Boron, carbon, and oxygen isotopic composition of brachiopod shells: Intra-shell variability, controls, and potential as a paleo-pH recorder

The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO2 on Pleistocene and Cenozoic timescales. Because of their excellent preservation and extensive fossil record throughout the Phanerozoic, brachiopods are a promising candidate for extending the boron isotope record as far back as the Cambrian. Here we present stable carbon, oxygen, and boron isotopic measurements of modern Terebratulid brachiopod calcite in comparison with environmental pH estimates calculated from oceanographic data. Geochemical transects along the length and depth of single shells confirm previously published trends in carbon and oxygen isotopic composition. In the outer surface (primary and outermost secondary layers), δ11B covaries with δ13C and δ18O, with more negative values in the outer and more positive values in the middle of the shell. However, δ11B deviates from δ13C and δ18O in the inner part of the secondary layer, where the δ13C and δ18O values are more positive and near equilibrium, whereas δ11B returns to more negative values. A comparison of different specimens of the species Terebratalia transversa (Sowerby, 1846) and Laqueus californianus (Küster, 1844) microsampled from the middle part of the fibrous secondary layer demonstrates a clear correlation to ambient pH with a sensitivity similar to other empirical calibration curves for cultured planktic foraminifers, corals, and inorganic calcite. The relationship in other species is less clear and significantly offset, necessitating the use of a single species or a cross-calibration method with other species in paleo-pH reconstructions

An assessment of sanidine from the Fire Clay tonstein as a Carboniferous 40Ar/39Ar monitor standard and for inter-method comparison to U-Pb zircon geochronology

Radioisotopic geochronology applied to the high-resolution calibration of Earth history requires a set of syn- thetic and natural reference materials for both 40Ar/39Ar and U-Pb techniques that permit both inter-laboratory and inter-technique comparisons. The sanidine- and zircon-bearing Carboniferous Fire Clay tonstein provides a potential natural Paleozoic reference for these two widely used radioisotopic systems. Here we report results for both radioisotopic systems, examining the suitability of this tonstein as a geochronologic reference. Sanidine crystals from the Fire Clay and co-irradiated monitors from eight irradiation positions were divided into eleven 40Ar/39Ar experiments. Single-grain sanidine 40Ar/39Ar analyses (n = 263) of the simplest 9 experiments have internal 2σ uncertainties at the ± 1 Myr level ( ± 0.3%), with a range of dates between ~315 and ~317 Ma (~1% precision), similar to the observed dispersion in the Fish Canyon sanidine monitor dates. Forty-one U-Pb analyses by the CA-ID-TIMS method on carefully selected single Fire Clay tonstein zircons have produced 206Pb/238U dates with an average 2σ precision of ± 0.23 Myr (0.14%). Our Fire Clay preferred mean 40Ar/39Ar date of 315.36 ± 0.10 Ma ( ± 1.10 Ma: fully propagated 2σ uncertainty, relative to a Fish Canyon age of 28.201 Ma) is consistent with our weighted mean 206Pb/238U zircon date of 314.629 ± 0.039 Ma ( ± 0.35 Ma: fully propagated 2σ uncertainty; n = 27). The good single-crystal reproducibility of the sanidine data and the overall consistency between the two chronometers suggest that the tonstein holds promise as a Paleozoic age reference material

Zircon U-Pb Geochronology Links the End-Triassic Extinction with the Central Atlantic Magmatic Province

The end-Triassic extinction is characterized by major losses in both terrestrial and marine diversity, setting the stage for dinosaurs to dominate Earth for the next 136 million years. Despite the approximate coincidence between this extinction and flood basalt volcanism, existing geochronologic dates have insufficient resolution to confirm eruptive rates required to induce major climate perturbations. Here, we present new zircon uranium-lead (U-Pb) geochronologic constraints on the age and duration of flood basalt volcanism within the Central Atlantic Magmatic Province. This chronology demonstrates synchroneity between the earliest volcanism and extinction, tests and corroborates the existing astrochronologic time scale, and shows that the release of magma and associated atmospheric flux occurred in four pulses over about 600,000 years, indicating expansive volcanism even as the biologic recovery was under way

