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Accurately determining the timing and mechanism of metallogenesis of ore deposits is essential for developing a robust genetic model for their exploration. In this paper, we analyze the formation conditions of cassiterite in five major deposits of southern Hunan Province, one of the most important tungsten-tin (W-Sn) provinces in South China, using a combination of cathodoluminescence imaging, in situ U-Pb geochronology, and trace-element concentration data. In situ cassiterite U-Pb geochronology constrains the main period of Sn mineralization to between 155.4 and 142.0 Ma, demonstrating a temporal and genetic relationship to silicic intrusive magmatism in the same area. Three stages of magmatic activity and metallogenic evolution are recognized: (1) Early Paleozoic and Triassic: the initial enrichment stage of tungsten and tin; (2) Jurassic: the metasomatic mineralization stage; and (3) Cretaceous: the magmatic-hydrothermal superposition stage. The cassiterite in these deposits takes four forms, i.e., quartz vein-type, greisen-skarn-type, greisen-type, and granite-type, representing a progression characterized by the increasing content and decreasing range of variation of high field strength elements (HFSEs), and reflecting a general increase in the degree of evolution of the associated granites. Rare earth element (REE) concentrations suggest that precipitation of cassiterite was insensitive to the redox state of the fluid and that precipitation of cassiterite in the southern Hunan Sn deposits did not require a high-fO2 environment. These findings provide new insights into tin mineralization processes and exploration strategies. [ABSTRACT FROM AUTHOR]

This study, along with our previous studies (Yuguchi et al. 2015, 2019a), reveals the hydrothermal alteration processes in a pluton, with a focus on the mass transfer between minerals and hydrothermal fluid. It also depicts the sequential variations in fluid chemistry as alteration progresses. Hydrothermal alteration of the Toki granite in Tono, Japan--the study area of this research--progressed through the successive processes of chloritization, plagioclase alteration, and precipitation of a carbonate. This paper describes the alteration processes of hornblende chloritization, K-feldspar chloritization, and the formation of fracture-filling chlorite through petrography and mineral chemistry. A set of singular value decomposition analyses was conducted to obtain reaction equations for the chloritization processes, which facilitates the quantitative assessment of mass transfer between the reactant and product minerals, and the inflow and outflow of components through the hydrothermal fluid. Several types of chloritization reactions (including biotite chloritization) can be characterized by their reaction with the inflow of Al3+, Fe2+, Mn2+, and Mg2+ and the outflow of H4SiO4, Ca2+, K+, and F-. The age and thermal conditions of hornblende chloritization (64-54 Ma and 330-190 °C), K-feldspar chloritization (68-53 Ma and 350-210 °C), and precipitation of fracture-filling chlorite (66 and 63 Ma, 340 and 320 °C) overlap with those of biotite chloritization (68-51 Ma and 350-180 °C). The chloritization reactions (this study and Yuguchi et al. 2015) and plagioclase alteration (Yuguchi et al. 2019a) represent sequential variations in fluid chemistry at temporal conditions from 68 to 51 Ma as the temperature decreased from 350 to 180 °C. As the alteration proceeds, the concentrations of aluminum, iron, manganese, and magnesium ions in the hydrothermal fluid decrease gradually, and those of calcium, hydrogen, and fluorine ions increase gradually. Hornblende chloritization is associated with formation of magnetite and ilmenite. The thermal conditions of the hydrothermal fluid yielding the formation of magnetite and ilmenite can be interpreted by the chemical characteristics of chlorite around their associated minerals. The formation temperature of magnetite was higher than that of ilmenite, implying a decrease in oxygen fugacity in the hydrothermal fluid with the decrease in temperature from 280-310 to 220-250 °C. [ABSTRACT FROM AUTHOR]

