More Like this

1. Eu speciation in apatite at 1 bar: An experimental study of valence-state partitioning by XANES, lattice strain, and Eu/Eu* in basaltic systems

   https://doi.org/10.2138/am-2022-8388  

   Tailby, Nicholas D.; Trail, Dustin; Watson, Bruce; Lanzirotti, Antonio; Newville, Matthew; Wang, Yanling (May 2023, American Mineralogist: Journal of Earth and Planetary Materials)

   Abstract Partition coefficients for rare earth elements (REEs) between apatite and basaltic melt were determined as a function of oxygen fugacity (fO2; iron-wüstite to hematite-magnetite buffers) at 1 bar and between 1110 and 1175 °C. Apatite-melt partitioning data for REE3+ (La, Sm, Gd, Lu) show near constant values at all experimental conditions, while bulk Eu becomes more incompatible (with an increasing negative anomaly) with decreasing fO2. Experiments define three apatite calibrations that can theoretically be used as redox sensors. The first, a XANES calibration that directly measures Eu valence in apatite, requires saturation at similar temperature-composition conditions to experiments and is defined by: ( E u 3 + ∑ E u ) Apatite  = 1 1 + 10 - 0.10 ± 0.01 × l o g ⁡ ( f o 2 ) - 1.63 ± 0.16 . The second technique involves analysis of Sm, Eu, and Gd in both apatite and coexisting basaltic melt (glass), and is defined by: ( Eu E u * ) D Sm × Gd = 1 1 + 10 - 0.15 ± 0.03 × l o g ⁡ ( f o 2 ) - 2.46 ± 0.41 . The third technique is based on the lattice strain model and also requires analysis of REE in both apatite and basalt. This calibration is defined by ( Eu E u * ) D lattice strain = 1 1 + 10 - 0.20 ± 0.03 × l o g ⁡ ( f o 2 ) - 3.03 ± 0.42 . The Eu valence-state partitioning techniques based on (Sm×Gd) and lattice strain are virtually indistinguishable, such that either methodology is valid. Application of any of these calibrations is best carried out in systems where both apatite and coexisting glass are present and in direct contact with one another. In holocrystalline rocks, whole rock analyses can be used as a guide to melt composition, but considerations and corrections must be made to either the lattice strain or Sm×Gd techniques to ensure that the effect of plagioclase crystallization either prior to or during apatite growth can be removed. Similarly, if the melt source has an inherited either a positive or negative Eu anomaly, appropriate corrections must also be made to lattice strain or Sm×Gd techniques that are based on whole rock analyses. This being the case, if apatite is primary and saturates from the parent melt early during the crystallization sequence, these corrections may be minimal. The partition coefficients for the REE between apatite and melt range from a maximum DEu3+ = 1.67 ± 0.25 (as determined by lattice strain) to DLu3+ = 0.69 ± 0.10. The REE partition coefficient pattern, as observed in the Onuma diagram, is in a fortuitous situation where the most compatible REE (Eu3+) is also the polyvalent element used to monitor fO2. These experiments provide a quantitative means of assessing Eu anomalies in apatite and how they be used to constrain the oxygen fugacity of silicate melts. 

   more » « less
2. Neogene faulting, basin development, and relief generation in the southern Klamath Mountains (USA)

   https://doi.org/10.1130/GES02612.1  

   Michalak, Melanie J; Cashman, Susan M; Langenheim, Victoria E; Team, Taylor C; Christensen, Dana J (December 2023, Geosphere)

