A high-resolution record of early Paleozoic climate

The spatial coverage and temporal resolution of the Early Paleozoic paleoclimate record are limited, primarily due to the paucity of well-preserved skeletal material commonly used for oxygen-isotope paleothermometry. Bulk-rock δ¹⁸O datasets can provide broader coverage and higher resolution, but are prone to burial alteration. We assess the diagenetic character of two thick Cambro–Ordovician carbonate platforms with minimal to moderate burial by pairing clumped and bulk isotope analyses of micritic carbonates. Despite resetting of the clumped-isotope thermometer at both sites, our samples indicate relatively little change to their bulk δ¹⁸O due to low fluid exchange. Consequently, both sequences preserve temporal trends in δ¹⁸O. Motivated by this result, we compile a global suite of bulk rock δ¹⁸O data, stacking overlapping regional records to minimize diagenetic influences on overall trends. We find good agreement of bulk rock δ¹⁸O with brachiopod and conodont δ¹⁸O trends through time. Given evidence that the δ¹⁸O value of seawater has not evolved substantially through the Phanerozoic, we interpret this record as primarily reflecting changes in tropical, nearshore seawater temperatures and only moderately modified by diagenesis. Focusing on the samples with the most enriched, and thus likely least-altered, δ¹⁸O values, we reconstruct Late Cambrian warming, Early Ordovician extreme warmth, and cooling around the Early–Middle Ordovician boundary. Our record is consistent with models linking the Great Ordovician Biodiversification Event to cooling of previously very warm tropical oceans. In addition, our high-temporal-resolution record suggests previously unresolved transient warming and climate instability potentially associated with Late Ordovician tectonic events

Microbial Activity and Neomorphism Influence the Composition and Microfabric of Ooids From Great Salt Lake, UT

The sediment along the shorelines of Great Salt Lake (GSL), Utah is dominated by ooids, concentrically-coated carbonate sand grains. Two characteristics differentiate GSL ooids from typical modern marine ooids: well-developed radial aragonite microfabrics and the ubiquitous occurrence of a Mg-silicate phase. The radial microfabrics have formed the basis of conceptual models applied to understand the formation of radial fabrics in ancient ooids, but the formation of the Mg-silicates, and the relationship between Mg-silicates and radial aragonite crystals have received little attention. The occurrence of Mg-silicates in GSL ooids is surprising because GSL lake water pH is ~8.3, too low for Mg-silicate precipitation (requires pH&gt;8.7). We use transmitted light microscopy, element mapping via wavelength-dispersive x-ray spectroscopy with electron microprobe, scanning electron microscopy, and synchrotron x-ray fluorescence (XRF) mapping and sulfur K-edge absorption spectroscopy to explore the spatial relationships between the mineral phases in GSL ooids. We observe large euhedral aragonite crystals penetrating Mg-silicate zones and cutting across laminar cortices, suggesting that the characteristic radial aragonitic fabrics in GSL ooids, traditionally interpreted as a primary structure, are enhanced, or in some cases entirely created via neomorphism. XRF maps reveal that Mg-silicate zones co-occur with elemental sulfur (S0), which we interpret as a metabolic intermediate of microbial sulfur cycling. This co-occurrence supports our hypothesis that microbial sulfur cycling plays a key role in the formation of GSL ooids by locally shifting pH beyond the threshold for Mg-silicate precipitation. This compositional fingerprint could serve as a biosignature in ancient lacustrine strata where Mg-silicates co-occur with carbonate minerals. &nbsp;</p

Active Ooid Growth Driven By Sediment Transport in a High-Energy Shoal, Little Ambergris Cay, Turks and Caicos Islands

