Open-system Behavior Research Articles

Molybdenum isotope behavior during subduction zone metamorphism

The molybdenum (Mo) isotope composition (defined as δ98Mo measured per mil relative to NIST-3134) of many modern arc systems and the upper continental crust is heavier than the mantle and most subducting slab lithologies. This observation has led to a model whereby fluids leaving the slab transfer isotopically heavy Mo preferentially to the mantle wedge, leaving the residual slab isotopically lighter. We explore this model via an Mo isotope study of the metasedimentary and mélange lithologies of the Catalina Schist in California. These rocks record subduction zone metamorphism over a wide range of high-pressure/low-to-medium temperature conditions.Mo isotope compositions of the metasedimentary rocks decrease with increasing metamorphic grade, from a δ98Momean of −0.04 ± 0.13 ‰ (1σ, n = 3) for the lawsonite albite facies to −0.38 ± 0.07 ‰ (1σ, n = 5) for the epidote–amphibolite facies. The highest grade [amphibolite facies] samples show a slight uptick in δ98Mo values, with a mean of −0.19± 0.14 ‰ (1σ, n = 4). When coupled with major and trace element variations, the changes in δ98Mo appear to reflect metamorphic effects rather than sedimentary source rock heterogeneity. The positive relationship between δ98Mo and [Mo] and negative relationship with Ce/Mo argue for progressive loss of Mo with isotope fractionation during increasing P-T conditions; the reversal of this trend, seen in the increase in δ98Mo between the epidote amphibolite and amphibolite facies may reflect a subsequent partial re-fertilization by fluids carrying isotopically heavy Mo. δ98Mo values in the mélange across all grades are highly variable, ranging from −1.75 to −0.19, consistent with large scale mobilization of Mo with isotope fractionation. A metasomatized amphibolite block and reaction rind show similar light isotope compositions and signs of Mo depletion and transport. Together these three whole-rock data sets demonstrate pervasive open system behavior and mobility of Mo in the Catalina Schist. LA-ICP-MS Mo measurement of minerals in the differing metasedimentary metamorphic grades indicates that Fe oxides and/or hydroxides, titanite, rutile, and epidote are important reservoirs of Mo but when comparing mineral Mo content and modal abundance to whole-rock Mo concentrations, several samples were found to have “missing Mo”, something that has been observed in other Mo inventory studies. We attribute this to sample heterogeneity between the thin section and whole-rock powder scales.

In situ Lu–Hf dating of allanite by LA-ICP-MS/MS: Implications for geochronology

Allanite is a common REE-rich accessory mineral found in various igneous and metamorphic rocks, and can record a variety of geological processes. Therefore, allanite geochronology has the potential to answer a range of important geological questions. Allanite U–Th–Pb geochronology is hampered by common open-system behavior in the system. In this study, we demonstrate the feasibility of in situ allanite Lu–Hf dating by LA–ICP–MS/MS. A total of nine allanite samples from different rock types (e.g., granite, pegmatite) were investigated. These allanite samples have ages ranging from ca. 2650 to ca.100 Ma, and Lu contents ranging from several to hundreds of μg g−1 levels and relatively high Lu/Hf ratios (> 30). At a mass shift of +82, the isobaric interferences 176Lu and 176Yb have extremely low reaction rates of ∼0.003 % and ∼ 0.0003 %, respectively, indicating the isobaric interference corrections are insignificant for the allanite samples (mean 175Lu/177Hf = ∼814; mean 172Yb/177Hf = ∼719). A two-step calibration strategy was proposed for the 176Lu/176Hf and 177Hf/176Hf ratio corrections using NIST SRM 610 (for instrument drift) and LE2808 (for matrix effect). The nine allanite samples contain common Hf contents (f176Hf) of ∼5 % to >90 %, and the data are plotted in inverse isochron diagrams. Unanchored inverse isochron ages exhibit a large deviation in accuracy (5–10 %), whilst anchored isochron ages have a better accuracy of <5 %. The uncertainty of anchor initial 176Hf/177Hf values was investigated and, in general, was insignificant (< 2.8 %) for samples with f176Hf < 80 %. Our results demonstrate that in situ allanite Lu–Hf dating by LA-ICP-MS/MS is feasible and can yield precise and accurate ages (< 5 %). Lu–Hf geochronometer captures the high-temperature process and may be more resistant during the late thermal event. Thus, it provides an alternative solution for those samples which are suffered by open-system behavior in U-Th-Pb system.

