What the ~1.4 Ga Xiamaling Formation can and cannot tell us about the mid‐Proterozoic ocean

Despite a surge of recent work, the evolution of mid‐Proterozoic oceanic–atmospheric redox remains heavily debated. Constraining the dynamics of Proterozoic redox evolution is essential to determine the role, if any, that anoxia played in protracting the development of eukaryotic diversity. We present a multiproxy suite of high‐resolution geochemical measurements from a drill core capturing the ~1.4 Ga Xiamaling Formation, North China Craton. Specifically, we analyzed major and trace element concentrations, sulfur and molybdenum isotopes, and iron speciation not only to better understand the local redox conditions but also to establish how relevant our data are to understanding the contemporaneous global ocean. Our results suggest that throughout deposition of the Xiamaling Formation, the basin experienced varying degrees of isolation from the global ocean. During deposition of the lower organic‐rich shales (130–85 m depth), the basin was extremely restricted, and the reservoirs of sulfate and trace metals were drawn down almost completely. Above a depth of 85 m, shales were deposited in dominantly euxinic waters that more closely resembled a marine system and thus potentially bear signatures of coeval seawater. In the most highly enriched sample from this upper interval, the concentration of molybdenum is 51 ppm with a δ⁹⁸Mo value of +1.7‰. Concentrations of Mo and other redox‐sensitive elements in our samples are consistent with a deep ocean that was largely anoxic on a global scale. Our maximum δ⁹⁸Mo value, in contrast, is high compared to published mid‐Proterozoic data. This high value raises the possibility that the Earth's surface environments were transiently more oxygenated at ~1.4 Ga compared to preceding or postdating times. More broadly, this study demonstrates the importance of integrating all available data when attempting to reconstruct surface O₂ dynamics based on rocks of any age.     

Late Cretaceous marine arthropods relied on terrestrial organic matter as a food source: Geochemical evidence from the Coon Creek Lagerstätte in the Mississippi Embayment

The Upper Cretaceous Coon Creek Lagerstätte of Tennessee, USA, is known for its extremely well‐preserved mollusks and decapod crustaceans. However, the depositional environment of this unit, particularly its distance to the shoreline, has long been equivocal. To better constrain the coastal proximity of the Coon Creek Formation, we carried out a multiproxy geochemical analysis of fossil decapod (crab, mud shrimp) cuticle and associated sediment from the type section. Elemental analysis and Raman spectroscopy confirmed the presence of kerogenized carbon in the crabs and mud shrimp; carbon isotope (δ¹³C) analysis of bulk decapod cuticle yielded similar mean δ¹³C values for both taxa (?25.1‰ and ?26‰, respectively). Sedimentary biomarkers were composed of n‐alkanes from C₁₆ to C₃₆, with the short‐chain n‐alkanes dominating, as well as other biomarkers (pristane, phytane, hopanes). Raman spectra and biomarker thermal maturity indices suggest that the Coon Creek Formation sediments are immature, which supports retention of unaltered, biogenic isotopic signals in the fossil organic carbon remains. Using our isotopic results and published calcium carbonate δ¹³C values, we modeled carbon isotope values of carbon sources in the Coon Creek Formation, including potential marine (phytoplankton) and terrestrial (plant) dietary sources. Coon Creek Formation decapod δ¹³C values fall closer to those estimated for terrigenous plants than marine phytoplankton, indicating that these organisms were feeding primarily on terrigenous organic matter. From this model, we infer that the Coon Creek Formation experienced significant terrigenous organic matter input via a freshwater source and thus was deposited in a shallow, nearshore marine environment proximal to the shoreline. This study helps refine the paleoecology of nearshore settings in the Mississippi Embayment during the global climatic shift in the late Campanian–early Maastrichtian and demonstrates for the first time that organic δ¹³C signatures in exceptionally preserved fossil marine arthropods are a viable proxy for use in paleoenvironmental reconstructions.     