Ooids are a common component of carbonate successions of all ages and present significant potential as paleoenvironmental proxies, if the mechanisms that control their formation and growth can be understood quantitatively. There are a number of hypotheses about the controls on ooid growth, each offering different ideas on where and how ooids accrete and what role, if any, sediment transport and abrasion might play. These hypotheses have not been well tested in the field, largely due to the inherent challenges of tracking individual grains over long timescales. This study presents a detailed field test of ooid-growth hypotheses on Little Ambergris Cay in the Turks and Caicos Islands, British Overseas Territories. This field site is characterized by westward net sediment transport from waves driven by persistent easterly trade winds. This configuration makes it possible to track changes in ooid properties along their transport path as a proxy for changes in time. Ooid size, shape, and radiocarbon age were compared along this path to determine in which environments ooids are growing or abrading. Ooid surface textures, petrographic fabrics, stable-isotope compositions (δ^(13)C, δ^(18)O, and δ^(34)S), lipid geochemistry, and genetic data were compared to characterize mechanisms of precipitation and degradation and to determine the relative contributions of abiotic (e.g., abiotic precipitation, physical abrasion) and biologically influenced processes (e.g., biologically mediated precipitation, fabric destruction through microbial microboring and micritization) to grain size and character. A convergence of evidence shows that active ooid growth occurs along the transport path in a high-energy shoal environment characterized by frequent suspended-load transport: median ooid size increases by more than 100 μm and bulk radiocarbon ages decrease by 360 yr westward along the ∼ 20 km length of the shoal crest. Lipid and 16S rRNA data highlight a spatial disconnect between the environments with the most extensive biofilm colonization and environments with active ooid growth. Stable-isotope compositions are indistinguishable among samples, and are consistent with abiotic precipitation of aragonite from seawater. Westward increases in ooid sphericity and the abundance of well-polished ooids illustrate that ooids experience subequal amounts of growth and abrasion—in favor of net growth—as they are transported along the shoal crest. Overall, these results demonstrate that, in the Ambergris system, the mechanism of ooid growth is dominantly abiotic and the loci of ooid growth is determined by both carbonate saturation and sediment transport mode. Microbes play a largely destructive, rather than constructive, role in ooid size and fabric

Pyrite-walled tube structures in a Mesoproterozoic sediment-hosted metal sulfide deposit

Unusual decimeter-scale structures occur in the sediment-hosted Black Butte Copper Mine Project deposit within lower Mesoproterozoic strata of the Belt Supergroup, Montana. These low domal and stratiform lenses are made up of millimeter-scale, hollow or mineral-filled tubes bounded by pyrite walls. X-ray micro−computed tomography (micro-CT) shows that the tube structures are similar to the porous fabric of modern diffuse hydrothermal vents, and they do not resemble textures associated with the mineralization of known microbial communities. We determined the sulfur isotopic composition of sulfide minerals with in situ secondary ion mass spectrometry (SIMS) and of texture-specific sulfate phases with multicollector−inductively coupled plasma−mass spectrometry (MC-ICP-MS). The sedimentological setting, ore paragenesis, sulfur isotope systematics, and porosity structure of these porous precipitates constrain the site of their formation to above the sediment-water interface where metalliferous hydrothermal fluids vented into the overlying water column. These data constrain the geochemistry of the Mesoproterozoic sediment-water interface and the site of deposition for copper-cobalt-silver mineralization. Metals in the hydrothermal fluids titrated sulfide in seawater to create tortuous fluid-flow conduits. Pyrite that precipitated at the vent sites exhibits large sulfur isotope fractionation (>50‰), which indicates a close association between the vents and sulfate-reducing microbiota. In the subsurface, base metal sulfides precipitated from sulfide formed during the reduction of early diagenetic barite, also ultimately derived from seawater. This model suggests dynamic bottom-water redox conditions at the vent site driven by the interplay between sulfate-reducing organisms and metalliferous fluid effluence

Sulfur isotopes in rivers : insights into global weathering budgets, pyrite oxidation, and the modern sulfur cycle

