat g sample % carbo compo sition % total compo sition Total Sample tube (g) (g) g) ion (g) (g) residue nate % TIC sition correct % TOC Carbon sition correc % TS Sulfur DFTF2.2 14.3454 21.4052 7.0598 17.0340 2.6886 38.08 61.92 7.43 0.26 0.26 0.10 7.53 1.33 1.43 0.54 7.97 DFTF3.6 13.3334 20.5523 7.2189 14.0460 0.7126 9.87 90.13 10.82 1.24 1.24 0.12 10.94 3.23 3.46 0.34 11.16 DFTF7.8 13.1785 21.3330 8.1545 16.9389 3.7604 46.11 53.89 6.47 0.19 0.19 0.09 6.55 0.96 1.03 0.47 6.94 DFTF8.6 13.2429 19.7585 6.5156 14.1162 0.8733 13.40 86.60 10.39 0.27 0.27 0.04 10.43 0.47 0.50 0.07 10.46 DFTF11.5 13.2436 20.7365 7.4929 14.4728 1.2292 16.40 83.60 10.03 0.52 0.52 0.09 10.12 1.78 1.91 0.31 10.34 DFTF16.1 13.2309 20.3361 7.1052 14.5650 1.3341 18.78 81.22 9.75 0.40 0.40 0.08 9.82 2.09 2.24 0.42 10.17 DFTF17 13.1355 20.7054 7.5699 13.1424 0.0069 0.09 99.91 11.99 0.49 0.49 0.00 11.99 1.00 1.07 0.00 11.99 DFTF22.3 13.1750 19.8984 6.7234 14.1885 1.0135 15.07 84.93 10.19 0.30 0.30 0.05 10.24 0.06 0.07 0.01 10.20 DFTF23.6 14.4271 22.2337 7.8066 15.8165 1.3894 17.80 82.20 9.86 0.31 0.31 0.05 9.92 0.07 0.08 0.01 9.88 DFTF25.1 13.3614 19.9783 6.6169 14.7972 1.4358 21.70 78.30 9.40 0.28 0.28 0.06 9.46 DFTF28 13.3501 21.2956 7.9455 13.6343 0.2842 3.58 96.42 11.57 0.39 0.39 0.01 11.58 0.15 0.17 0.01 11.58 DFTF30.5 13.1778 19.9114 6.7336 13.9670 0.7892 11.72 88.28 10.59 0.84 0.84 0.10 10.69 1.35 1.45 0.17 10.76 DFTF32.6 13.1185 20.1854 7.0669 14.1800 1.0615 15.02 84.98 10.20 0.50 0.50 0.07 10.27 0.25 0.28 0.04 10.24 DFtop 3 12.9348 21.0896 8.1548 16.8350 3.9002 47.83 52.17 6.26 0.32 0.32 0.15 6.42 1.58 1.69 0.81 7.07 DFtop2 13.3360 19.8342 6.4982 15.8926 2.5566 39.34 60.66 7.28 0.17 0.17 0.07 7.34 0.90 0.96 0.38 7.66 DFtop4 14.2797 21.1144 6.8347 14.6963 0.4166 6.10 93.90 11.27 0.27 0.27 0.02 11.29 1.84 1.97 0.12 11.39 DFtop6 14.3859 21.9443 7.5584 17.5355 3.1496 41.67 58.33 7.00 0.19 0.19 0.08 7.08 0.07 0.08 0.03 7.03 DFtop7 14.3365 22.8577 8.5212 17.9800 3.6435 42.76 57.24 6.87 0.98 0.98 0.42 7.29 1.44 1.54 0.66 7.53 DFtop8 14.3083 20.7265 6.4182 15.9140 1.6057 25.02 74.98 9.00 0.19 0.19 0.05 9.04 DFtop9 14.2578 19.8202 5.5624 17.9487 3.6909 66.35 33.65 4.04 0.24 0.24 0.16 4.20

Table A.8 - Summary of chemical signals for each sample

Summary of chemical signals in samplesHeight % above d13C d13C Carbo sample_ID datum Carbonate Organic nate d34S d18O 01292016_REP_Fishbeck_DFTF_0-0.raw 0 01292016_REP_Fishbeck_DFTF_1-5.raw 1.5 -2.61 -6.59