Revisiting marine redox conditions during the Ediacaran Shuram carbon isotope excursion

The Neoproterozoic carbonate record contains multiple carbon isotope anomalies, which are the subject of intense debate. The largest of these anomalies, the Shuram excursion (SE), occurred in the mid-Ediacaran (~574–567 Ma). Accurately reconstructing marine redox landscape is a clear path toward making sense of the mechanism that drives this δ¹³C anomaly. Here, we report new uranium isotopic data from the shallow-marine carbonates of the Wonoka Formation, Flinders Ranges, South Australia, where the SE is well preserved. Our data indicate that the δ²³⁸U trend during the SE is highly reproducible across globally disparate sections from different depositional settings. Previously, it was proposed that the positive shift of δ²³⁸U values during the SE suggests an extensive, near-modern level of marine oxygenation. However, recent publications suggest that the fractionation of uranium isotopes in ferruginous and anoxic conditions is comparable, opening up the possibility of non-unique interpretations of the carbonate uranium isotopic record. Here, we build on this idea by investigating the SE in conjunction with additional geochemical proxies. Using a revised uranium isotope mass balance model and an inverse stochastic carbon cycle model, we reevaluate models for δ¹³C and δ²³⁸U trends during the SE. We suggest that global seawater δ²³⁸U values during the SE could be explained by an expansion of ferruginous conditions and do not require a near-modern level of oxygenation during the mid-Ediacaran.     

Lake-based climate reconstruction in Africa: progress and challenges

Lake sediments are and will continue to be the principal source of information on the climate history of tropical Africa. However, unequivocal interpretation of the various sedimentological, biological, and geochemical climate-proxy data extracted from lake sediments with respect to past variations in temperature, rainfall, and wind is an extremely complex and challenging exercise. Outstanding problems are: (1) the inherent conflict between a lake's sensitivity to climate change (its ability to respond to and record relatively modest, short-lived climatic anomalies) and its persistence as an archive of climate change (the probability that it survived the most arid events without desiccation or erosion, allowing it to preserve a continuous record of climate history); (2) the scarcity of annually laminated sediment records, which in other regions can provide superior chronological precision to lake-based climate reconstructions; (3) lack of a quantitative (sometimes even qualitative) mechanistic understanding of the chain of cause and effect linking sedimentary climate-proxy indicators to particular climatic variables; and (4) lack of a proxy indicator for past temperature changes unaffected by simultaneous changes in moisture balance. Clearly, a climate-proxy record with high stratigraphic resolution does not represent a high-resolution record of past climate change without demonstration that the sedimentary archive is continuous and undisturbed; that the lake system responds to climate variability at the appropriate time scale; and that any threshold effects in the relationship between the proxy indicator and climate are accounted for. Calibration and validation of climate-proxy indicators is tantamount to establishing accurate reconstructions, but in Africa historical validation of proxy indicators is handicapped by the scarcity of long-term lake-monitoring data. The reliability of lake-based climate reconstructions is enhanced when inferences derived from several proxy indicators (sedimentological, biological, or geochemical), that each have an independent mechanistic link to climate, show a high level of coherence. Given the scarcity of annually-resolved sediment records in tropical Africa, we may have to accept the limitations of ²¹⁰Pb- and ¹⁴C-based chronologies when evaluating the synchrony of reconstructed climate events between sites and regions; however, careful site selection and detailed lithostratigraphic analyses can go a long way to optimise depth-age models and reduce uncertainty in the timing of past climate changes.     

Connecting local environmental sequences to global climate patterns: evidence from the hominin-bearing Hadar Formation, Ethiopia

Central to the debate surrounding global climate change and Plio-Pleistocene hominin evolution is the degree to which orbital-scale climate patterns influence low-latitude continental ecosystems and how these influences can be distinguished from regional volcano-tectonic events and local environmental effects. The Pliocene Hadar Formation of Ethiopia preserves a record of hominin paleoenvironments from roughly 3.5 to 2.2 Ma at a temporal resolution relevant to evolutionary change within hominins and other taxa. This study integrates the high-resolution sedimentological and paleontological records at Hadar with climate proxies such as marine core isotope, dust, and sapropel records. Consistent cycling observed both between and within fluvial and lacustrine depositional environments prior to 2.9 Ma at Hadar appears to be predominantly climatic in nature. In contrast a significant change in depositional facies after 2.9 Ma to sequences dominated by conglomerate cut-and-fill cycles indicates a strong tectonic signature related to regional developments in the Main Ethiopian Rift. While specific events seen in marine proxy records may have parallels in the Hadar environmental archive, their overall patterns of high versus low variability may be even more relevant. For example, periods of relatively high-amplitude climate oscillations between 3.15 and 2.95 Ma may be linked to noted size-related morphological changes within the Hadar Australopithecus afarensis lineage and a significant increase in more arid-adapted bovid taxa. Increased aridity in East Africa during this period is also indicated by peaks in eolian dust in the marine core record. Conversely, the dominant lacustrine phase at Hadar ca. 3.3 Ma coincides with the least variable period in several climate proxy records, including marine core foraminifera delta(18)O values and eolian dust concentration. This phase is also coeval with low insolation variability and a very distinct and significant long-term period of low dust percentage in circum-Africa marine cores.     