Lu-Hf and U-Pb dating of the Zayanderud eclogites: Implications for Jurassic subduction initiation along the Neotethys margin in Iran

The time at which the Neotethys Ocean started to subduct along the southern margin of Eurasia within Iran has been debated in recent years. This margin, referred to as the Sanandaj-Sirjan Zone (SaSZ), features a series of Jurassic calc-alkaline igneous formations which were emplaced at c. 170 Ma. However, an alternative model suggests that subduction initiation occurred during the Cretaceous period. To address this age controversy, we utilized the Lu-Hf isochron method and employed SIMS U-Pb zircon and rutile geochronology to determine the metamorphic history of the earliest known Neotethyan eclogite outcrop along the upper Zayanderud River section of the SaSZ. Two eclogites separated by ∼25 km yielded Lu-Hf garnet dates of 175.1 ± 1.0 Ma and 172.5 ± 0.6 Ma. Rare <20 μm eclogitic zircon crystals in one of the eclogites are strongly zoned and yielded U-Pb dates for which a 177 ± 10 Ma rim age was deconvolved. The relatively low Dy/Yb of these zircon rims suggests that they crystallized prior to garnet formation, or retrograde in disequilibrium with garnet. Homogeneous U-Pb rutile ages averaging 162 ± 7 Ma are only marginally younger than the Lu-Hf garnet ages, consistent with the petrographic observation that rutile is predominantly found in the matrix or within garnet rims, and open-system behavior of radiogenic Pb during cooling. The newly obtained ages are close to previously published 40Ar/39Ar phengite dates and indicate a narrow time window during the Middle Jurassic for deep burial within a subduction channel, followed by eclogitization and rapid exhumation. These new constraints on the metamorphic history support subduction initiation along the SaSZ margin in the Jurassic period.

Deciphering the U-Pb dates of sedimentary phosphates: A complex example from the Upper Cretaceous-Lower Paleogene series in northwestern Morocco

Uranium‑lead geochronology rapidly generates dates of rock deposition/formation with reasonable precision and accuracy using laser ablation inductively coupled plasma mass spectrometry, which is needed for bracketing stratigraphy. However, previous radiometric U-Pb dating of biogenic (i.e., bones and teeth) and sedimentary phosphate minerals have had limited success, probably because of the nanometric to micrometric crystallites that generate open system behavior. Sediment lithification inhibiting trace element exchange between minerals and porewaters and thus forcing phosphorus-rich crystallites to adopt a closed system behavior has been suggested for interpreting U-Pb dating of carbonate fluorapatite (CFA). Despite these insights, what remains lacking is extensive U-Pb CFA dating at the regional scale to test whether several processes influence the timing of U-Pb system closure by inhibiting U and Pb exchanges. Here, we report U-Pb CFA dating from four sampling sites in northwestern Morocco to understand better the meaning of U-Pb dates in CFA. The Upper Cretaceous-Lower Paleogene phosphate series yields anomalously low 207Pb/206Pb initial ratios and young dates ranging from 37.3 ± 2.4 Ma to 22.7 ± 0.7 Ma, which does not agree with the terrestrial lead model composition for Paleogene ages and the known biostratigraphic ages, respectively. We argue that ancient radiogenic Pb from leached polymetallic mineralizations of the regional environment have been incorporated into CFA and that a 25 to 40 Ma-long widespread resetting of the U-Pb system has affected the northwestern Moroccan phosphates. Neither CFA-hosted CO32− concentrations nor rare earth element and yttrium contents indicate post-depositional modifications of the chemical nature of phosphate-bearing rocks. Burial diagenesis promoting sediment lithification is one of the mechanisms that have triggered final closure of the U-Pb system of CFA minerals and, interestingly, the sedimentation rate was probably not a controlling factor. Unexpectedly, U-Pb dates of ∼23 Ma from three stratigraphic levels separated by several million years seem to be concomitant with the regional emersion and generalized continentalization of northwestern Morocco, allowing CFA to behave as a closed system. We conclude that the laser ablation inductively coupled mass spectrometry U-Pb dating of biogenic and sedimentary CFA minerals must be carefully employed to date the timing of fossilization or sediment deposition.