This research was funded by a Foster and Coco Stanback postdoctoral fellowship and a Marie Curie Career Integration Grant (CIG14-631752) to AB. JFA acknowledges the support of NSF-OCE grant 1340174 and NSF-EAR grant 1349858. WF acknowledges the support of a grant from the David and Lucile Packard Foundation.The biogeochemical sulfur cycle is intimately linked to the cycles of carbon, iron, and oxygen, and plays an important role in global climate via weathering reactions and aerosols. However, many aspects of the modern budget of the global sulfur cycle are not fully understood. We present new δ34S measurements on sulfate from more than 160 river samples from different geographical and climatic regions—more than 46% of the world's freshwater flux to the ocean is accounted for in this estimate of the global riverine sulfur isotope budget. These measurements include major rivers and their tributaries, as well as time series, and are combined with previously published data to estimate the modern flux-weighted global riverine δ34S as 4.4 ± 4.5‰ (V-CDT), and 4.8 ± 4.9‰ when the most polluted rivers are excluded. The sulfur isotope data, when combined with major anion and cation concentrations, allow us to tease apart the relative contributions of different processes to the modern riverine sulfur budget, resulting in new estimates of the flux of riverine sulfate due to the oxidative weathering of pyrites (1.3 ± 0.2 Tmol S/y) and the weathering of sedimentary sulfate minerals (1.5 ± 0.2 Tmol S/y). These data indicate that previous estimates of the global oxidative weathering of pyrite have been too low by a factor of two. As pyrite oxidation coupled to carbonate weathering can act as a source of CO2 to the atmosphere, this global pyrite weathering budget implies that the global CO2 weathering sink is overestimated. Furthermore, the large range of sulfur isotope ratios in modern rivers indicates that secular changes in the lithologies exposed to weathering through time could play a major role in driving past variations in the δ34S value of seawater.PostprintPostprintPostprintPeer reviewe

Active Ooid Growth Driven By Sediment Transport in a High-Energy Shoal, Little Ambergris Cay, Turks and Caicos Islands

Ooids are a common component of carbonate successions of all ages and present significant potential as paleoenvironmental proxies, if the mechanisms that control their formation and growth can be understood quantitatively. There are a number of hypotheses about the controls on ooid growth, each offering different ideas on where and how ooids accrete and what role, if any, sediment transport and abrasion might play. These hypotheses have not been well tested in the field, largely due to the inherent challenges of tracking individual grains over long timescales. This study presents a detailed field test of ooid-growth hypotheses on Little Ambergris Cay in the Turks and Caicos Islands, British Overseas Territories. This field site is characterized by westward net sediment transport from waves driven by persistent easterly trade winds. This configuration makes it possible to track changes in ooid properties along their transport path as a proxy for changes in time. Ooid size, shape, and radiocarbon age were compared along this path to determine in which environments ooids are growing or abrading. Ooid surface textures, petrographic fabrics, stable-isotope compositions (δ^(13)C, δ^(18)O, and δ^(34)S), lipid geochemistry, and genetic data were compared to characterize mechanisms of precipitation and degradation and to determine the relative contributions of abiotic (e.g., abiotic precipitation, physical abrasion) and biologically influenced processes (e.g., biologically mediated precipitation, fabric destruction through microbial microboring and micritization) to grain size and character. A convergence of evidence shows that active ooid growth occurs along the transport path in a high-energy shoal environment characterized by frequent suspended-load transport: median ooid size increases by more than 100 μm and bulk radiocarbon ages decrease by 360 yr westward along the ∼ 20 km length of the shoal crest. Lipid and 16S rRNA data highlight a spatial disconnect between the environments with the most extensive biofilm colonization and environments with active ooid growth. Stable-isotope compositions are indistinguishable among samples, and are consistent with abiotic precipitation of aragonite from seawater. Westward increases in ooid sphericity and the abundance of well-polished ooids illustrate that ooids experience subequal amounts of growth and abrasion—in favor of net growth—as they are transported along the shoal crest. Overall, these results demonstrate that, in the Ambergris system, the mechanism of ooid growth is dominantly abiotic and the loci of ooid growth is determined by both carbonate saturation and sediment transport mode. Microbes play a largely destructive, rather than constructive, role in ooid size and fabric