Local paleoenvironmental controls on the carbon‐isotope record defining the Bitter Springs Anomaly

Large magnitude (>10‰) carbon‐isotope (δ¹³C) excursions recorded in carbonate‐bearing sediments are increasingly used to monitor environmental change and constrain the chronology of the critical interval in the Neoproterozoic stratigraphic record that is timed with the first appearance and radiation of metazoan life. The ~10‰ Bitter Springs Anomaly preserved in Tonian‐aged (1000–720 Ma) carbonate rocks in the Amadeus Basin of central Australia has been offered as one of the best preserved examples of a primary marine δ¹³C excursion because it is regionally reproducible and δ¹³C values covary in organic and carbonate carbon arguing against diagenetic exchange. However, here we show that δ¹³C values defining the excursion coincide with abrupt lithofacies changes between regularly cyclic grainstone and microbial carbonates, and desiccated red bed mudstones with interbedded evaporite and dolomite deposits, recording local environmental shifts from restricted marine conditions to alkaline lacustrine and playa settings that preserve negative (?4‰) and positive (+6‰) δ¹³C values, respectively. The stratigraphic δ¹³C pattern in both organic and carbonate carbon recurs within the basin in a similar way to associated sedimentary facies, reflecting the linkage of local paleoenvironmental conditions and δ¹³C values. These local excursions may be time transgressive or record a relative sea‐level influence manifest through exposure of sub‐basins isolated by sea‐level fall below shallow sills, but are independent of secular seawater variation. As the shallow intracratonic setting of the Bitter Springs Formation is typical of other Neoproterozoic carbonate successions used to construct the present δ¹³C seawater record, it identifies the potential for local influences on δ¹³C excursions that are neither diagenetic nor representative of the global exogenic cycle.     

Carbonate facies‐specific stable isotope data record climate,hydrology, and microbial communities in Great Salt Lake,UT

Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ¹⁸O_water, δ¹³C_DIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ¹⁸O_carb, δ¹³C_carb, ?₄₇), as well as carbon isotopic compositions of bulk organic matter (δ¹³C_org) and dissolved inorganic carbon (DIC; δ¹³C_DIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ?₄₇ isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(?₄₇)), δ¹⁸O_carb, and calculated δ¹⁸O_water in isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.     

The Sirius Passet Lagerstätte of North Greenland—A geochemical window on early Cambrian low‐oxygen environments and ecosystems

The early Cambrian Sirius Passet fauna of northernmost Greenland (Cambrian Series 2, Stage 3) contains exceptionally preserved soft tissues that provide an important window to early animal evolution, while the surrounding sediment holds critical data on the palaeodepositional water‐column chemistry. The present study combines palaeontological data with a multiproxy geochemical approach based on samples collected in situ at high stratigraphic resolution from Sirius Passet. After careful consideration of chemical alterations during burial, our results demonstrate that fossil preservation and biodiversity show significant correlation with iron enrichments (Fe_HR/Fe_T), trace metal behaviour (V/Al), and changes in nitrogen cycling (δ¹⁵N). These data, together with Mo/Al and the preservation of organic carbon (TOC), are consistent with a water column that was transiently low in oxygen concentration, or even intermittently anoxic. When compared with the biogeochemical characteristics of modern oxygen minimum zones (OMZs), geochemical and palaeontological data collectively suggest that oxygen concentrations as low as 0.2–0.4 ml/L restricted bioturbation but not the development of a largely nektobenthic community of predators and scavengers. We envisage for the Sirius Passet biota a depositional setting where anoxic water column conditions developed and passed over the depositional site, possibly in association with sea‐level change, and where this early Cambrian biota was established in conditions with very low oxygen.     