Multi-scale, open-system magmatic and sub-solidus processes contribute to the chemical and isotopic characteristics of the Jurassic Guadalupe Igneous Complex, Sierra Nevada, California, USA

Abstract The chemical and isotopic characteristics of a solidified pluton represent the integration of magmatic and sub-solidus processes operating across a range of spatial and temporal scales during pluton construction, crystallization, and cooling. Disentangling these processes and understanding where chemical and isotopic signatures were acquired requires the combination of multiple tools tracing processes at different time and length scales. We combine whole-rock oxygen and Sr-Nd isotopes, zircon oxygen isotopes and trace elements, and mineral compositions with published high-precision U-Pb zircon geochronology to evaluate differentiation within the bimodal Guadalupe Igneous Complex, Sierra Nevada, California (USA). The complex was constructed in ~300 k.y. between 149 and 150 Ma. Felsic magmas crystallized as centimeter- to meter-sized segregations in gabbros in the lower part of the complex and as granites and granophyres structurally above the gabbros. A central mingling zone separates the mafic and felsic units. Pluton-wide δ18O(whole-rock), δ18O(zircon), and Sr-Nd isotopic ranges are too large to be explained by in situ, closed-system differentiation, instead requiring open-system behavior at all scales. Low δ18O(whole-rock) and δ18O(zircon) values indicate assimilation of hydrothermally altered marine host rocks during ascent and/or emplacement. In situ differentiation processes operated on a smaller scale (meters to tens of meters) for at least ~200 k.y. via (1) percolation and segregation of chemically and isotopically diverse silicic interstitial melt from a heterogeneous gabbro mush; (2) crystal accumulation; and (3) sub-solidus, high-temperature, hydrothermal alteration at the shallow roof of the complex to modify the chemical and isotopic characteristics. Whole-rock and mineral chemistry in combination with geochronology allows deciphering open-system differentiation processes at the outcrop to pluton scale from magmatic to sub-solidus temperatures over time scales of hundreds of thousands to millions of years.

Tracing the Scale of Fluid Flow in Subduction Zone Forearcs: Implications from Fluid-Mobile elements

Despite the importance of fluids in subduction zone processes, the extent of mass transfer and fluid circulation from the subducting plate through the forearc region remain unclear. To estimate the fluid budget and scale of fluid circulation in subducted sediments, we assess the distribution and retention of fluid-mobile elements (FME) in metamorphically equivalent metapelites from the Kodiak complex (Alaska) and the Shimanto Belt (Japan). The temperature range of interest is 230–350 °C, i.e., encompasses the base of the seismogenic zone. We examine the Li, B, Rb, Sr, Cs, and Ba concentrations in the bulk rock, as well as in fluid inclusions and individual minerals by (LA-) ICP-MS.The whole-rock composition in metapelites from Kodiak shows no significant loss of FME, which is in contrast to Shimanto where between 10% and 55% of FME (particularly Li, B and Cs) are leached out of rocks. The FME budget in Kodiak is consistent with a redistribution of elements between metamorphic illite and chlorite, whereas in Shimanto the loss of Li, B and Cs as temperature increases is the result of decreasing concentrations in illite and chlorite. The semi-quantitative analysis of fluid inclusions is consistent with a significant enrichment in all analyzed trace elements relative to seawater and interstitial pore fluids of seafloor sediments.Combining the fluid compositions with the whole-rock compositions, mass balance calculations were performed for B, Cs, and Ba. In the Kodiak complex the mass balance calculations are consistent with closed-system behavior, wherein the fluid is an insignificant reservoir for FME. Conversely, in the Shimanto Belt the mass balance calculations are consistent with open-system behavior, wherein large amounts of fluid percolated through rocks and the mass water-rock ratios correspond to 0.5–2.2. We infer that such an open system behavior was promoted by a larger amount of internal strain and the proximity to a large-scale fault zone. Moreover, fluid compositions observed in this study exhibit similarities to the composition of mud volcano fluids. This similarity is consistent with extensive, focused fluid circulation originating from depths of at least 15 km and ascending to the surface through a substantial damage zone associated with an out-of-sequence thrust.

Mineralogy and geochemistry of multi-coloured sapphires at the Portezuelo de Pajas Blancas' deposits, northern Chile: revealing crystal growth processes

Portezuelo de Pajas Blancas' primary metasomatic deposits host sapphires that differ in size, colour, and colour distribution through different lithological units. The discovery of sapphire-bearing secondary aeolian placer deposits enabled a detailed analysis of sapphire types to determine the causes of this heterogeneity. Representative single sapphires from the primary and secondary deposits were analysed using various techniques, including SEM-CL, OM-CL, Micro-XRF, Raman spectroscopy, and polarised transmitted light multi-focus optical microscopy. Based on the results, seven sapphire types were identified according to their colours and colour distribution. Fe and Ti concentrations mainly contribute to the colour and micro-textures occurrence. The primary growth textures include cores, progressive, oscillatory, and diffusion zoning, whereas the secondary alteration features correspond to micro-brecciation, re-arrangement, and overgrowth. Inclusions such as euhedral andalusite, anhedral anhydrite, and anhedral rutile were identified in the sapphires. The formation of Portezuelo de Pajas Blancas sapphires can be divided into five genetic stages: (i) core growth development; (ii) chemical imbalance due to open system behaviour that produces progressive and oscillatory zoning; (iii) low-temperature deformations that produce micro-brecciation; (iv) re-arrangement of pre-formed sapphire fragments and subsequent sapphire overgrowth; (v) diffusion zoning that produce Fe- and Ti-enriched outer rims. In conclusion, the Portezuelo de Pajas Blancas' sapphires were formed through at least five stages of oxidised contact metasomatism at varying temperatures and low pressures, where a heterogeneous forming condition predominates during sapphire formation.Graphical

