We present the δ11B of well‐preserved brachiopod fossils coupled with geochemical modeling to examine how seawater boron responded to abrupt and dynamic climate changes in the Late Paleozoic. The Late Carboniferous, a time of major coal formation and glacioeustatic sea level changes, is characterized by relatively stable brachiopod δ11B of 15–17‰, similar to values seen in modern brachiopods. Brachiopod δ11B dropped by ~5‰ in the early Permian and then restabilized at a new value of 10‰ within a few million years. Mass balance models of seawater δ11B reproduced the overall trends in our brachiopod data but failed to capture the large drop in δ11B in the early Permian. Published seawater87Sr/86Sr and δ44/40Ca data based on brachiopod shells also shift to lower values in the early Permian, suggesting a common control on all three seawater isotope systems. The Permian terrestrial record of evaporites and eolian deposits suggests a prolonged reduced delivery of dissolved weathering products to the ocean, accounting for the change in seawater87Sr/86Sr. This reduced weathering, in turn, led to increased atmospheric CO2and lowered seawater pH, which may have significantly decreased major removal mechanisms for seawater calcium and boron leading to declines in both isotope systems. We propose that boron removal via coprecipitation in carbonates and adsorption onto clay minerals was significantly diminished due to a reduction in the availability of the borate aqueous species caused by lowered seawater pH.
Chlorine, lithium, and boron are trace elements in rhyolite but are enriched in groundwater flowing through rhyolite because they tend to partition into the fluid phase during high‐temperature fluid‐rock reactions. We present a large data set of major element and δ37Cl, δ7Li, and δ11B compositions of thermal water and rhyolite from Yellowstone Plateau Volcanic Field (YPVF). The Cl/B, Cl/Li, δ37Cl (−0.2‰ to +0.7‰), and δ11B (−6.2‰ to −5.9‰) values of alkaline‐chloride thermal waters reflect high‐temperature leaching of chlorine, lithium, and boron from rhyolite that has δ37Cl and δ11B values of +0.1‰ to +0.9‰ and −6.3‰ to −6.2‰, respectively. Chlorine and boron are not reactive, but lithium incorporation into hydrothermal alteration minerals results in a large range of Cl/Li, B/Li, and δ7Li (−1.2‰ to +3.8‰) values in thermal waters. The relatively large range in δ7Li values of thermal waters reflects a large range of values in rhyolite. Large volumes of rhyolite must be leached to account for the chloride, lithium and boron fluxes, implying deep groundwater flow through rhyolite flows and tuffs representing Yellowstone's three eruptive cycles (∼2.1 Ma). Lower Cl/B values in acid‐sulfate waters result from preferential partitioning of boron into the vapor phase and enrichment in the near‐surface water condensate. The Cl/B, Cl/Li, δ7Li (−0.3‰ to +2.1‰), and δ11B (−8.0‰ to −8.1‰) values of travertine depositing calcium‐carbonate thermal waters which discharge in the northern and southern YPVF suggest that chlorine, lithium, and boron are derived from Mesozoic siliciclastic sediments which contain detrital material from the underlying metamorphic basement.
more » « less- NSF-PAR ID:
- 10449906
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Geochemistry, Geophysics, Geosystems
- Volume:
- 22
- Issue:
- 4
- ISSN:
- 1525-2027
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2
s ). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ11B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ11B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO2and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, thein situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s ). -
more » « less
Abstract The structure of liquid lithium pyroborate, Li4B2O5(
J = Li/B = 2), has been measured over a wide temperature range by high‐energy X‐ray diffraction, and compared to that of its glass and borate liquids of other compositions. The results indicate a gradual increase in tetrahedral boron fraction from 3(1)% to 6(1)% during cooling fromT = 1271(15) to 721(8) K, consistent with the largerN 4 = 10(1)% found for the glass, and literature11B nuclear magnetic resonance measurements. van't Hoff analysis based on a simple boron isomerization reaction BØ3O2–⇌ BØO22–yields ΔH = 13(1) kJ mol–1and ΔS = 40(1) J mol–1 K–1for the boron coordination change from 4 to 3, which are, respectively, smaller and larger than found for singly charged isomers forJ ≤ 1. With these, we extend our model forN 4(J ,T ), nonbridging oxygen fractionf nbr(J ,T ), configurational heat capacity , and entropyS conf(J ,T ) contributions up toJ = 3. A maximum is revealed in atJ = 1, and shown semi‐quantitatively to lead to a corresponding maximum in fragility contribution, akin to that observed in the total fragilities by temperature‐modulated differential scanning calorimetry. Lithium is bound to 4.6(2) oxygen in the pyroborate liquid, with 2.7(1) bonds centered around 1.946(8) Å and 1.9(1) around 2.42(1) Å. In the glass,n LiO= 5.4(4), the increase being due to an increase in the number of short Li–O bonds. -
more » « less
Abstract The structures of glasses in the lithium–bismuth orthoborate composition range deviate significantly from the short‐range order structure of the two crystalline end‐members. Although binary Li3BO3and BiBO3are solely of comprised trigonal orthoborate anions, all glasses formed by their combination contain four‐coordinated borate tetrahedra. We analyze the structure of (75−1.5
x )Li2O–x Bi2O3–(25+0.5x )B2O3glasses in increments ofx = 5, with11B magic‐angle spinning nuclear magnetic resonance (NMR), infrared (IR), and Raman spectroscopy. For the full series, the oxygen‐to‐boron ratio remains constant at O/B = 3:1. NMR quantifies an increase in the fraction of tetrahedral boron with increasing bismuth oxide content. Evolution of the mid‐IR profile suggests multiple types of tetrahedral boron sites. Raman spectroscopy reveals that Bi2O3tends to cluster within the lithium borate matrix when initially introduced and that this behavior transforms into a bismuthate network with increasing bismuth oxide content. In all cases, mixed Bi–O–B linkages are observed. The dual role of bismuth as network modifier and network former is likewise observed in the far IR. The glass transition temperature continuously increases with bismuth oxide content; however, the glass stability displays a maximum in the multicomponent glass ofx = 40. -
more » « less
Abstract Rising global temperatures are expected to decrease the precipitation amount that falls as snow, causing greater risk of water scarcity, groundwater overdraft, and fire in areas that rely on mountain snowpack for their water supply. Streamflow in large river basins varies with the amount, timing, and type of precipitation, evapotranspiration, and drainage properties of watersheds; however, these controls vary in time and space making it difficult to identify the areas contributing most to flow and when. In this study, we separate the evaporative influences from source values of water isotopes from the Snake River basin in the western United States to relate source area to flow dynamics. We developed isoscapes (δ2H and δ18O) for the basin and found that isotopic composition of surface water in small watersheds is primarily controlled by longitude, latitude, and elevation. To examine temporal variability in source contributions to flow, we present a 6‐years record of Snake River water isotopes from King Hill, Idaho, after removing evaporative influences. During periods of low flow, source water values were isotopically lighter indicating a larger contribution to flow from surface waters in the highest elevation, eastern portion of the basin. River evaporation increases were evident during summer likely reflecting climate, changing water availability, and management strategies within the basin. Our findings present a potential tool for identifying critical portions of basins contributing to river flow as climate fluctuations alter flow dynamics. This tool can be applied in other continental‐interior basins where evaporation may obscure source water isotopic signatures.