Understanding the formation of high-silica rhyolites (HSRs, SiO2 > 75 wt%) is critical to revealing the evolution of felsic magma systems and magma chamber processes. This paper addresses HSR petrogenesis by investigating an integrated data set of whole-rock geochemistry, geochronology, and mineral composition of the ~74 Ma Nuocang HSR (SiO2 = 74.5–79.3 wt%) from the Coqen region in southern Tibet. Cathodoluminescence (CL) images show that zircons from the Nuocang HSRs can be divided into two textural types: (1) those with dark-CL cores displaying resorption features and overgrown by light-CL rims, and (2) those comprising a single light-CL zone, without dark-CL cores. In situ single-spot data and scanning images demonstrate that these two types of zircon have similar U-Pb ages (~74 Ma) and Hf isotopic compositions [εHf(t) = –9.09 to –5.39], indicating they were generated by the same magmatic system. However, they have different abundances of trace elements and trace element ratios. The dark-CL cores are likely crystallized from a highly evolved magma as indicated by their higher U, Th, Hf, Y, and heavy rare earth elements concentrations, lower Sm/Yb ratio, and more negative Eu anomalies. In contrast, the uniformly light-CL zircons and the light-CL rims are likely crystallized from less evolved and hotter magma, as indicated by their lower U-Th-REE abundances and higher Ti-in-zircon temperatures. This is consistent with the Ti-in-quartz geother-mometer in quartz phenocrysts that reveals that the light-CL zones are hotter than dark-CL cores. We propose that the composition and temperature differences between cores and rims of zircons and quartz record a recharge and reheating event during the formation of the Nuocang HSRs. This implies that HSR is a result of mixing between a hotter, less evolved silicic magma and a cooler, highly evolved, and crystal-rich mush. This study shows that zircon and quartz with distinct internal textures can be combined to disentangle the multi-stage evolution of magma reservoirs, providing critical insights into the origin of HSRs. [ABSTRACT FROM AUTHOR]

Accessory minerals like zircon, rutile and monazite are routinely studied to inform about the timing and nature of geological processes. These studies are underpinned by our understanding of the transfer processes of trace elements and the assumption that the isotopic systems remain undisturbed. However, the presence of microstructures or Pb-bearing phases in minerals can lead to the alteration of the Pb isotopic composition. To gain insight into the relationship between Pb isotopic alterations from inclusions and microstructures, this study focused on inclusions from an ultra-high-temperature metamorphic rutile. The studied inclusions are submicrometer monazites, a common mineral rich in Pb but normally not present in rutile. The sample is sourced from Mt. Hardy, Napier Complex, East Antarctica, an ultra-high-temperature (UHT) metamorphic terrane. By applying correlative analytical techniques, including electron backscatter diffraction mapping, transmission electron microscopy (TEM), and atom probe tomography, it is shown that monazite inclusions are often in contact with low-angle boundaries and yield no preferred orientation. TEM analysis shows the monazite core has a mottled texture due to the presence of radiation damage and nanoclusters associated with the radiation damage defects that are rich in U, Pb, and Ca. Some monazites exhibit a core-rim structure. The rim yields clusters composed of Ca- and Li-phosphate that enclose Pb nanoclusters that are only present in small amounts compared to the core, with Pb likely diffused into the rutile-monazite interface. These textures are the result of two stages of Pb mobility. Initial Pb segregation was driven by volume diffusion during UHT metamorphism (2500 Ma). The second stage is a stress-induced recrystallization during exhumation, leading to recrystallization of the monazite rim and trace element transport. The isotopic signature of Pb trapped within the rutile-monazite interface constrains the timing of Pb mobility to ca. 550 Ma. [ABSTRACT FROM AUTHOR]

The source of sulfuric acid and associated aqueous alteration of ancient martian sedimentary rocks remain under debate in the context of divergent models of jarosite formation. Here, we report the formation of sulfates, including jarosite in K-bentonites within shallow-water facies of the Permian-Triassic (P-T) transition at Xiakou in South China. In these strata, jarosite is dispersed in the clay matrix or forms aggregates in pore spaces, has a euhedral morphology, and coexists with variably 34S-depleted paragenetic gypsum and bassanite (δ34S = –37.23‰ to +3.20‰ VCDT). Subaqueous alteration of volcanic tuffs concurrently with oxidation of upwelled, biogenically sourced H2S is the process of jarosite formation in the Xiakou K-bentonites. This mechanism of jarosite precipitation and stability over geological time challenges the long-held view of acidic, water-limited conditions leading to iron(III) sulfate precipitation and would be consistent with possible microbial or nanobial life on early Mars. [ABSTRACT FROM AUTHOR]