Geochronological and geochemical effects of zircon chemical abrasion: insights from single-crystal stepwise dissolution experiments

Abstract. Chemical abrasion in hydrofluoric acid (HF) is routinely applied to zircon grains prior to U–Pb dating by isotope dilution thermal ionization mass spectrometry (ID-TIMS) to remove radiation-damaged portions of grains affected by Pb loss. Still, many chemically abraded datasets exhibit evidence of residual Pb loss. Here we test how the temperature and duration of chemical abrasion affect zircon U–Pb and trace element systematics in a series of 4 h, single-crystal stepwise dissolution experiments at 180 and 210 ∘C. Microtextural data for the zircon samples studied are presented in a companion paper by McKanna et al. (2023). We find that stepwise dissolution at 210 ∘C is more effective at eliminating material affected by open-system behavior and enriched in U, common Pb (Pbc), and light rare earth elements (LREEs); reduces the presence of leaching-induced artifacts that manifest as reverse discordance; and produces more consistent and concordant results in zircon from the three rocks studied. We estimate that stepwise dissolution in three 4 h steps is roughly equivalent to a single ∼ 8 h leaching step due to the insulating properties of the PTFE sleeve in the Parr pressure dissolution vessel, whereas traditionally labs utilize a single 12 h leaching step. We conclude that a single 8 h leaching step at 210 ∘C should remove Pb loss effects in the majority of zircon and that this can be used as an effective approach for routine analysis. Further, we calculate time-integrated alpha doses for leachates and residues from measured radionuclide concentrations to investigate (1) the alpha dose of the material dissolved under the two leaching conditions and (2) the apparent minimum alpha dose required for Pb loss susceptibility: ≥ 6×1017 α g−1.

A Log‐Ratio‐Based Algorithm for Petrologic Mass‐Balance Problems and Uncertainty Assessment

AbstractWe provide a new algorithm for mass‐balance calculations in petrology and geochemistry based on the log‐ratio approach championed initially by John Aitchison (e.g., Aitchison, 1982, https://doi.org/10.1111/j.2517-6161.1982.tb01195.x; Aitchison, 1984, https://doi.org/10.1007/bf01029316) along with the underlying principles, mathematical frameworks, and data requirements. Log‐ratio Inversion of Mixed End‐members (LIME) is written in MATLAB and calculates phase proportions in an experiment or rock given a bulk composition, the composition of each phase, and the associated compositional uncertainties. An important advantage of LIME is that performing the mass‐balance calculation in inverse log‐ratio space constrains phase proportions to be between 0 and 100 wt.%. Further, the resulting LIME phase proportions provide realistic estimates of uncertainty regardless of data distribution. These two characteristics of LIME improve upon standard multiple linear regression techniques, which may yield negative values for phase proportions if non‐constrained or report oversimplified symmetric errors. Primary applications of LIME include estimating phase abundances, calculating melting and metamorphic reaction stoichiometries, and checking for open system behavior in phase equilibria experiments. The technique presented here covers whole‐rock analysis, mineralogy, and phase abundance, but could be extended to isotopic tracers, trace element modeling, and regolith component un‐mixing. We highlight the importance of uncertainty estimations for phase abundances to the fields of petrology and geochemistry by comparing our results from LIME to previously published mass‐balance calculations. Furthermore, we present case studies that demonstrate the role of mass‐balance calculations in determining magma crystallinity and defining melting reactions.