10292015_DFTF_2.2.raw 2.2 -2.88 -26.85 61.92 -13.33 -8.35 01292016_REP_Fishbeck_DFTF_2-4.raw 2.4 -3.12 -8.45 01292016_REP_Fishbeck_DFTF_3-6.raw 3.6 -3.47 -30.96 90.13 6.96 -9.54 10292015_DFTF_4.raw 4 -3.71 -8.58 01292016_REP_Fishbeck_DFTF_5-0.raw 5 -5.27 -9.16 01292016_REP_Fishbeck_DFTF_7-8_1.raw 7.8 -1.96 -27.69 53.89 7.64 -5.27 01292016_REP_Fishbeck_DFTF_7-8_2.raw 7.8 -2.07 -27.69 53.89 7.64 -5.3 10292015_DFTF_8.3.raw 8.3 -3.8 -6.08 01292016_REP_Fishbeck_DFTF_8-6.raw 8.6 -2.61 -26.8 86.6 22.3 -5.55 10292015_DFTF_10.1.raw 10.1 -1.4 -8.51 01292016_REP_Fishbeck_DFTF_10-3.raw 10.3 -2.33 -8.07 10292015_DFTF_10.4.raw 10.4 -1.65 -8.96 01292016_REP_Fishbeck_DFTF_11-5.raw 11.5 -1.72 -26.79 83.6 5.93 -8.4 10292015_DFTF_11.8.raw 11.8 -1.61 -6.16 10292015_DFTF_12.8.raw 12.8 -2.89 -8.84 01292016_REP_Fishbeck_DFTF_13-9.raw 13.9 -1.79 -8.75 01292016_REP_Fishbeck_DFTF_14-8.raw 14.8 -2.63 -7.73 01292016_REP_Fishbeck_DFTF_16-1.raw 16.1 -3.63 -28.38 81.22 -0.98 -9.07 01292016_REP_Fishbeck_DFTF_17.raw 17 -6.79 -27.75 10.12 -6.78 01292016_REP_Fishbeck_DFTF_21-5.raw 21.5 -3.41 -5.77 10292015_DFTF_22.raw 22 -4.12 -5.55 01292016_REP_Fishbeck_DFTF_22-3_1.raw 22.3 -4.97 -28.76 84.93 15.89 -8.02 01292016_REP_Fishbeck_DFTF_22-3_2.raw 22.3 -4.55 -28.76 84.93 15.89 -8.82 01292016_REP_Fishbeck_DFTF_23-2.raw 23.2 -0.29 -6.16 10292015_DFTF_23.5_1.raw 23.5 -5.83 -8.32 10292015_DFTF_23.5_2.raw 23.5 -2.97 -8.96 10292015_DFTF_23.6_1.raw 23.6 -4.63 -28.63 82.2 17.72 -9.01 10292015_DFTF_23.6_2.raw 23.6 -5.11 -28.63 82.2 17.72 -7.56 10292015_DFTF_23.6_3.raw 23.6 -5.45 -28.63 82.2 17.72 -7.86 01292016_REP_Fishbeck_DFTF_25-1.raw 25.1 -2.65 -30.09 78.3 -5.55

10292015_DFTFA_27.raw 27 -2.44 -6.64 01292016_REP_Fishbeck_DFTF_27-5.raw 27.5 0.09 -6.26 01292016_REP_Fishbeck_DFTF_28.raw 28 -7.15 -28.04 96.42 5.27 -6.78 01292016_REP_Fishbeck_DFTF_30-5.raw 30.5 -2.16 -29.98 88.28 7.93 -6.34 10292015_DFTF_32.raw 32 -1.08 -6.23 01292016_REP_Fishbeck_DFTF_32-6_1.raw 32.6 -3.13 -29.51 84.98 22.33 -5.87 01292016_REP_Fishbeck_DFTF_32-6_2.raw 32.6 -3.17 -29.51 84.98 22.33 -5.69 01292016_REP_Fishbeck_DFTF_32-9.raw 32.9 -2.69 -5.63 01292016_REP_Fishbeck_DFtop1.raw 34 -1.64 -5.87 01292016_REP_Fishbeck_DFTF_34-3_1.raw 34.3 -2.63 -8.85 01292016_REP_Fishbeck_DFTF_34-3_2.raw 34.3 -2.6 -9.31 01292016_REP_Fishbeck_DFtop2_1.raw 35 -1.53 -27.95 60.66 9.36 -5.88 01292016_REP_Fishbeck_DFtop2_2.raw 35 -1.47 -27.95 60.66 9.36 -5.94

01292016_REP_Fishbeck_DFtop11.raw 35 0.05 -7.8 01292016_REP_Fishbeck_DFtop3.raw 36 -1.9 -28.5 93.9 9.8 -6.74 01292016_REP_Fishbeck_DFtop10.raw 36 -0.1 -27.22 52.17 -5.74