The dendroclimatic value of oak stable isotopes

Tree-ring stable oxygen and carbon isotope ratios (δ¹⁸O and δ¹³C) are an important archive for climate reconstructions. However, it remains unclear whether the polyvinyl acetate emulsion, often used for the preservation and fixation of wood samples, influences δ¹⁸O and δ¹³C signals. Further uncertainties are associated with the possible effects of geographical origin and cambial age of historical samples. Here, we present annually-resolved and absolutely-dated δ¹⁸O and δ¹³C measurements of 21 living oaks (Quercus robur and Q. petraea) from the Czech Republic. We find that the δ¹⁸O and δ¹³C signals in the extracted alpha-cellulose are not affected by polyvinyl acetate treatment. Covering the entire 20^th century and reaching until 2018 CE, our dataset reveals spatial and temporal coherency within and between the individual δ¹⁸O and δ¹³C chronologies of different oak species, sample locations, and tree ages. Highly significant (p < 0.01) Pearson’s correlation coefficients of the site-specific δ¹³C and δ¹⁸O chronologies range from 0.48–0.77 and 0.36–0.56, respectively. The isotopic inter-series correlations of Q. robur and Q. petraea from the same site are 0.75 and 0.43 for the mean δ¹³C and δ¹⁸O values, respectively. Significant (p < 0.01) correlations of 0.49 and 0.84 are found for δ¹³C and δ¹⁸O, respectively, when all measurements from all sampling locations and tree ages are included. Our study shows that non-pooled oak δ¹⁸O and δ¹³C measurements from both species, different locations, and diverse tree ages can be combined into robust isotopic chronologies for climate reconstructions.     

Strengthening of the East Asian summer monsoon revealed by a shift in seasonal patterns in diet and climate after 2-3 Ma in northwest China

To examine climate variability in northwest China in the late Cenozoic and to test hypotheses regarding the development of C₄ ecosystems and the dynamics of the Asian monsoons, the carbon and oxygen isotopic compositions of 32 bulk and 368 serial tooth enamel samples from herbivores in the Linxia Basin (Gansu Province), ranging in age from 25 Ma to the present, were determined. The results corroborate and improve the record previously obtained from the area, showing that all mammals in the Linxia Basin lived in habitats consisting primarily of C₃ vegetation prior to 2-3 Ma and that C₄ grasses did not become a significant component of local ecosystems until the Quaternary. The data also show that shifts in climate to drier and/or warmer conditions after about 14, 9.5, 7, and 2.5 Ma, as indicated by positive δ¹⁸O excursions in the bulk enamel-δ¹⁸O record, were accompanied by increased seasonality; whereas negative δ¹⁸O shifts in the bulk data after about 11, 6, and 1.2 Ma, which indicate shifts to wetter and/or cooler climate, were associated with decreases in seasonality. Intra-tooth δ¹³C and δ¹⁸O profiles reveal significant changes in the seasonal patterns of diet and climate after ~ 2-3 Ma. Prior to ~ 2-3 Ma, there was little or no seasonal variation in herbivores' diets and all herbivores fed on C₃ vegetation year around. After that time, the data show a significant seasonal variation in the diets of horses and bovids, ranging from a pure C₃ to a mixed C₃/C₄ diet (with C₄ plants accounting for up to ~ 60% of the diet). An inverse relationship (or negative correlation) between δ¹³C and δ¹⁸O values within individual teeth — a pattern characteristic of the summer monsoon regime — is observed in younger (< 2-3 Ma) horses and bovids but not in older fossils. These changes in intra-tooth isotopic patterns provide strong evidence for an enhanced monsoon climate since about 2-3 Ma.     

The Neoarchaean surficial sulphur cycle: An alternative hypothesis based on analogies with 20th‐century atmospheric lead