   Abstract Development and evaluation of models for tectonic evolution in the Cascadia forearc require understanding of along-strike heterogeneity of strain distribution, uplift, and upper-plate characteristics. Here, we investigated the Neogene geologic record of the Klamath Mountains province in southernmost Cascadia and obtained apatite (U-Th)/He (AHe) thermochronology of Mesozoic plutons, Neogene graben sediment thickness, detrital zircon records from Neogene grabens, gravity and magnetic data, and kinematic analysis of faults. We documented three aspects of Neogene tectonics: early Miocene and younger rock exhumation, development of topographic relief sufficient to isolate Neogene graben-filling sediments from sources outside of the Klamath Mountains, and initiation of mid-Miocene or younger right-lateral and reverse faulting. Key findings are: (1) 10 new apatite AHe mean cooling ages from the Canyon Creek and Granite Peak plutons in the Trinity Alps range from 24.7 ± 2.1 Ma to 15.7 ± 2.1 Ma. Inverse thermal modeling of these data and published apatite fission-track ages indicate the most rapid rock cooling between ca. 25 and 15 Ma. One new AHe mean cooling age (26.7 ± 3.2 Ma) from the Ironside Mountain batholith 40 km west of the Trinity Alps, combined with previously published AHe ages, suggests geographically widespread latest Oligocene to Miocene cooling in the southern Klamath Mountains province. (2) AHe ages of 39.4 ± 5.1 Ma on the downthrown side and 22.7 ± 3.0 Ma on the upthrown side of the Browns Meadow fault suggest early Miocene to younger fault activity. (3) U-Pb detrital zircon ages (n = 862) and Lu-Hf isotope geochemistry from Miocene Weaverville Formation sediments in the Weaverville, Lowden Ranch, Hayfork, and Hyampom grabens south and southwest of the Trinity Alps can be traced to entirely Klamath Mountains sources; they suggest the south-central Klamath Mountains had, by the middle Miocene, sufficient relief to isolate these grabens from more distal sediment sources. (4) Two Miocene detrital zircon U-Pb ages of 10.6 ± 0.4 Ma and 16.7 ± 0.2 Ma from the Lowden Ranch graben show that the maximum depositional age of the upper Weaverville Formation here is younger than previously recognized. (5) A prominent steep-sided negative gravity anomaly associated with the Hayfork graben shows that both the north and south margins are fault-controlled, and inversion of gravity data suggests basin fill is between 1 km and 1.9 km thick. Abrupt elevation changes of basin fill-to-bedrock contacts reported in well logs record E-side-up and right-lateral faulting at the eastern end of the Hayfork graben. A NE-striking gravity gradient separates the main graben on the west from a narrower, thinner basin to the east, supporting this interpretation. (6) Of fset of both the base of the Weaverville Formation and the cataclasite-capped La Grange fault surface by a fault on the southwest margin of the Weaverville basin documents 200 m of reverse and 1500 m of right-lateral strike-slip motion on this structure, here named the Democrat Gulch fault; folded and steeply dipping strata adjacent to the fault confirm that faulting postdated deposition of the Weaverville Formation. Based on these findings, we suggest that Miocene rock cooling recorded by AHe ages, accompanying graben formation, and development of topographic relief record early to middle Miocene initiation of underplating or “subcretion” in the southern Cascadia subduction zone beneath the southern Klamath Mountains. 

   more » « less
3. An ab-initio study on the thermodynamics of disulfide, sulfide, and bisulfide incorporation into apatite and the development of a more comprehensive temperature, pressure, pH, and composition-dependent model for ionic substitution in minerals

   https://doi.org/10.2138/am-2022-8250  

   Kim, YoungJae; Konecke, Brian; Simon, Adam; Fiege, Adrian; Becker, Udo (November 2022, American Mineralogist)

   Abstract The mineral apatite, Ca10(PO4)6(F,OH,Cl)2, incorporates sulfur (S) during crystallization from S-bearing hydrothermal fluids and silicate melts. Our previous studies of natural and experimental apatite demonstrate that the oxidation state of S in apatite varies systematically as a function of oxygen fugacity (fO2). The S oxidation states –1 and –2 were quantitatively identified in apatite crystallized from reduced, S-bearing hydrothermal fluids and silicate melts by using sulfur K-edge X-ray absorption near-edge structure spectroscopy (S-XANES) where S 6+/ΣS in apatite increases from ~0 at FMQ-1 to ~1 at FMQ+2, where FMQ refers to the fayalite-magnetite-quartz fO2 buffer. In this study, we employ quantum-mechanical calculations to investigate the atomistic structure and energetics of S(-I) and S(-II) incorporated into apatite and elucidate incorporation mechanisms. One S(-I) species (disulfide, S22−) and two S(-II) species (bisulfide, HS−, and sulfide, S2−) are investigated as possible forms of reduced S species in apatite. In configuration models for the simulation, these reduced S species are positioned along the c-axis channel, originally occupied by the column anions F, Cl, and OH in the end-member apatites. In the lowest-energy configurations of S-incorporated apatite, disulfide prefers to be positioned halfway between the mirror planes at z = 1/4 and 3/4. In contrast, the energy-optimized bisulfide is located slightly away from the mirror planes by ~0.04 fractional units in the c direction. The energetic stability of these reduced S species as a function of position along the c-axis can be explained by the geometric and electrostatic constraints of the Ca and O planes that constitute the c-axis channel. The thermodynamics of incorporation of disulfide and bisulfide into apatite is evaluated by using solid-state reaction equations where the apatite host and a solid S-bearing source phase (pyrite and Na2S2(s) for disulfide; troilite and Na2S(s) for sulfide) are the reactants, and the S-incorporated apatite and an anion sink phase are the products. The Gibbs free energy (ΔG) is lower for incorporation with Na-bearing phases than with Fe-bearing phases, which is attributed to the higher energetic stability of the iron sulfide minerals as a source phase for S than the sodium sulfide phases. The thermodynamics of incorporation of reduced S is also evaluated by using reaction equations involving dissolved disulfide and sulfide species [HnS(aq)(2−n) and HnS(aq)(2−n); n = 0, 1, and 2] as a source phase. The ΔG of S-incorporation increases for fluorapatite and chlorapatite, and decreases for hydroxylapatite, as these species are protonated (i.e., as n changes from 0 to 2). These thermodynamic results demonstrate that the presence of reduced S in apatite is primarily controlled by the chemistry of magmatic and hydrothermal systems where apatite forms (e.g., an abundance of Fe; solution pH). Ultimately, our methodology developed for evaluating the thermodynamics of S incorporation in apatite as a function of temperature, pH, and composition is highly applicable to predicting the trace and volatile element incorporation in minerals in a variety of geological systems. In addition to solid-solid and solid-liquid equilibria treated here at different temperatures and pH, the methodology can be easily extended to different pressure conditions by just performing the quantum-mechanical calculations at elevated pressures. 