Unusual open-system behaviour revealed by LA-MC-ICP-MS U–Th dating of coral and coralline algae bio-carbonates

Unusual open-system behaviour revealed by LA-MC-ICP-MS U–Th dating of coral and coralline algae bio-carbonates

Phase equilibrium modelling of partial melting in the upper mantle: A comparison between different modelling methodologies and experimental results

Recent advances in thermodynamic modelling now allow phase equilibrium studies of partial melting in mafic and ultramafic sources under upper mantle conditions. This potentially offers several advantages over experimental investigations, including the fact that capsule-sample interactions are avoided, there is no uncertainty over the volatile content of the charge, the process is much faster, and open system behaviour can be investigated with relative ease. Two different thermodynamic datasets are in common use for phase equilibrium investigations of mantle rocks, compiled alongside a range of constantly evolving phase solution models. This study compares the results of published experimental studies on partial melting in the upper mantle with phase equilibrium modelling results from the popular pMELTS software (Ghiorso et al., 2002), which uses an embedded dataset from Berman (1988), and with results from the Rcrust software (Mayne et al., 2016), which uses the dataset of Holland & Powell (2011). The aim of this comparative study is to investigate the suitability of each combination of software specific calculation routines, thermodynamic datasets and phase solution models to provide a viable alternative to conventional experimental techniques when studying magma genesis from the upper mantle. The main points of interest are how the phase assemblages, proportions, and compositions predicted by the modelling compare with those produced in the experiments. The set of experimental results used for comparison includes both peridotitic and eclogitic compositions, investigated over a pressure range of 1.0–3.0 GPa and a temperature range of 1165–1950 °C. The results indicate that using the Holland & Powell (2011) dataset and appropriately selected phase solution models provides the best match with experimental results in terms of melt volume, melt composition and the assemblage of coexisting phases produced during partial melting under upper mantle conditions.

Robust laser ablation Lu–Hf dating of apatite: an empirical evaluation

Abstract Recent developments in laser-ablation Lu–Hf dating have opened a new opportunity to rapidly obtain apatite ages that are potentially more robust to isotopic resetting compared to traditional U–Pb dating. However, the robustness of the apatite Lu–Hf system has not been systematically examined. To address this knowledge gap, we conducted four case studies to determine the resistivity of the apatite Lu–Hf system compared to the zircon and apatite U–Pb system. In all cases, the apatite U–Pb system records a secondary (metamorphic or metasomatic) overprint. The apatite Lu–Hf system, however, preserves primary crystallization ages in unfoliated granitoids at temperatures of at least c. 660°C. Above c. 730°C, the Lu–Hf system records isotopic resetting by volume diffusion. Hence, in our observations for apatites of ‘typical’ grain sizes in granitoids ( c. 0.01–0.03 mm 2 ), the closure temperature of the Lu–Hf system is between c. 660 and c. 730°C, consistent with theoretical calculations. In foliated granites, the Lu–Hf system records the timing of recrystallization, while the apatite U–Pb system tends to record younger cooling ages. We also present apatite Lu–Hf dates for lower crustal xenoliths erupted with young alkali basalts, demonstrating that the Lu–Hf system can retain a memory of primary ages when exposed to magmatic temperatures for a relatively short duration. Hence, the apatite Lu–Hf system is a new insightful addition to traditional zircon (or monazite) U–Pb dating, particularly when zircons/monazites are absent or difficult to interpret due to inheritance or when U and Pb isotopes display open system behaviour. The laser-ablation-based Lu–Hf method allows campaign-style studies to be conducted at a similar rate to U–Pb studies, opening new opportunities for magmatic and metamorphic studies.

Pre-eruptive dynamics at the Campi Flegrei Caldera: from evidence of magma mixing to timescales estimates

We review pre-eruptive dynamics and evidence of open-system behavior in the volcanic plumbing system beneath Campi Flegrei Caldera, together with estimates of magma residence time, magma ascent, and mixing-to-eruption timescales. In detail, we compile pre- and syn-eruptive dynamics reported in the literature for (a) the Campanian Ignimbrite ~ 40 ka, (b) the Neapolitan Yellow Tuff (~ 15 ka), and (c) the recent activity within the Phlegrean area. We first summarize geochemical and textural evidence (e.g., magma mixing, crystal disequilibria, vertical zonings, and isotopic records) of open-system behavior for the pyroclasts erupted in the last 40 ky at Campi Flegrei Caldera. We show that the fingerprint of open-system dynamics is ubiquitous in the deposits associated with the volcanic activity at the Campi Flegrei Caldera in the last 40 ky. Then, we describe the results of geophysical and petrological investigations that allow us to hypothesize the structure of the magma feeding system. We point to a trans-crustal magmatic feeding system characterized by a main storage reservoir hosted at ~ 9 km that feeds and interacts with shallow reservoirs, mainly placed at 2–4 km. Finally, we define a scenario depicting pre-eruptive dynamics of a possible future eruption and provide new constraints on timescales of magma ascent with a physical model based on magma-driven ascending dyke theory. Results show that considerably fast ascent velocities (i.e., of the order of m/s) can be easily achieved for eruptions fed by both shallow (i.e., 3–4 km) and deep (i.e., ~ 9 km) reservoirs. Comparing the results from experimental and numerical methods, it emerges that mixing-to-eruption timescales occurring at shallow reservoirs could be on the order of minutes to hours. Finally, we highlight the volcanological implications of our timescale estimates for magma ascent and mixing to eruption. In particular, explosive eruptions could begin with little physical ‘warning’, of the order of days to months. In this case, the onset of volatile saturation might provide pre-eruptive indicators.Graphical