We revisit the S‐isotope systematics of sedimentary pyrite in a shaly limestone from the ca. 2.52 Ga Gamohaan Formation, Upper Campbellrand Subgroup, Transvaal, South Africa. The analysed rock is interpreted to have been deposited in a water depth of ca. 50–100 m, in a restricted sub‐basin on a drowning platform. A previous study discovered that the pyrites define a nonzero intercept δ³⁴S_V‐CDT–Δ³³S data array. The present study carried out further quadruple S‐isotope analyses of pyrite, confirming and expanding the linear δ³⁴S_V‐CDT–Δ³³S array with an δ³⁴S zero intercept at ?³³S ca. +5. This was previously interpreted to indicate mixing of unrelated S‐sources in the sediment environment, involving a combination of recycled sulphur from sulphides that had originally formed by sulphate‐reducing bacteria, along with elemental sulphur. Here, we advance an alternative explanation based on the recognition that the Archaean seawater sulphate concentration was likely very low, implying that the Archaean ocean could have been poorly mixed with respect to sulphur. Thus, modern oceanic sulphur systematics provide limited insight into the Archaean sulphur cycle. Instead, we propose that the 20th‐century atmospheric lead event may be a useful analogue. Similar to industrial lead, the main oceanic input of Archaean sulphur was through atmospheric raindown, with individual giant point sources capable of temporally dominating atmospheric input. Local atmospheric S‐isotope signals, of no global significance, could thus have been transmitted into the localised sediment record. Thus, the nonzero intercept δ³⁴S_V‐CDT–Δ³³S data array may alternatively represent a very localised S‐isotope signature in the Neoarchaean surface environment. Fallout from local volcanic eruptions could imprint recycled MIF‐S signals into pyrite of restricted depositional environments, thereby avoiding attenuation of the signal in the subdued, averaged global open ocean sulphur pool. Thus, the superposition of extreme local S‐isotope signals offers an alternative explanation for the large Neoarchaean MIF‐S excursions and asymmetry of the Δ³³S rock record.     

Oxygen and carbon isotope variations in Chamelea gallina shells: Environmental influences and vital effects

Stable isotopes in mollusc shells, together with variable growth rates and other geochemical properties, can register different environmental clues, including seawater temperature, salinity and primary productivity. However, the strict biological control over the construction of biominerals exerted by many calcifying organisms can constrain the use of these organisms for paleoenvironmental reconstructions. Biologically controlled calcification is responsible for the so called vital effects that cause a departure from isotopic equilibrium during shell formation, resulting in lower shell oxygen and carbon compared to the equilibrium value. We investigated shell oxygen and carbon isotopic composition of the bivalve Chamelea gallina in six sites along with a latitudinal gradient on the Adriatic Sea (NE Mediterranean Sea). Seawater δ¹⁸O and δ¹³C_DIC varied from North to South, reflecting variations in seawater temperature, salinity, and chlorophyll concentration among sites. Shell δ¹⁸O and δ¹³C differed among sites and exhibited a wide range of values along with the ~400 km latitudinal gradient, away from isotopic equilibrium for both isotopes. These results hampered the utilization of this bivalve as a proxy for environmental reconstructions, in spite of C. gallina showing promise as a warm temperature proxy. Rigorous calibration studies with a precise insight of environment and shell growth are crucial prior to considering this bivalve as a reliable paleoclimatic archive.     

Geological summary of the Busidima Formation (Plio-Pleistocene) at the Hadar paleoanthropological site, Afar Depression, Ethiopia

The Hadar paleoanthropological site in Ethiopia preserves a record of hominin evolution spanning from approximately 3.45 Ma to 0.8 Ma. An angular unconformity just above the ca. 2.95 Ma BKT-2 complex divides the sediments into the Hadar Formation (ca. 3.8-2.9 Ma) and the Busidima Formation (ca. 2.7-0.15 Ma). The unconformity is likely a response to a major tectonic reorganization in the Afar Depression, and activation of the As Duma fault near the Ethiopian Escarpment (west of Hadar) created a half-graben in which the Busidima Formation was deposited. The pattern and character of sedimentation in the region changed dramatically above the unconformity, as cut-and-fill channel conglomerates and silt-dominated paleosols that comprise the Busidima Formation stand in sharp contrast to the underlying deposits of the Hadar Formation. Conglomerate deposition has been related to both the perennial, axial paleo-Awash and ephemeral, escarpment-draining tributaries. Overbank silts have yielded fossils attributed to early Homo and Oldowan stone tools. Numerous tuffaceous deposits exist within the Busidima Formation, but they are often spatially limited, fine-grained, and reworked. Recent work on the tephrostratigraphic framework of the Busidima Formation at Hadar has identified at least 12 distinct vitric tephras and established the first geochemical-based correlations between Hadar and the neighboring project areas of Gona and Dikika. Compared to Gona and Dikika, where Busidima Formation sediments are exposed over large areas, the highly discontinuous sediments at Hadar comprise less than 40 m in composite section and are exposed over an area of <20 km², providing only snapshots into the 2.7-0.15 Ma window. The stratigraphic record at Hadar confirms the complex depositional history of the Busidima Formation, and also provides important details on regional stratigraphic correlations and the pattern of deposition and erosion in the lower Awash Valley reflective of its tectonic history.     