The timing of partial melting in high-grade metamorphic rocks is critical for constraining tectonic histories and processes. However, uncertainties exist about the behavior of monazite and zircon during partial melting, especially about the timing of crystallization with respect to melting reactions. This study is focused on a single sample (16TG143) of finely layered, migmatitic gneiss from the Adirondack Highlands, New York, interpreted to have undergone extensive biotite dehydration melting (i.e., Bt + Pl + Als + Qz = Grt + Kfs + melt). The rock contains one distinct leucosome layer. The non-leucosome (gray gneiss) portion of the migmatite has millimeter-scale sublayers with distinct differences in modes and mineralogy. The layers are interpreted to reflect the differential preservation of reactants and products formed during the forward and reverse progress of the melting reaction. Monazite and zircon modes, and to some degree, texture, composition, and geochronology all vary from layer to layer. Both minerals have up to three domains: ca. 1150 Ma anhedral cores, ca. 1050 Ma monazite mantles/fir tree textured zircon, and ca. 1030 Ma rims. The heterogeneous layered gray gneiss provides robust constraints on the timing of melting (ca. 1050 Ottawan orogenesis), melt crystallization, and post-melting retrogression, in addition to information about earlier metamorphic events. Early-formed monazite and zircon grains were largely dissolved during progressive melting, except where preserved as relicts or inclusions. Monazite mantles and fir tree zircon grains precipitated upon cooling during progressive melt crystallization between temperatures of 800 and 750 °C. Rims are interpreted to have precipitated during subsolidus, solid-state retrogression after ca. 1050 Ma. Correlations between the gneissic layering, melting reactions, and the character of geochronometers emphasize the importance of characterizing the layer-forming and chronometer petrogenesis processes as a critical part of deconvoluting the history of migmatitic gneisses. [ABSTRACT FROM AUTHOR]

The mineral zircon is used widely to constrain the age of rocks and the processes that formed them. Although zircon is robust to a range of physical and chemical processes, it may show evidence for rapid re-equilibration that is generally considered to reflect interaction with hydrous fluids. Here, we show that zircon grains that crystallized from melt produced during the catastrophic meltdown of the Chernobyl nuclear reactor exhibit re-equilibration textures that occurred in an environment without free water. The process of re-equilibration involved a melt-mediated interface-coupled dissolutionreprecipitation that took place over a few days to produce textures that are commonly observed in igneous and anatectic systems. Thus, the composition of zircon can be modified even in the absence of hydrous fluids in a short time frame. Through this process, zircon crystals may track the timing of the last silicate melt they interacted with. [ABSTRACT FROM AUTHOR]

Numerous skarn-type Sn deposits have been identified in the Nanling Range (South China), of which the Shizhuyuan W-Sn-Bi-Mo, Xianghualing Sn, Jinchuantang Sn-Bi, and Hehuaping Sn deposits are the largest. The Xianghualing deposit, which is the focus of this study, hosts a resource of 0.17 Mt Sn grading 0.93–1.39 wt% SnO2. Whether the distal skarn-type mineralization and the cassiteritesulfide vein-type orebody in the Xianghualing district are genetically related to the Laiziling granitic pluton, which produced the proximal skarn-type Sn mineralization, however, is still unknown. The Xianghualing Sn mineralization occurs exclusively as cassiterite and has been subdivided into four ore-types: (1) lenticular proximal skarn ore (Cst I) containing the mineral assemblage cassiteritepyrrhotite-chalcopyrite-actinolite-wollastonite; (2) layered distal skarn ore (Cst II) containing the mineral assemblage cassiterite-pyrrhotite-chalcopyrite-actinolite; (3) vein cassiterite-sulfide ore (Cst III) distal from the skarn and associated granite containing the mineral assemblage cassiterite-arsenopyrite-pyrrhotite-muscovite-fluorite; and (4) veinlet Sn-Pb-Zn ore (Cst IV) distal from the skarn and associated granite containing the mineral assemblage cassiterite-galena-sphalerite-topaz-quartz. Here, we report the results of in situ laser ablation inductively coupled plasma mass spectrometric (LA-ICP-MS) U-Pb age determinations for garnet from the Xianghualing skarn and the above four types of cassiterite. Our age determinations indicate that there were two independent magmatic-hydrothermal events at ~160 and 156~150 Ma, both of which led to Sn mineralization. The first Sn mineralization event at ~160 Ma (Cst IV U-Pb ages of 159.6 ± 1.4 to 158.5 ± 0.8 Ma) is interpreted to have been associated with a speculative unexposed granitic pluton, which is coeval with the nearby Jianfengling granite intrusion. The second Sn mineralization event at 156~150 Ma (Cst I to Cst III U-Pb ages of 155.9 ± 0.7 to 152.3 ± 1.1 Ma and garnet U-Pb ages of 153.6 ± 7.6 to 151.5 ± 3.5 Ma) is genetically related to the adjacent Laiziling granitic intrusion (152.8 ± 1.2 Ma, zircon U-Pb age). This event was responsible for the bulk of the Sn resource (>95%). Our age determinations provide convincing evidence for superimposed Jurassic Sn mineralizing systems at Xianghualing. They also show the value of combining garnet and cassiterite U-Pb age determinations to constrain the timing of skarn and Sn mineralization and distinguish discrete Sn mineralizing events in a protracted metallogenic history. [ABSTRACT FROM AUTHOR]

