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This study develops and optimizes a new protocol to measure lithium isotope ratios using a single collector quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) operated under hot plasma (1550 W) conditions with a sample-standard bracketing method. Our Q-ICP-MS method reduces sample consumption to 2.5 ng of Li and achieves a high long-term precision of 1.1‰ (2SD). This Q-ICP-MS method exhibits high matrix tolerance (Na/Li < 100), suitable for ng-sized and high-matrix geological samples. We also developed a dual-column system for Li separation, with large loading capacity (29.6 meq), complete recovery (∼100%) and satisfactory purification (Na/Li m m-1 < 1), as well as a fixed elution range for Li fractions (28-60 mL). This new chromatography method has been applied to chemically diverse materials, producing consistent results. In addition, we report the Li isotope compositions of 13 geostandards, and our measurements agree well with reported data within analytical uncertainties. This study documents that Li element concentration and Li isotope composition can be routinely measured using a single collector ICP-MS, which is convenient and commercially affordable for future Li isotope research across the fields of Earth and Environmental Sciences.

Inferring redox conditions for ancient marine environments is critical to our understanding of biogeochemical cycles over Earth history. Because of the redox sensitivity of cerium (Ce) relative to other rare earth elements (REEs) and its uptake in marine carbonates, the Ce anomaly (Ce/Ce*) is widely applied to ancient carbonates as a proxy for local redox conditions in the water column. However, carbonate sediments and rocks are particularly vulnerable to multiple stages and styles of post-depositional diagenetic alteration where the diagenetic redox conditions and fluid compositions can vary widely from overlying seawater. Evaluations of the effects of this post-depositional alteration for the Ce anomaly have mostly been limited to ancient carbonate rocks rather than recent, well-characterized analog facies. Here, we report on analyses of REE plus yttrium concentrations (REY) and Ce anomalies in bulk carbonate samples from drill cores collected in the Bahamas (Clino and Unda) that allow us to track loss or retention of primary signals of initial oxic deposition through a range of subsequent alteration scenarios mostly under anoxic conditions. Specifically, these materials have experienced well-constrained overprints linked to meteoric processes and marine burial diagenesis, including dolomitization. Our results show that, regardless of mineralogy, diagenetic fluid composition, and redox state, the REY patterns in these carbonates, including the Ce anomaly, are similar to those of modern oxic seawater, indicating that they likely record the seawater signatures of primary deposition. As such, the Ce anomaly in shallow marine carbonates has the potential to preserve records of primary deposition even when subject to multiple stages and styles of diagenetic alteration, confirming its utility in studies of ancient marine redox.

The early Paleogene was a dynamic period marked by long-term climatic trends and rapid climate events superimposed upon a hot greenhouse state. The response of the terrestrial hydrological cycle to these climate variations can be investigated at the continental scale by analysis of Paleogene strata in Laramide basins and the Gulf of Mexico. New U-Pb geochronologic data from detrital zircons in Paleogene fluvial strata of the Tornillo Basin in west Texas indicate relatively continuous deposition from 63 to 47 Ma. The combination of detrital zircon ages with existing carbon isotope chemostratigraphic data allows us to revise the age model of these strata and to correlate stratigraphic changes with Paleogene climate variations. Sedimentologic data indicate that, during the Paleocene (63-55.5 Ma), high-sinuosity, fluvial systems meandered on a forested floodplain with well-developed soils and swamps. The fluvial regime changed abruptly to lowsinuosity, braided fluvial systems with floodplains characterized by intermittent wetting at the Paleocene-Eocene thermal maximum (55.5 Ma). Braided fluvial regimes persisted thereafter and culminated during the early Eocene climate optimum (52-50 Ma) with deposition of a coarse sheet of sand and gravel. We interpret the transition from meandering to braided fluvial systems as a shift in discharge and sediment supply associated with the more seasonal precipitation of the hot, subtropical monsoonal climate of the early Eocene. After 54 Ma, this shift in fluvial regime is superimposed by an upwardcoarsening grain-size trend probably driven by enhanced regional Laramide tectonism. These data provide the first reconstruction of Paleogene subtropical fluvial dynamics in western North America and correlate with regional and global changes in Paleogene climate and landscapes.