Linking sedimentary sulfur and iron biogeochemistry to growth patterns of a cold‐water coral mound in the Porcupine Basin,S.W. Ireland (IODP Expedition 307)

Challenger Mound, a 150‐m‐high cold‐water coral mound on the eastern flank of the Porcupine Seabight off SW Ireland, was drilled during Expedition 307 of the Integrated Ocean Drilling Program (IODP). Retrieved cores offer unique insight into an archive of Quaternary paleo‐environmental change, long‐term coral mound development, and the diagenetic alteration of these carbonate fabrics over time. To characterize biogeochemical carbon–iron–sulfur transformations in the mound sediments, the contents of dithionite‐ and HCl‐extractable iron phases, iron monosulfide and pyrite, and acid‐extractable calcium, magnesium, manganese, and strontium were determined. Additionally, the stable isotopic compositions of pore‐water sulfate and solid‐phase reduced sulfur compounds were analyzed. Sulfate penetrated through the mound sequence and into the underlying Miocene sediments, where a sulfate–methane transition zone was identified. Small sulfate concentration decreases (<7 mm ) within the top 40 m of the mound suggested slow net rates of present‐day organoclastic sulfate reduction. Increasing δ³⁴S‐sulfate values due to microbial sulfate reduction mirrored the decrease in sulfate concentrations. This process was accompanied by oxygen isotope exchange with water that was indicated by increasing δ¹⁸O‐sulfate values, reaching equilibrium with pore‐water at depth. Below 50 mbsf, sediment intervals with strong ³⁴S‐enriched imprints on chromium‐reducible sulfur (pyrite S), high degree‐of‐pyritization values, and semi‐lithified diagenetic carbonate‐rich layers characterized by poor coral preservation, were observed. These layers provided evidence for the occurrence of enhanced microbial sulfate‐reducing activity in the mound in the past during periods of rapid mound aggradation and subsequent intervals of non‐deposition or erosion when geochemical fronts remained stationary. During these periods, especially during the Early Pleistocene, elevated sulfate reduction rates facilitated the consumption of reducible iron oxide phases, coral dissolution, and the subsequent formation of carbonate cements.     

Exploring cycad foliage as an archive of the isotopic composition of atmospheric nitrogen

Molecular nitrogen (N₂) constitutes the majority of Earth's modern atmosphere, contributing ~0.79 bar of partial pressure (pN₂). However, fluctuations in pN₂ may have occurred on 10⁷–10⁹ year timescales in Earth's past, perhaps altering the isotopic composition of atmospheric nitrogen. Here, we explore an archive that may record the isotopic composition of atmospheric N₂ in deep time: the foliage of cycads. Cycads are ancient gymnosperms that host symbiotic N₂‐fixing cyanobacteria in modified root structures known as coralloid roots. All extant species of cycads are known to host symbionts, suggesting that this N₂‐fixing capacity is perhaps ancestral, reaching back to the early history of cycads in the late Paleozoic. Therefore, if the process of microbial N₂ fixation records the δ¹⁵N value of atmospheric N₂ in cycad foliage, the fossil record of cycads may provide an archive of atmospheric δ¹⁵N values. To explore this potential proxy, we conducted a survey of wild cycads growing in a range of modern environments to determine whether cycad foliage reliably records the isotopic composition of atmospheric N₂. We find that neither biological nor environmental factors significantly influence the δ¹⁵N values of cycad foliage, suggesting that they provide a reasonably robust record of the δ¹⁵N of atmospheric N₂. Application of this proxy to the record of carbonaceous cycad fossils may not only help to constrain changes in atmospheric nitrogen isotope ratios since the late Paleozoic, but also could shed light on the antiquity of the N₂‐fixing symbiosis between cycads and cyanobacteria.     

Bioturbation and directionality in Earth's carbon isotope record across the Neoproterozoic–Cambrian transition