Neodymium Isotope Geochemistry of a Subterranean Estuary

Rare earth elements (REE) and Nd isotope compositions of surface and groundwaters from the Indian River Lagoon in Florida were measured to investigate the influence of submarine groundwater discharge (SGD) on these parameters in coastal waters. The Nd flux of the terrestrial component of SGD is around 0.7 ± 0.03 μmol Nd/day per m of shoreline across the nearshore seepage face of the subterranean estuary. This translates to a terrestrial SGD Nd flux of 4 ± 0.2 mmol/day for the entire 5,880 m long shoreline of the studied portion of the lagoon. The Nd flux from bioirrigation across the nearshore seepage face is 1 ± 0.05 μmol Nd/day per m of shoreline, or 6 ± 0.3 mmol/day for the entire shoreline. The combination of these two SGD fluxes is the same as the local, effective river water flux of Nd to the lagoon of 12.7 ± 5.3 mmol/day. Using a similar approach, the marine-sourced SGD flux of Nd is 31.4 ± 1.6 μmol Nd/day per m of shoreline, or 184 ± 9.2 mmol/day for the investigated portion of the lagoon, which is 45 times higher than the terrestrial SGD Nd flux. Terrestrial-sourced SGD has an εNd(0) value of -5 ± 0.42, which is similar to carbonate rocks (i.e., Ocala Limestone) from the Upper Floridan Aquifer (-5.6), but more radiogenic than the recirculated marine SGD, for which εNd(0) is -7 ± 0.24. Marine SGD has a Nd isotope composition that is identical to the εNd(0) of Fe(III) oxide/oxyhydroxide coated sands of the surficial aquifer (-7.15 ± 0.24 and -6.98 ± 0.36). These secondary Fe(III) oxides/oxyhydroxides formed during subaerial weathering when sea level was substantially lower during the last glacial maximum. Subsequent flooding of these surficial sands by rising sea level followed by reductive dissolution of the Fe(III) oxide/oxyhydroxide coatings can explain the Nd isotope composition of the marine SGD component. Surficial waters of the Indian River Lagoon have an εNd(0) of -6.47 ± 0.32, and are a mixture of terrestrial and marine SGD components, as well as the local rivers (-8.63 and -8.14). Nonetheless, the chief Nd source is marine SGD that has reacted with Fe(III) oxide/oxyhydroxide coatings on the surficial aquifer sands of the subterranean estuary

A calcite reference material for LA-ICP-MS U-Pb geochronology

U-Pb dating of calcite is an emerging but rapidly growing field of application in geochronology with great potential to inform problems in landscape, basin and mountain belt evolution, through age determination of diagenetic cements, vein mineralisation and geological formations difficult to date otherwise. In this brief, we present isotope dilution U-Pb isotope measurements on a sample of calcite (WC-1) that has been and will continue to be used as a reference material for in-situ U-Pb Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) dating, and which is suitable to be distributed to the geochronological community. We present in-situ measurements using LA-ICP-MS to demonstrate the suitability of WC-1 for use as a U-Pb dating reference material, in spite of it not being isotopically homogeneous. The WC-1 calcite sample is 254.4 ± 6.4 Ma old, and comprised of 85 to 98% radiogenic lead. It presents a suitable reference material that can facilitate dating of calcite ranging in age from Precambrian to late Neogene age

Deciphering the diagenetic history of the El Abra Formation of eastern Mexico using reordered clumped isotope temperatures and U-Pb dating

Carbonates form ubiquitously throughout the history of deposition, burial, and uplift of basins. As such, they potentially record the environmental conditions at the time of formation. Carbonate clumped isotopes provide the temperature of precipitation but can be internally reordered if the host rock is exposed to elevated temperatures over geologic time scales. Here, we exploited this kinetic behavior by analyzing multiple generations of cements that capture the range of environments experienced by the El Abra Formation from eastern Mexico. From this, we developed a quantitative diagenetic history for these different phases of cementation. We observed a 70 °C range in clumped isotope temperatures from 64 °C to 134 °C for these cements, which is not compatible with their inferred precipitation environments. This suggests that bond reordering occurred during burial but did not fully reorder all cements to a common apparent temperature. We reconstructed original cement growth temperatures and the isotopic signature of the parent fluids to show that precipitation from a marine pore fluid began at 125 Ma, contemporaneous with deposition, and continued throughout burial to temperatures of at least 138 °C at 42 Ma. We show that precipitation of equant cements, which occluded 90% of the pore space, was coincident with Laramide-related burial to depths greater than 3800 m. A U-Pb age of diagenetic calcite of 77.1 ± 3.6 Ma provides independent support for our estimates of the absolute timing of precipitation of two distinct phases of the paragenesis. This is the first demonstration of the utility of integrating U-Pb age dating with reordered clumped isotope temperatures to provide quantitative constraints on the time-temperature history of cementation. Such information may ultimately lead to advances in our understanding of the formational environments and geological processes that drive diagenesis in carbonates for temperatures below the clumped isotope “blocking temperature.