Reliability of petrogenetic information obtained from the distribution of trace elements in zircon in light of the complex infusion by foreign-element-bearing low temperature solutions

The increasing application of minor elements such as REE, Ti, Fe in zircon as petrogenetic indicators depends on zircon remaining a closed chemical system over a history that can include metamorphic events, erosion, transport, and sedimentation. Whereas examples have been described of UPb loss and element exchange during metamorphic reactions, for over 50 years there have been reports of the accumulation of a range of non-formula elements such as Ca, Al, Fe, in zircons with no metamorphic history that have been tentatively related to hydrothermal action or some other process such as weathering. This open system behaviour of zircons needs further explanation and in this contribution we present data from three zircons from a late Archaean granite from Western Australia that confirm previous observations on the distribution of non-formula elements in radiation damaged zircon and support our earlier conclusion that elements are added from percolating low temperature weathering solutions and provide new insights into the mechanisms and processes controlling access of weathering fluids into the zircon. These include radiation damage accumulation over time from the decay of U and Th to produce domains of porous amorphous material that vary in porosity and the presence of weaknesses along the boundaries of oscillatory zones which allow the penetration of low temperature groundwater fluids carrying solute elements. Also important is the size of particles of the solute elements such as Al and Ca, which depends on Eh - pH of the groundwater and porous domains within the zircon structure. This low temperature fluid interaction is distinguished from hydrothermal activity by a lack of any reaction fronts or annealing of the radiation damage and a lack of any modification of existing zircon structures. Capillary action is proposed as the mechanism driving the penetration of weathering solutions into radiation damage expansion fractures and the radiation damaged zonal structure. The susceptibility of radiation damaged zircon to infusion by low temperature fluids and deposition of accompanying solute elements has implications for the application of zircon trace element chemistry as a petrogenetic and temperature indicator as well as a geochronometer and host for nuclear waste.

Tectonic fluid expulsion: U-Pb evidence for punctuated hydrothermal fluid flow and hydraulic fracturing during orogenesis

Tectonic fluid expulsion has been linked to fluid flow in permeable foreland basin sequences, but it is unclear how fluids migrate through underlying low-permeability successions. Here we report U-Pb data which indicate that fluids expelled during tectonic compression migrated through older compacted shales inboard of the deforming craton margin by fracture permeability and enhanced diffusion. From a ∼350 m drill-core interval of Neoarchean shale (drill-hole ABDP9), Hamersley region, Australia, we document abundant bedding-parallel veins indicating pervasive hydraulic fracturing. Thermometry of vein-filling chlorite indicates temperatures between 329-374°C, which is higher than estimates (175-280°C) from metamorphic assemblages in underlying basalts, implying the passage of hydrothermal fluids. New in situ secondary ion mass spectrometry (SIMS) U-Pb geochronology of monazite and xenotime in bedding-parallel veins verifies and expands earlier results, showing that microfracturing and hydrothermal fluid flow spanned ∼650 million years and was restricted to five short intervals: 2.30 Ga, 2.20 Ga, 2.10 Ga, 2.05 Ga and 1.65 Ga. Three of the five age populations coincide with known fabric-forming orogenic events (i.e. 2.30 Ga Sylvania orogeny; 2.22-2.15 Ga Ophthalmia orogeny; 1.68-1.65 Ga Mangaroon orogeny), which are focused along the southern Pilbara Craton margin. Our results show that the timing of veining was not random, but coeval with major orogenic events, linking fluid overpressure and hydraulic fracturing to the expulsion of heated orogenic fluids 100s of km inboard of the craton margin. The crack-seal veins indicate repeated cycles of fluid overpressure resulting in hydrofracturing and fluid drainage, followed by cavity collapse. The tectonic expulsion of pressurized hydrothermal fluids produced fracture and matrix permeability in Earth's upper crust, leading to episodic open-system behaviour with enhanced fluid-rock reactions and the large-scale transfer of heat and mass.