A comparison of hydrothermal monazite and rutile geochronology in the gold deposits Monazite and rutile are common accessory minerals in different types of gold deposits, and their U-Pb isotopes are often used to determine the ore formation ages of gold mineralization ([8]; [53]; [48]). Recent researchers have elaborated on the chronology and genesis of ore-hosting granites, ore deposit geology, structural characteristics, gold mineralization ages, fluid inclusions, and H-O-S-Pb isotopes of the Katbasu gold-copper deposit ([19]; [24]; [79]; [15]; [40]; [80]). Keywords: Hydrothermal monazite; rutile; geochronology; Katbasu Au-Cu deposit; Western Tianshan EN Hydrothermal monazite rutile geochronology Katbasu Au-Cu deposit Western Tianshan 1201 1215 15 06/01/22 20220601 NES 220601 Introduction The formation ages of ore deposits are critical for understanding their genesis and making exploration strategies. As a newly discovered large Au-Cu deposit in the western Tianshan, the genetic type of the Katbasu deposit remains controversial, with some researchers relating them to orogenic gold deposits ([79]; [80]) and others interpreting them as magmatic-hydrothermal gold deposits ([15]; [40]). [Extracted from the article]

Pyrite trace element (TE) chemistry is now widely employed in studies of past ocean chemistry. Thus far the main proof of concept has been correlation between large data sets of pyrite and bulk analyses emphasizing redox sensitive TE data from ancient samples spanning geologic time. In contrast, pyrite TE data from modern settings are very limited. The sparse available data are averages from samples from the Cariaco Basin without stratigraphic resolution and from estuarine sediments. To fill this gap, we present TE data (Co, Ni, Cu, Zn, Mo, Ag, Pb, Bi) from the two largest euxinic basins on Earth today, locations where the majority of the pyrite formed within the water column, the Black Sea and Cariaco Basin. These locations have different water column TE contents due to their relative degrees of restriction from the open ocean, thus providing an ideal test of the relationship between pyrite precipitated under euxinic conditions from basins with different degrees of basin restriction and dissolved TE concentration. At each site we observed that down-core trends for pyrite increase before reaching relatively steady values for most TE. This observation suggests that instead of all the TE being sourced directly from the water column, some are incorporated from the sediments, presumably desorbing from detrital materials. However, since much of the adsorbed TE is adsorbed from the overlying water, the pyrite chemistry still seems to reflect the water chemistry at or near the surface. Indeed, for Mo, there is less variation in pyrite than in bulk sediment. Additionally, we found that pyrite formed during diagenesis due to sulfide difusion into iron-rich muds revealed low-TE contents, except for siderophile elements likely to have been adsorbed onto Fe (hydr)oxides, highlighting the risk of potential false negatives from pyrite formed under these conditions. This relationship highlights the need for detailed understanding of the full context, including the use of complementary geochemical data such as sulfur isotope trends, in eforts to use pyrite TE to interpret conditions in the global ocean. [ABSTRACT FROM AUTHOR]