Lithium isotopes have been identified as a promising tracer of subducted materials in arc lavas due to the observable variations in related reservoirs such as subducting sediments and altered oceanic crust. The Tonga–Kermadec arc–Lau back-arc provides an end-member of subduction zones with the coldest thermal structure on Earth. Reported here are Li isotope data for 14 lavas from the arc front and 7 back-arc lavas as well as 12 pelagic and volcaniclastic sediments along a profile through the sedimentary sequence at DSDP Site 204. The arc and back-arc lavas range from basalts to dacites in composition with SiO 2 = 48.3–65.3 wt% over which Li concentrations increase from 2 ppm to 16 ppm. Li/Y ratios range from 0.08 to 0.77 and from 0.24 to 0.65 in the arc and back-arc lavas, respectively. The majority of the lavas have δ 7 Li that ranges from 2.5 ‰ to 5.0 ‰ with an average of (3.6 ±0.7) ‰, similar to that reported from other arcs and there is no distinction between the arc front and back-arc lavas. The pelagic sediments have variable Li concentrations (33–133 ppm) and δ 7 Li that ranges from 1.2 ‰ to 10.2 ‰ while the volcaniclastic sediments have an even greater range of Li concentrations (3.6–165 ppm) and generally higher δ 7 Li values (8–14 ‰). However, δ 7 Li in the lavas does not correlate with commonly used trace element ratio or isotope signatures indicative of slab-derived fluids or the sediments. This is probably because the range of δ 7 Li in the lavas and sediments overlap. Calculated sediment mass-balance models require significantly more sediment than previous estimates based on Th–Nd–Be isotopes. This may indicate that a sizeable proportion of the total Li budget in the lavas is provided by Li-enriched fluids from the subducting sediments and/or altered oceanic crust.

The terminal Ediacaran Period witnessed the first appearance of macroscopic organisms including the earliest biomineralizing animals in Earth history (Narbonne et al., 2012; Xiao et al., 2016). However, the biogeochemical context for this evolutionary milestone remains uncertain due to the absence of radiometric constraints for key events recorded in paleontological and chemostratigraphic datasets, and to uncertainties in the correlation of these biogeochemical events worldwide. Moreover, soft-bodied Ediacara biotas are typically preserved as impressions in fine-grained siliciclastic rocks (Gehling, 1999), which offer limited opportunities for paleoenvironmental analysis using geochemical tools. In contrast, two rare soft-bodied Ediacara assemblages are preserved in well-exposed marine carbonate successions of the Dengying Formation in South China (Chen et al., 2014) and the Khatyspyt Formation in Arctic Siberia (Grazhdankin et al., 2008), where comprehensive chemostratigraphic studies have recently been completed (Gamper, 2014; Schiffbauer et al., 2014; Cui et al., 2016a; Cui et al., 2016b; Bykova et al., 2017; Zhang et al., 2018; Cui et al., 2019). In the Gaojiashan Member of the Dengying Formation, integrated bio- and chemo-stratigraphic profiles (Cui et al., 2016b; Cui et al., 2019) show that the first appearance of biomineralizing animal fossil Cloudina is closely associated with positive anomalies of δ13Ccarb, δ34Spyrite, and Sr/Ca values (Fig.1). In contrast, S isotope values of carbonate‐associated sulfate (δ34SCAS) remain steady throughout the succession, resulting in anomalously large (>70‰) sulfur isotope fractionations (Δ34SCAS-pyrite) in the lower half of the member that decline to ~30‰ in the upper half. This fractionation trend likely relates to changes in microbial communities, with sulfur disproportionation dominating in the lower interval, whereas microbial sulfate reduction was the principal metabolic pathway in the upper. We propose that the coupled paleontological and biogeochemical transition may have coincided with an increase in terrestrial weathering fluxes of sulfate (evidenced by gypsum pseudomorphs), alkalinity (evidenced by Sr/Ca positive anomaly), and nutrients to the depositional basin, which stimulated primary productivity (evidenced by high δ13Ccarb values) and the spread of an oxygen minimum zone (evidenced by high δ15N and low δ238U values). Enhanced production and burial of organic matter is thus directly connected to the δ13Ccarb anomaly, and through bottom water anoxia likely promoting microbial sulfate reduction and pyritization as the main taphonomic pathway for Conotubus and other soft‐bodied Ediacara biota. These results suggest that environmental and physiological pressures from an increase in seawater alkalinity (Cui et al., 2016b; Cui et al., 2019) – likely coupled with ecological pressures from predation (Hua et al., 2003; Hua et al., 2007) – set the stage for the evolutionary novelty of animal biomineralization. In the Khatyspyt Formation, the profound sulfur isotope fractionation trend seen in the Dengying is preserved, with δ34Spyrite values rising from ca. – 20‰ to ca. 50‰ through an interval of general invariance in δ34SCAS (Fig.2). The step function shift in sulfur isotope compositions is closely associated with the first occurrence of soft-bodied Ediacara biotas preserved in thinly bedded limestones, which suggests a possible link between seawater redox conditions and the distribution of these enigmatic macroscopic organisms (Cui et al., 2016a). Based on multiple lines of sedimentological and geochemical evidence, we propose that the development of oceanic euxinia — which could be widespread in the continental margins due to enhanced oxidative weathering (delivering both nutrients and sulfate to ocean margins) in the terminal Ediacaran Period — may have locally prohibited the colonization of Ediacara-type organisms. The progressive secular transition from euxinic to non-euxinic and more habitable conditions may have allowed for the colonization of Ediacara-type and other macro-organisms in the upper part of the studied section of the Khatyspyt Formation. In summary, our results reveal dramatic changes in biogeochemical cycles during the terminal Ediacaran Period, many of which are closely coupled with evolutionary transitions in the corresponding fossil records. Dynamic redox conditions may have caused a profound impact on early animal evolution. Our work highlights the significance of integrated bio-, litho-, and chemo-stratigraphy in geobiology research of the deep time. Keywords: chemostratigraphy; redox condition; early macroorganisms; biogeochemical cycles; geobiology, animal biomineralization, alkalinity, Cloudina