Lu–Hf, Sm–Nd, and U–Pb isotopic coupling and decoupling in apatite

Apatite is a useful geochronological tool due to its common occurrence and incorporation of a variety of radioactive parent isotopes during crystallisation. However, an understanding of the geological conditions recorded by each of these isotopic systems in apatite is necessary for their effective application to geological problems. In this study, U–Pb, Sm–Nd, and Lu–Hf dates for apatite grains from samples of ∼3.0 Ga TTG gneisses in the Akia terrane of the North Atlantic Craton (south-western Greenland) were obtained in order to better understand the conditions under which isotopic re-equilibration in apatite is achieved. This isotopic data records at least two thermotectonic events subsequent to the initial magmatic crystallisation of these rocks. Whereas the Lu–Hf and Sm–Nd isotopic systems in these apatites record a regional high temperature metamorphic event at ∼2.7 Ga, the U–Pb system records a milder thermal event at ∼1.7 Ga. This decoupling of the U–Pb from the Sm–Nd and Lu–Hf systems in apatite reflects a difference in closure temperature. The regional thermal effects of the ∼1.7 Ga Nagssugtoqidian orogeny in adjacent parts of the North Atlantic Craton resulted in partial to complete reequilibration of the U–Pb systems in apatite across the Akia terrane but were insufficient to cause open system behaviour of Sm–Nd or Lu–Hf. The indistinguishable apatite Sm–Nd and Lu–Hf ages produced in each analysed sample suggest that these systems are similarly susceptible to isotopic re-equilibration. The older ages produced by the Sm–Nd and Lu–Hf systems relative to U–Pb in apatite demonstrate that the former are more robust and thus more likely to faithfully record high temperature events than the U–Pb system.

230Th dating of gypsum from lacustrine, brackish-marine and terrestrial environments

Gypsum is an important environmental archive in hyperarid settings, but its application in earth sciences has been hampered by the limited availability of suitable dating methods. Here we re-evaluate the potential of 230Th/U dating for sedimentary gypsum as well as anhydrite samples in different depositional environments. We provide a robust analytical protocol based on a simple dissolution using nitric acid followed by a two-column separation procedure using anion exchange resin. Isotope analyses were performed using MC-ICPMS and a mixed 229Th-233U-236U tracer. We applied the method to a suite of samples that likely reached secular equilibrium as well as to three suites of younger (<300 ka old) samples, two from the Atacama Desert in Chile and one from a drill core of a saline playa lake in southern Spain. We employed a selective sampling approach targeting the least visually altered and clearest parts of the samples largely devoid of detritus and analysed multiple subsamples.The results demonstrate the general applicability of the 230Th/U method to gypsum as well as anhydrite, and recrystallization of gypsum to anhydrite does not significantly affect the U-series isotope system. However, there is evidence for open-system behaviour, which needs to be carefully assessed. Our results suggest that α-recoil processes as well as uptake or loss of uranium are important processes biasing the results of gypsum dating. Furthermore, we see signs of multiple-phase contamination in our case studies involving detrital components and authigenic phases. Based on these results we propose geochemical criteria in to identify biased 230Th/U gypsum ages.The application of our protocol to a suite of selenite samples deposited by brine outflows on the lowest terrace of Cerro Soledad (Atacama Desert, Chile) provides a mean age of 212 ± 8 ka, indicating a relatively humid climate interval with local rainfall in this area that is coinciding with marine isotope stage 7C. Selenites deposited in the paleo-lake Soledad system (Atacama Desert, Chile) yield 230Th/U ages ranging from 250 to 320 ka, in agreement with previous age estimates for the drainage of this paleo-lake obtained by cosmogenic nuclide dating. Application to a suite of gypsum crystals recovered from a drill core in the Laguna de Fuente de Piedra (South Spain) shows good agreement with their stratigraphic context, however, multiple-phase contamination produces larger age uncertainties for these ages.

U-series and radiocarbon cross dating of speleothems from Nerja Cave (Spain): Evidence of open system behavior. Implication for the Spanish rock art chronology