   more » « less
4. What we can learn in the kitchen sink: an example from garnet granulite

   Stowell, H.H. (January 2021, America Geophysical Union)

   Interpretation of geochronological and petrological data from partially-melted granulite is challenging. However, integration of multiple chronometers and mineral assemblage diagrams (MAD) can be used to estimate the nature and duration of processes. Excellent lower-crustal exposures of garnet granulite from the Malaspina Pluton, Fiordland New Zealand provide an ideal place to employ this kitchen sink approach. We use zircon U-Pb ages from LA-ICPMS, SHRIMP-RG, and CA-TIMS, garnet Lu-Hf and Sm-Nd ages, and MAD in order to evaluate local partial melting vs. melt injection, equilibrium volumes, P-T conditions, and the duration of lower crustal thermal events. Host diorite (H), garnet-clinopyroxene reaction zones (GRZ), coarse garnet selvages, and tonalite veins provide a record of intrusion and granulite facies partial melting. Zircon U-Pb ages range from 123 to 107 Ma (all); LA-ICPMS ages contain the entire range; CA-TIMS ages range from 118.30±0.13 to 115.7±0.18 Ma; and SHRIMP-RG ages range from 121.4±2 to 109.8±1.8 Ma. The latter two techniques are interpreted to indicate primary igneous crystallization from ~119 to ~116 Ma and the youngest ~110 Ma ages are interpreted as metamorphic zircon growth. Garnet ages for ~1 cm grains are ~113 Ma (Lu-Hf & Sm-Nd) and record metamorphic growth, and <0.3 mm grains with Sm-Nd ages from 113 to 104 Ma reflect high temperature intracrystalline diffusion and isotopic closure during cooling to amphibolite facies. Zircon trace-element compositions indicate 2 distinct crystallization trends reflecting evolution of primary magma batches. MAD indicate that garnet was not in equilibrium with sampled rock compositions. Instead, garnet shows apparent equilibrium with a modeled mixture of the GRZ and the H and grew in equilibrium with an effective bulk composition that shifted toward the leucosome. This would produce the observed increase in garnet grossular content. We conclude that: Malaspina rocks from Crooked Arm preserve evidence for 2 igneous layers which evolved as discrete magmas, igneous crystallization lasted 2 to 3 m.y., granulite metamorphism peaked ~ 3 m.y. after intrusion, metamorphism lasted ≥3 m.y., cooling occurred at ~20°C/m.y., and granulite minerals equilibrated with a mixture of solid phases and melt at ~14 kbar and 920°C (based on garnet compositions and MAD). 

   more » « less
5. Cretaceous magmatism in the Antarctic Peninsula and its tectonic implications

   https://doi.org/10.1144/jgs2022-067  

   Bastias, Joaquin; Spikings, Richard; Riley, Teal; Chew, David; Grunow, Anne; Ulianov, Alexey; Chiaradia, Massimo; Burton-Johnson, Alex (December 2022, Journal of the Geological Society)

   Periods of cessation, resumption and enhanced arc activity are recorded in the Cretaceous igneous rocks of the Antarctic Peninsula. We present new geochronological (laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U–Pb) analyses of 36 intrusive and volcanic Cretaceous rocks, along with LA-ICP-MS apatite U–Pb analyses (a medium-temperature thermochronometer) of 28 Triassic–Cretaceous igneous rocks of the Antarctic Peninsula. These are complemented by new zircon Hf isotope data along with whole-rock geochemistry and isotope (Nd, Sr and Pb) data. Our results indicate that the Cretaceous igneous rocks of the Antarctic Peninsula have geochemical signatures consistent with a continental arc setting and were formed during the interval c. 140–79 Ma, whereas the main peak of magmatism occurred during c. 118–110 Ma. Trends in ε Hf t (zircon) combined with elevated heat flow that remagnetized rocks and reset apatite U–Pb ages suggest that Cretaceous magmatism formed within a prevailing extensional setting that was punctuated by periods of compression. A noteworthy compressive period probably occurred during c. 147–128 Ma, triggered by the westward migration of South America during opening of the South Atlantic Ocean. Cretaceous arc rocks that crystallized during c. 140–100 Ma define a belt that extends from southeastern Palmer Land to the west coast of Graham Land. This geographical distribution could be explained by (1) a flat slab with east-dipping subduction of the Phoenix Plate, or (2) west-dipping subduction of the lithosphere of the Weddell Sea, or (3) an allochthonous origin for the rocks of Alexander Island. A better understanding of the geological history of the pre-Cretaceous rocks of Alexander Island and the inaccessible area of the southern Weddell Sea is required. Supplementary material: A description of the methods used in this study and the complete dataset are available at https://doi.org/10.6084/m9.figshare.c.6089274 

   more » « less