Diamonds have long been mined from alluvial terrace deposits within the rainforest of Guyana, South America. No primary kimberlite deposits have been discovered in Guyana, nor have there been previous studies on the mineralogy and origin of the diamonds. Paleoproterozoic terranes in Guyana are prospective to diamond occurrences because the most productive deposits are associated spatially with the eastern escarpment of the Paleoproterozoic Roraima Supergroup. Geographic proximity suggests that the diamonds are detrital grains eroding from the <1.98 Ga conglomerates, metamorphosed to zeolite and greenschist facies. The provenance and paragenesis of the alluvial diamonds are described using a suite of placer diamonds from different locations across the Guiana Shield. Guyanese diamonds are typically small, and those in our collection range from 0.3 to 2.7 mm in diameter; octahedral and dodecahedral, with lesser cubic and minor macle forms. The diamonds are further subdivided into those with abraded and non-abraded surfaces. Abraded diamonds show various colors in cathodoluminescence, whereas most non-abraded diamonds appear blue. In all populations, diamonds are predominantly colorless, with lesser brown to yellow and very rare white. Diamonds are predominantly Type IaAB and preserve moderate nitrogen aggregation and total nitrogen concentrations ranging from trace to ~1971 ppm. The kinetics of nitrogen aggregation indicate mantle-derived residence temperatures of 1124 ± 100 °C, assuming residence times of 1.3 and 2.6 Ga for abraded and non-abraded diamonds, respectively. The diamonds are largely sourced from the peridotitic to eclogitic lithospheric upper mantle based on both δ13C values of –5.82 ± 2.45‰ (VPDB-LSVEC) and inclusion suites predominantly comprised of forsterite, enstatite, Cr-pyrope, chromite, rutile, clinopyroxene, coesite, and almandine garnet. Detrital, accessory minerals are non-kimberlitic. Detrital zircon geochronology indicates diamondiferous deposits are predominantly sourced from Paleoproterozoic rocks of 2079 ± 88 Ma. [ABSTRACT FROM AUTHOR]

Initial excess protactinium (231Pa) is a frequently suspected source of discordance in baddeleyite (ZrO2) geochronology, which limits accurate U/Pb dating, but such excesses have never been directly demonstrated. In this study, Pa incorporation in late Holocene baddeleyite from Somma-Vesuvius (Campanian Volcanic Province, central Italy) and Laacher See (East Eifel Volcanic Field, western Germany) was quantified by U-Th-Pa measurements using a large-geometry ion microprobe. Bad-deleyite crystals isolated from subvolcanic syenites have average U concentrations of ~200 ppm and are largely stoichiometric with minor abundances of Nb, Hf, Ti, and Fe up to a few weight percent. Measured (231Pa)/(235U) activity ratios are significantly above the secular equilibrium value of unity and range from 3.4(8) to 14.9(2.6) in Vesuvius baddeleyite and from 3.6(9) to 8.9(1.4) in Laacher See baddeleyite (values within parentheses represent uncertainties in the last significant figures reported as 1σ throughout the text). Crystallization ages of 5.12(56) ka (Vesuvius; MSWD = 0.96, n = 12) and 15.6(2.0) ka (Laacher See; MSWD = 0.91, n = 10) were obtained from (230Th)/(238U) disequilibria for the same crystals, which are close to the respective eruption ages. Applying a corresponding age correction indicates average initial (231Pa)/(235U)0 of 8.8(1.0) (Vesuvius) and 7.9(5) (Laacher See). For reasonable melt activities, model baddeleyite-melt distribution coefficients of DPa/DU = 5.8(2) and 4.1(2) are obtained for Vesuvius and Laacher See, respectively. Speciation-dependent (Pa4+ vs. Pa5+) partitioning coefficients (D values) from crystal lattice strain models for tetra- and pentavalent proxy ions significantly exceed DPa/DU inferred from direct analysis of 231Pa for Pa5+. This is consistent with predominantly reduced Pa4+ in the melt, for which D values similar to U4+ are expected. Contrary to common assumptions, baddeleyite-crystallizing melts from Vesuvius and Laacher See appear to be dominated by Pa4+ rather than Pa5+. An initial disequilibrium correction for baddeleyite geochronology using DPa/DU = 5 ± 1 is recommended for oxidized phonolitic melt compositions. [ABSTRACT FROM AUTHOR]