The Neoproterozoic Hüttenberg Formation in northeastern Namibia records a remarkable δ13Ccarb positive excursion with a sustained plateau of values up to +12‰ (i.e., the Hüttenberg anomaly). High-resolution chemostratigraphic analyses of drill core samples spanning the upper Elandshoek and Hüttenberg formations reveal multiple new observations: (1) overall high but oscillatory δ13Ccarb values; (2) δ18Ocarb values ranging from −8‰ to −2‰; (3) significant enrichment of 13C in organic carbon and a broad co-variation between δ13Ccarb and δ13Corg; (4) a profound negative excursion in δ34Spyrite from +30‰ to −10‰; (5) an overall inverse δ13C–δ34S relationship; and (6) 87Sr/86Sr values down to 0.7074 in limestone samples. The new data suggest that the Hüttenberg anomaly records dynamic fluctuations in marine redox conditions, which may include an oxygenation event during the height of the δ13Ccarb positive excursion and a deoxygenation event at its termination. The δ34Spyrite negative excursion suggests the buildup of the marine sulfate reservoir, likely due to enhanced pyrite oxidation during the oxygenation event. The δ34Spyrite increase at the end of the Hüttenberg anomaly may result from a seawater sulfate concentration drawdown towards pre-anomaly conditions. On one hand, the Hüttenberg anomaly may reflect restricted basin signals that are deviated from the Ediacaran open ocean; on the other hand, the Ediacaran Hüttenberg anomaly, together with the Cryogenian δ13Ccarb positive excursions, suggests a stepwise pattern of the Neoproterozoic Oxygenation Event. Both local and global environmental factors may have contributed to the Hüttenberg anomaly. The Hüttenberg anomaly therefore represents a local enhancement of global oxygenation signals. Our data support the emerging view that the Neoproterozoic Oxygenation Event may have facilitated the evolution of early life at that time.