Variability in Sulfur Isotope Records of Phanerozoic Seawater Sulfate

The δ³⁴S of seawater sulfate reflects processes operating at the nexus of sulfur, carbon, and oxygen cycles. However, knowledge of past seawater sulfate δ³⁴S values must be derived from proxy materials that are impacted differently by depositional and postdepositional processes. We produced new time series estimates for the δ³⁴S value of seawater sulfate by combining 6,710 published data from three sedimentary archives—marine barite, evaporites, and carbonate‐associated sulfate—with updated age constraints on the deposits. Robust features in multiple records capture temporal trends in the δ³⁴S value of seawater and its interplay with other Phanerozoic geochemical and stratigraphic trends. However, high‐frequency discordances indicate that each record is differentially prone to depositional biases and diagenetic overprints. The amount of noise, quantified from the variograms of each record, increases with age for all δ³⁴S proxies, indicating that postdepositional processes obscure detailed knowledge of seawater sulfate's δ³⁴S value deeper in time

A high-resolution record of early Paleozoic climate

The spatial coverage and temporal resolution of the Early Paleozoic paleoclimate record are limited, primarily due to the paucity of well-preserved skeletal material commonly used for oxygen-isotope paleothermometry. Bulk-rock δ¹⁸O datasets can provide broader coverage and higher resolution, but are prone to burial alteration. We assess the diagenetic character of two thick Cambro-Ordovician carbonate platforms with minimal to moderate burial by pairing clumped and bulk isotope analyses of micritic carbonates. Despite resetting of the clumped-isotope thermometer at both sites, our samples indicate relatively little change to their bulk δ¹⁸O due to low fluid exchange. Consequently, both sequences preserve temporal trends in δ¹⁸O. Motivated by this result, we compile a global suite of bulk rock δ¹⁸O data, stacking overlapping regional records to minimize diagenetic influences on overall trends. We find good agreement of bulk rock δ¹⁸O with brachiopod and conodont δ¹⁸O trends through time. Given evidence that the δ¹⁸O value of seawater has not evolved substantially through the Phanerozoic, we interpret this record as primarily reflecting changes in tropical, nearshore seawater temperatures and only moderately modified by diagenesis. Focusing on the samples with the most enriched, and thus likely least-altered, δ¹⁸O values, we reconstruct Late Cambrian warming, Early Ordovician extreme warmth, and cooling around the Early-Middle Ordovician boundary. Our record is consistent with models linking the Great Ordovician Biodiversification Event to cooling of previously very warm tropical oceans. In addition, our high-temporal-resolution record suggests previously unresolved transient warming and climate instability potentially associated with Late Ordovician tectonic events

Biosignature preservation aided by organic-cation interactions in Proterozoic tidal environments

The preservation of organic biosignatures during the Proterozoic Eon required specific taphonomic windows that could entomb organic matter to preserve amorphous kerogen and even microbial body fossils before they could be extensively degraded. Some of the best examples of such preservation are found in early diagenetic chert that formed in peritidal environments. This chert contains discrete domains of amorphous kerogen and sometimes kerogenous microbial mat structures and microbial body fossils. Our understanding of how these exquisite microfossils were preserved and the balance between organic degradation and mineral formation has remained incomplete. Here, we present new insights into organic preservation in Proterozoic peritidal environments facilitated through interactions among organic matter, cations, and silica. Organic matter from Proterozoic peritidal environments is not preserved by micro- or cryptocrystalline quartz alone. Rather, preservation includes cation-rich nanoscopic phases containing magnesium, calcium, silica, and aluminum that pre-date chert emplacement and may provide nucleation sites for silica deposition and enable further chert development. Using scanning electron microscopy and elemental mapping with energy dispersive X-ray spectroscopy, we identify cation enrichment in Proterozoic organic matter and cation-rich nanoscopic phases that pre-date chert. We pair these analyses with precipitation experiments to investigate the role of cations in the precipitation of silica from seawater. Our findings suggest that organic preservation in peritidal environments required rapid formation of nanoscopic mineral phases through the interactions of organic matter with seawater. These organic-cation interactions likely laid the initial foundation for the preservation and entombment of biosignatures, paving the way for the development of the fossiliferous chert that now contains these biosignatures and preserves a record of Proterozoic life.</p