01292016_REP_Fishbeck_DFtop4.raw 37 -0.4 -26.78 58.33 17.18 -8.66 01292016_REP_Fishbeck_DFtop9.raw 37 -1.4 -5.25 01292016_REP_Fishbeck_DFtop5.raw 38 -1.94 -8.33 01292016_REP_Fishbeck_DFtop8.raw 38 -2.88 -27.3 33.65 -5.48 01292016_REP_Fishbeck_DFtop7.raw 39 -0.92 -29.35 74.98 24.03 -6.32 42 01292016_REP_Fishbeck_DFtop6.raw 40 -0.38 -27.96 57.24 22.39 -5.43 Table A.9 - Summary of textures present in each sample

Height above Mudcracks sample_ID datum Intraclastic? Fossils? Vugs? ? Pyrite? 01292016_REP_Fishbeck_DFTF_0-0.raw 0 01292016_REP_Fishbeck_DFTF_1-5.raw 1.5

10292015_DFTF_2.2.raw 2.2 01292016_REP_Fishbeck_DFTF_2-4.raw 2.4 Intraclastic 01292016_REP_Fishbeck_DFTF_3-6.raw 3.6 10292015_DFTF_4.raw 4 01292016_REP_Fishbeck_DFTF_5-0.raw 5 01292016_REP_Fishbeck_DFTF_7-8_1.raw 7.8 01292016_REP_Fishbeck_DFTF_7-8_2.raw 7.8 10292015_DFTF_8.3.raw 8.3 01292016_REP_Fishbeck_DFTF_8-6.raw 8.6 10292015_DFTF_10.1.raw 10.1 slightly fossilferous Pyrite 01292016_REP_Fishbeck_DFTF_10-3.raw 10.3 slightly fossiliferous 10292015_DFTF_10.4.raw 10.4 slightly fossilferous Pyrite 01292016_REP_Fishbeck_DFTF_11-5.raw 11.5 slightly fossiliferous 10292015_DFTF_11.8.raw 11.8 Intraclastic 10292015_DFTF_12.8.raw 12.8 fossiliferous 01292016_REP_Fishbeck_DFTF_13-9.raw 13.9 01292016_REP_Fishbeck_DFTF_14-8.raw 14.8 sample containing fossils sample containing pyrite 01292016_REP_Fishbeck_DFTF_16-1.raw 16.1 sample containing fossils 01292016_REP_Fishbeck_DFTF_17.raw 17 Vuggy 01292016_REP_Fishbeck_DFTF_21-5.raw 21.5 10292015_DFTF_22.raw 22 01292016_REP_Fishbeck_DFTF_22-3_1.raw 22.3 sample containing fossils Vuggy 01292016_REP_Fishbeck_DFTF_22-3_2.raw 22.3 sample containing fossils Vuggy 01292016_REP_Fishbeck_DFTF_23-2.raw 23.2 10292015_DFTF_23.5_1.raw 23.5 slightly fossiliferous 10292015_DFTF_23.5_2.raw 23.5 fossiliferous Vuggy 10292015_DFTF_23.6_1.raw 23.6 Mudcracked 10292015_DFTF_23.6_2.raw 23.6 fossiliferous Mudcracked 10292015_DFTF_23.6_3.raw 23.6 slightly fossiliferous Mudcracked 01292016_REP_Fishbeck_DFTF_25-1.raw 25.1

10292015_DFTFA_27.raw 27 Intraclastic 01292016_REP_Fishbeck_DFTF_27-5.raw 27.5 01292016_REP_Fishbeck_DFTF_28.raw 28 01292016_REP_Fishbeck_DFTF_30-5.raw 30.5 10292015_DFTF_32.raw 32 01292016_REP_Fishbeck_DFTF_32-6_1.raw 32.6 Vuggy 01292016_REP_Fishbeck_DFTF_32-6_2.raw 32.6 Vuggy Mudcracks? 01292016_REP_Fishbeck_DFTF_32-9.raw 32.9 01292016_REP_Fishbeck_DFtop1.raw 34 Intraclastic 01292016_REP_Fishbeck_DFTF_34-3_1.raw 34.3 01292016_REP_Fishbeck_DFTF_34-3_2.raw 34.3 01292016_REP_Fishbeck_DFtop2_1.raw 35 Intraclastic Pyrite 01292016_REP_Fishbeck_DFtop2_2.raw 35 Intraclastic Pyrite

01292016_REP_Fishbeck_DFtop11.raw 35 01292016_REP_Fishbeck_DFtop3.raw 36 01292016_REP_Fishbeck_DFtop10.raw 36

01292016_REP_Fishbeck_DFtop4.raw 37 sample containing fossils Sample containing pyrite 01292016_REP_Fishbeck_DFtop9.raw 37 01292016_REP_Fishbeck_DFtop5.raw 38 slightly fossiliferous 01292016_REP_Fishbeck_DFtop8.raw 38 01292016_REP_Fishbeck_DFtop7.raw 39 01292016_REP_Fishbeck_DFtop6.raw 40