Investigating boron isotopes for identifying nitrogen sources supplied by submarine groundwater discharge to coastal waters

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Tamborski, J., Brown, C., Bokuniewicz, H., Cochran, J. K., & Rasbury, E. T. Investigating boron isotopes for identifying nitrogen sources supplied by submarine groundwater discharge to coastal waters. Frontiers in Environmental Science, 8, (2020): 126, doi:10.3389/fenvs.2020.00126.Stable isotopes of oxygen, nitrogen, and boron were used to identify the sources of nitrate (NO3–) in submarine groundwater discharge (SGD) into a large tidal estuary (Long Island Sound, NY, United States). Potential contaminants such as manure, septic waste and fertilizer overlap in δ15N and δ18O but have been shown to have distinctive δ11B in non-coastal settings. Two distinct subterranean estuaries were studied with different land-use up gradient, representative of (1) mixed medium-density residential housing and (2) agriculture. These sites have overlapping δ15N and δ18O measurements in NO3– and are unable to discriminate between different N sources. Boron isotopes and concentrations are measurably different between the two sites, with little overlap. The subterranean estuary impacted by mixed medium-density residential housing shows little correlation between δ11B and [B] or between δ11B and salinity, demonstrating that direct mixing relationships between fresh groundwater and seawater were unlikely to account for the variability. No two sources could adequately characterize the δ11B of this subterranean estuary. Groundwater N at this location should be derived from individual homeowner cesspools, although measured septic waste has much lower δ11B compared to the coastal groundwaters. This observation, with no trend in δ11B with [B] indicates multiple sources supply B to the coastal groundwaters. The agricultural subterranean estuary displayed a positive correlation between δ11B and [B] without any relationship with salinity. Binary mixing between sea spray and fertilizer can reasonably explain the distribution of B in the agricultural subterranean estuary. Results from this study demonstrate that δ11B can be used in combination with δ15N to trace sources of NO3– to the subterranean estuary if source endmember isotopic signatures are well-constrained, and if the influence of seawater on δ11B signatures can be minimized or easily quantified.This research was funded by New York Sea Grant projects R/CMC-13 and R/CMC-13-NYCT. The MC-ICP-MS used for this work was funded through NSF-MRI 0959524

The Boron Budget in Waters of the Mono Basin, California

Mono Lake in eastern California has the highest natural boron concentrations measured in a natural water body. Inputs to Mono Lake are from creeks that drain from the Sierra Nevada, accounting for over 80% of the total water input, and springs account for most of the rest of the water budget. We measured boron concentrations and isotope compositions of water sources in the lake and lake water collected over several seasons. The δ11B offset of at least +2.5‰ between Mono Lake water compared to its inputs suggests that, like seawater, the boron isotopic composition of the lake is influenced by the removal of light boron by coprecipitation and/or sorption of borate. Given the alkalinity of the lake, boron fractionation likely occurs before or as the water sources enter the lake. The famous tufa towers around the lake are a physical representation of a ‘chemical delta’ that alters the boron isotopic composition of the source fluids as they enter the lake. Based on different combinations of the measured end members, the residence time of boron in Mono Lake is estimated to be within the range of 5~80 ka

Extreme isotopic heterogeneity in impact melt rocks: Implications for Martian meteorites

Lead isotope ratios have been determined in multiple feldspar grains from hand samples of impact melt rock at the Manicouagan and Sudbury impact structures in Canada. The results reveal an extreme range of isotope values. This indicates that melt sheets are not homogeneous with respect to Pb at the millimeter scale. Such heterogeneity is significantly larger than that seen in non-impact-generated igneous rocks. Individual Pb isotope ratios of feldspars from Martian shergottites show a large range in 206Pb/204Pb values within one sample, more similar to the terrestrial impact melt sheets than to nonimpact igneous rocks. We suggest crystallization from impact melt sheets rather than volcanic sources as a petrogenetic model for some of the Martian shergottites.12 month embargo; first published 07 February 2023This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]