Two stalagmites from Nerja cave (Andalusia, Spain) were studied. The cave is well known because of its long human occupation from the Upper Palaeolithic to the Chalcolithic and its abundant parietal prehistoric Art. The aims of this study were twofold: i) to compare uranium/thorium (230Th/234U) and Carbon-14 (14C) ages obtained all along the growth axis of the stalagmites in order to understand the consequences of diagenetic processes on the validity of radiometric ages; ii) as one of the stalagmites contains black layers, attributed to combustion soot, to establish when these intense hearths were used and by which culture.230Th/234U and 14C ages were coupled with mineralogical studies using FTIR (Fourier-transform infrared spectroscopy) and thin section observations. The first stalagmite (GN16-9b) displays 230Th/234U ages in stratigraphic order, and compatible with 14C ages corrected for a few percent of dead carbon. Homogeneous composition of aragonitic crystals characterized by their needle-like texture is observed throughout this speleothem. For the second stalagmite (GN16-7), in contrast, 230Th/234U ages display large significant inversions and discordant results on the upper part and at the base of the stalagmite, suggesting a possible open system behavior for this chronometer. Interestingly, 14C ages are in stratigraphic order all along the stalagmite and are compatible with 230Th/234U ages only in its central part. Mineralogical studies display evidence of aragonite to calcite transformation at the top and a complex mineralogical assemblage with interlayered silicates (possibly clays) and calcitic mineralogy for the base of GN16-7. In these parts, discordant 230Th/234U ages were measured. In the middle part of the stalagmite, however, where the fibrous aragonite is well preserved, the 14C and 230Th/234U ages agree. Our data suggest that in the case of aragonite to calcite transformation as shown here, 230Th/234U ages are biased, but 14C ages seem to remain accurate, as already observed in aragonitic marine bio minerals. 14C ages obtained are used for the chronology of the soot layer, determined here between 7900 and 5500 years Cal BP, coherent with previous analysis of charcoals in the same sector of the cave. This study highlights the importance of working with at least two chronometers when stratigraphic age verification is not possible, as is the case of some parietal CaCO3 thin layers used for rock art dating. Recent 230Th/234U ages published for carbonate deposits on Spanish parietal Art are discussed in light of this demonstration.

Development of Tourmaline-Bearing Lithologies of the Peraluminous Tusaquillas Composite Granitic Batholith, NW Argentina: Evidence from Quartz and Tourmaline

ABSTRACT Textural and chemical characteristics of quartz and tourmaline found in tourmaline-rich orbicules, greisens, pegmatites, and tourmalinite segregations associated with the peraluminous leucogranitic Tusaquillas Batholith Complex of northwest Argentina exhibit both magmatic and hydrothermal features. Imaging of quartz by optical cathodoluminescence and scanning electron microscopy cathodoluminescence shows three stages of development. Stage-1 quartz, considered magmatic, develops as large grains in pegmatites that have optical cathodoluminescence homogeneity; as anhedral relict grains partially replaced by stage-2 hydrothermal quartz in tourmalinite segregations, orbicules, and greisens; and as idiomorphic grains with irregularly spaced oscillatory zoning seen in scanning electron microscopy cathodoluminescence in orbicules. Stage-2 quartz, interpreted as hydrothermal, partially replaces stage-1 quartz and generation-1 tourmaline in most lithologies. Stage-3 quartz, a late hydrothermal stage, occurs in all lithologies as weakly luminescing quartz in healed quartz fractures with abundant fluid inclusions, commonly associated with the crystallization of irregular late-stage tourmaline. Multiple generations of tourmaline span magmatic to hydrothermal phases of development. In all lithologies, generation-1 tourmaline is compositionally similar: highly aluminous (range of average values of Altotal = 6.31–6.95 apfu), markedly Fe- and X□-rich (XMg = 0.01–0.17, X□= 0.21–0.51), and having variable F and WO (F = 0.00–0.57 apfu, WO = 0.00–0.40). Generation-1 tourmaline is interpreted as magmatic with compositions reflecting the chemical environment of the host lithologies and with compositional zoning patterns characteristic of both closed- and open-system behavior, possibly related to the transition to subsolidus conditions. Similar to generation-1 tourmaline, later-stage generations-2 and -3 tourmaline compositions are highly aluminous (range of average values of Altotal = 6.38–6.79 apfu), markedly Fe- and X□-rich (XMg = 0.00–0.20, X□= 0.28–0.40), and variably F- and WO-enriched (F = 0.07–0.57 apfu, WO = 0.00–0.31), but notably poorer in Ca and Ti (&amp;lt;0.01 apfu). The later-stage tourmaline is considered to have developed during the subsolidus hydrothermal conditions. External chemical contributions to tourmaline compositions from the country rocks appear to be minor to nonexistent. The X-site and W-site occupancies of the late-generation tourmaline implies subsolidus invasive alkaline, saline aqueous fluids with high Na but minimal Ca contents derived from the crystallizing leucogranites and related rocks across the solidus-to-subsolidus transition.

Comment on “190Pt-186Os geochronometer reveals open system behaviour of 190Pt-4He isotope system” by Luguet et al. (2019)

Comment on “190Pt-186Os geochronometer reveals open system behaviour of 190Pt-4He isotope system” by Luguet et al. (2019)