Mixing of sediments by moving animals becomes apparent in the trace fossil record from about 550 million years ago (Ma), loosely overlapping with the tail end of the extreme carbonate carbon isotope δ¹³C_carbonate fluctuations that qualitatively distinguish the Proterozoic geochemical record from that of the Phanerozoic. These Precambrian‐scale fluctuations in δ¹³C_carbonate (PSF‐δ¹³C_carbonate) remain enigmatic, due to their high amplitude and inclusion of global‐scale negative δ¹³C_carbonate values, below anything attributable to mantle input. Here, we note that different biogeochemical‐model scenarios plausibly explaining globally synchronous PSF‐δ¹³C_carbonate converge: via mechanistic requirements for extensive anoxia in marine sediments to support sedimentary build‐up of ¹³C‐depleted carbon. We hypothesize that bioturbation qualitatively reduced marine sediment anoxia by exposing sediments to oxygenated overlying waters, which ultimately contributed to decreasing the carbon cycle's subsequent susceptibility to PSF‐ δ¹³C_carbonate. Bioturbation may also have reduced the quantity of (isotopically light) organic‐derived carbon available to contribute to PSF‐ δ¹³C_carbonate via ocean crust carbonatization at depth. We conduct a comparative modelling exercise in which we introduce bioturbation to existing model scenarios for PSF‐ δ¹³C_carbonate: expressing both the anoxic proportion of marine sediments, and the global organic carbon burial efficiency, as a decreasing function of bioturbation. We find that bioturbation's oxygenating impact on sediments has the capacity to prevent PSF‐ δ¹³C_carbonate caused by authigenic carbonate precipitation or methanogenesis. Bioturbation's impact on the f‐ratio via remineralization is partially offset by liberation of organic phosphate, some of which feeds back into new production. We emphasize that this study is semiquantitative, exploratory and intended merely to provide a qualitative theoretical framework within which bioturbation's impact on long‐term, first‐order δ¹³C_carbonate can be assessed (and it is hoped quantified in more detail by future work). With this proviso, we conclude that it is entirely plausible that bioturbation made a decisive contribution to the enigmatic directionality in the δ¹³C_carbonate record, from the Neoproterozoic–Cambrian boundary onwards.     

Mass-independent fractionation of sulfur isotopes in sulfides from the pre-3770 Ma Isua Supracrustal Belt, West Greenland

Redox chemistry of the coupled atmosphere–hydrosphere system has coevolved with the biosphere, from global anoxia in the Archean to an oxygenated Proterozoic surface environment. However, to trace these changes to the very beginning of the rock record presents special challenges. All known Eoarchean (c. 3850–3600 Ma) volcanosedimentary successions (i.e. supracrustal rocks) are restricted to high‐grade gneissic terranes that seldom preserve original sedimentary structures and lack primary organic biomarkers. Although complicated by metamorphic overprinting, sulfur isotopes from Archean supracrustal rocks have the potential to preserve signatures of both atmospheric chemistry and metabolic fractionation from the original sediments. We present a synthesis of multiple sulfur isotope measurements (³²S, ³³S and ³⁴S) performed on sulfides from amphibolite facies banded iron‐formations (BIFs) and ferruginous garnet‐biotite (metapelitic) schists from the pre‐3770 Ma Isua Supracrustal Belt (ISB) in West Greenland. Because these data come from some of the oldest rocks of interpretable marine sedimentary origin, they provide the opportunity to (i) explore for possible biosignatures of sulfur metabolisms in early life; (ii) assess changes in atmospheric redox chemistry from ～3.8 Ga; and (iii) lay the groundwork to elucidate sulfur biogeochemical cycles on the early Earth. We find that sulfur isotope results from Isua do not unambiguously indicate microbially induced sulfur isotopic fractionation at that time. A significantly expanded data set of Δ³³S analyses for Isua dictates that the atmosphere was devoid of free oxygen at time of deposition and also shows that the effects of post‐depositional metamorphic remobilization and/or dilution can be traced in mass‐independently fractionated sulfur isotopes.     