Rare earth elements (REEs) signatures in the dissolved loads of rivers serve as excellent monitors of weathering processes within a basin. However, quantifying REE behavior spatially (along a river's profile) and temporally (seasonable variations) is rare. This investigation reports REE concentrations of dissolved river loads collected during four sampling seasons at five monitoring stations along the Neuse River, North Carolina. The areal percentage of the Neuse River's catchment lithology composition, Post Archean Australian Shale (PAAS) normalized REE patterns, inter-REE ratios, and calculated anomalous REE values (i.e. cerium anomaly, gadolinium anomaly) were determined at each site in four seasons over a year. Our results show slight differences among inter-REE relationships and anomalous REE values in the dissolved loads along the length of the river. PAAS normalized REE patterns of dissolved water loads vary slightly spatially and temporally among the five sampling stations, and experience varying values of anomalous REE values. Collected data indicates that both variations in localized REE patterns and local bedrock occur along the river profile. Significant gadolinium (Gd) anomalies varied seasonally and spatially at select sites, suggesting changes in REE behavior along a river result from both natural and anthropogenic processes.

Ingestion of inorganic arsenic through food and water can have severe adverse health effects on the human body. Therefore, government regulations and health guidelines for arsenic concentrations in water have been established around the world to avoid or mitigate these health effects. In recent decades, analysis of groundwater in many locations around the world have revealed arsenic concentrations that exceed government regulation levels. The section of the Carolina Terrane located in North Carolina is one of such recently discovered areas. This study investigates the relationship between the geologic units of the Carolina terrane and arsenic concentrations in well water samples in Orange County, North Carolina. Kriging interpolation mapping and multivariate analysis reveals spatial and geochemical connections between wells of detectable arsenic and the Neoproterozoic epiclastics unit and geochemical variables such as F−, pH, and alkalinity. These associations imply that arsenic in Orange County, NC is being mobilized from authigenic arsenic-bearing sulfide minerals in the Neoproterozoic epiclastics bedrock unit by oxidative release likely associated with increased F−, pH, and alkalinity.

The Ediacaran Period witnessed the first appearance of macroscopic animal life in Earth's history. However, the biogeochemical context for the stratigraphic occurrence of early metazoans is largely uncertain, in part due to the dearth of integrated paleobiological and chemostratigraphic datasets. In this study, a comprehensive geochemical analysis was conducted on the fossiliferous Khatyspyt Formation in Arctic Siberia, in order to gain insights into the Ediacaran paleoenvironments. This study was designed to specifically address the relationship between paleoredox conditions and Ediacaran fossil occurrences in the Khatyspyt Formation. Our data reveal a dramatic shift in pyrite sulfur isotope compositions (δ34Spyrite) from ca. − 20‰ to ca. 55‰, and this shift is intriguingly associated with the first occurrence of Ediacara-type macrofossils at the studied section, suggesting a possible link between seawater redox conditions and distribution of early macroscopic organisms. Based on multiple lines of sedimentological and geochemical evidence, we propose that the development of oceanic euxinia — which may be widespread in the continental margins due to enhanced oxidative weathering in the terminal Ediacaran Period — may have locally prohibited the colonization of Ediacara-type organisms and resulted in low δ34Spyrite values in the lower Khatyspyt Formation. In the middle and upper Khatyspyt Formation, progressive secular transition from euxinic to non-euxinic and more habitable conditions may have allowed for the colonization of Ediacara-type and other macro-organisms.

Porous NiTi shape memory alloy (SMA) with 48% porosity and an average pore size of 50–800 μm was synthesized by capsule-free hot isostatic pressing (CF-HIP). To enhance the surface bioactivity, the porous NiTi SMA was subjected to H2O2 and subsequent NaOH treatment. Scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses revealed that a porous sodium titanate (Na2TiO3) film had formed on the surface of the porous NiTi SMA. An apatite layer was deposited on this film after immersion in simulated body fluid at 37°C, while no apatite could be found on the surface of the untreated porous NiTi SMA. The formation of the apatite layer infers that the bioactivity of the porous NiTi SMA may be enhanced by surface chemical treatment, which is favorable for its application as bone implants.