Chromium isotopic composition of core‐top planktonic foraminifera

The chromium isotope system (⁵³Cr/⁵²Cr expressed as δ⁵³Cr relative to NIST SRM 979) is potentially a powerful proxy for the redox state of the ocean–atmosphere system, but a lack of temporally continuous, well‐calibrated archives has limited its application to date. Marine carbonates could potentially serve as a common and continuous Cr isotope archive. Here, we present the first evaluation of planktonic foraminiferal calcite as an archive of seawater δ⁵³Cr. We show that single foraminiferal species from globally distributed core tops yielded variable δ⁵³Cr, ranging from 0.1‰ to 2.5‰. These values do not match with the existing measurements of seawater δ⁵³Cr. Further, within a single core‐top, species with similar water column distributions (i.e., depth habitats) yielded variable δ⁵³Cr values. In addition, mixed layer and thermocline species do not consistently exhibit decreasing trends in δ⁵³Cr as expected based on current understanding of Cr cycling in the ocean. These observations suggest that either seawater δ⁵³Cr is more heterogeneous than previously thought or that there is significant and species‐dependent Cr isotope fractionation during foraminiferal calcification. Given that the δ⁵³Cr variability is comparable to that observed in geological samples throughout Earth's history, interpreting planktonic foraminiferal δ⁵³Cr without calibrating modern foraminifera further, and without additional seawater measurements, would lead to erroneous conclusions. Our core‐top survey clearly indicates that planktonic foraminifera are not a straightforward δ⁵³Cr archive and should not be used to study marine redox evolution without additional study. It likewise cautions against the use of δ⁵³Cr in bulk carbonate or other biogenic archives pending further work on vital effects and the geographic heterogeneity of the Cr isotope composition of seawater.     

Stable oxygen isotope signatures of early season wood in New Zealand kauri (Agathis australis) tree rings: Prospects for palaeoclimate reconstruction

One of the longest Southern Hemisphere tree ring chronologies that has potential to provide past climate reconstructions has been produced using New Zealand kauri (Agathis australis). Work to date on kauri has been limited to reconstructions from whole-ring width analysis. In this study, we present the first replicated stable oxygen isotopic composition of early season alpha-cellulose from calendar-dated kauri tree rings within the natural growth range of the species. We also use newly established kauri physiology information about stomatal conductance and a mechanistic model to place initial interpretations on kauri δ¹⁸O signatures.Kauri early season δ¹⁸O has a range from 26 to 34‰ (V-SMOW) for a site located at Lower Huia Dam in west Auckland, and the mean δ¹⁸O chronology from that site is significantly correlated (p < 0.05) to October-December vapor pressure, May-December relative humidity and other associated hydroclimatic variables. The observed statistical relationships are consistent with mechanistic δ¹⁸O simulations using the forward model of Barbour et al. (2004) that incorporates a leaf temperature energy balance model to calculate transpiration as forced with local meteorological variables and a range of physiological parameters. The correlation results and mechanistic model simulations suggest kauri δ¹⁸O early season wood has the potential to provide new quantitative past climate information for northern New Zealand, and also complement whole ring-width reconstructions of past regional climate variability – a component of which is previously established as sensitive to El Niño-Southern Oscillation activity. Additional work is required to determine whether the observed relationships are consistent across the growth range of kauri and what the optimum sample depth is before long isotope-based palaeoclimate reconstructions from modern and sub-fossil kauri sites are undertaken.     

The late‐stage “ferruginization” of the Ediacara Member (Rawnsley Quartzite,South Australia): Insights from uranium isotopes

The paleoenvironmental setting in which the Ediacara Biota lived, died, and was preserved in the eponymous Ediacara Member of the Rawnsley Quartzite of South Australia is an issue of long‐standing interest and recent debate. Over the past few decades, interpretations have ranged from deep marine to shallow marine to terrestrial. One of the key features invoked by adherents of the terrestrial paleoenvironment hypothesis is the presence of iron oxide coatings, inferred to represent the upper horizons of paleosols, along fossiliferous sandstone beds of the Ediacara Member. We find that these surficial oxides are characterized by (²³⁴U/²³⁸U) values which are not in secular equilibrium, indicating extensive fluid‐rich alteration of these surfaces within the past approximately 2 million years. Specifically, the oxide coatings are characterized by (²³⁴U/²³⁸U) values >1, indicating interaction with high‐(²³⁴U/²³⁸U) fluids derived from alpha‐recoil discharge. These oxides are also characterized by light “stable” δ^238/235U values, consistent with a groundwater U source. These U isotope data thus corroborate sedimentological observations that ferric oxides along fossiliferous surfaces of the Ediacara Member consist of surficial, non‐bedform‐parallel staining, and sharply irregular patches, strongly reflecting post‐depositional, late‐stage processes. Therefore, both sedimentological and geochemical evidence indicate that Ediacara iron oxides do not reflect synsedimentary ferruginization and that the presence of iron oxides cannot be used to either invoke a terrestrial paleoenvironmental setting for or reconstruct the taphonomic pathways responsible for preservation of the Ediacara Biota. These findings demonstrate that careful assessment of paleoenvironmental parameters is essential to the reconstruction of the habitat of the Ediacara Biota and the factors that led to the fossilization of these early complex ecosystems.