Migmatites are common in the hinterland of orogenic belts. The timing and mechanism (in situ vs. external, P-T conditions, reactions, etc.) of melting are important for understanding crustal rheology, tectonic history, and orogenic processes. The Adirondack Highlands has been used as an analog for mid/deep crustal continental collisional tectonism. Migmatites are abundant, and previous workers have interpreted melting during several different events, but questions remain about the timing, tectonic setting, and even the number of melting events. We use multiscale compositional mapping combined with in situ geochronology and geochemistry of monazite to constrain the nature, timing, and character of melting reaction(s) in one locality from the eastern Adirondack Highlands. Three gray migmatitic gneisses, studied here, come from close proximity and are very similar in microscopic and macroscopic (outcrop) appearance. Each of the rocks is interpreted to have undergone biotite dehydration melting (i.e., Bt + Pl + Als + Qz = Grt + Kfs + melt). Full-section compositional maps show the location of reactants and products of the melting reaction, especially prograde and retrograde biotite, peritectic K-feldspar, and leucosome, in addition to all monazite and zircon in context. In addition, the maps provide constraints on kinematics during melting and a context for interpretation of accessory phase composition and geochronology. More so than zircon, monazite serves as a monitor of melting and melt loss. The growth of garnet during melting leaves monazite depleted in Y and HREEs while melt loss from the system leaves monazite depleted in U. Results show that in all three localities, partial melting occurred during at ca. 1160–1150 Ma (Shawinigan orogeny), but the samples show high variability in the location and degree of removal of the melt phase, from near complete to segregated into layers to dispersed. All three localities experienced a second high-T event at ca. 1050 Ma, but only the third (non-segregated) sample experienced further melting. Thus, in addition to bulk composition, the fertility for melting is an important function of the previous history and the degree of mobility of earlier melt and fluids. Monazite is also a sensitive monitor of retrogression; garnet breakdown leads to increased Y and HREE in monazite. Results here suggest that all three samples remained at depth between the two melting events but were rapidly exhumed after the second event. [ABSTRACT FROM AUTHOR]

Subduction is a component of plate tectonics, which is widely accepted as having operated in a manner similar to the present-day back through the Phanerozoic Eon. However, whether Earth always had plate tectonics or, if not, when and how a globally linked network of narrow plate boundaries emerged are matters of ongoing debate. Earth's mantle may have been as much as 200-300 °C warmer in the Mesoarchean compared to the present day, which potentially required an alternative tectonic regime during part or all of the Archean Eon. Here we use a data set of the pressure (P), temperature (T), and age of metamorphic rocks from 564 localities that vary in age from the Paleoarchean to the Cenozoic to evaluate the petrogenesis and secular change of metamorphic rocks associated with subduction and collisional orogenesis at convergent plate boundaries. Based on the thermobaric ratio (T/P), metamorphic rocks are classified into three natural groups: high T/P type (T/P > 775 °C/GPa, mean T/P ~1105 °C/GPa), intermediate T/P type (T/P between 775 and 375 °C/GPa, mean T/P ~575 °C/GPa), and low T/P type (T/P < 375 °C/GPa, mean T/P ~255 °C/GPa). With reference to published thermal models of active subduction, we show that low T/P oceanic metamorphic rocks preserving peak pressures >2.5 GPa equilibrated at P-T conditions similar to those modeled for the uppermost oceanic crust in a wide range of active subduction environments. By contrast, those that have peak pressures <2.2 GPa may require exhumation under relatively warm conditions, which may indicate subduction of young oceanic lithosphere or exhumation during the initial stages of subduction. However, low T/P oceanic metamorphic rocks with peak pressures of 2.5-2.2 GPa were exhumed from depths where, in models of active subduction, the slab and overriding plate change from being decoupled (at lower P) to coupled (at higher P), possibly suggesting a causal relationship. In relation to secular change, the widespread appearance of low T/P metamorphism in the Neoproterozoic represents a "modern" style of cold collision and deep slab breakoff, whereas rare occurrences of low T/P metamorphism in the Paleoproterozoic may reveal atypical localized regions of cold collision. Low T/P metamorphism is not known from the Archean geological record, but the absence of blueschists in particular is unlikely to reflect secular change in the composition of the oceanic crust. In addition, the premise that the formation of lawsonite requires abnormally low thermal gradients and the postulate that oceanic subduction-related rocks register significantly lower maximum pressures than do continental subduction-related rocks, and imply different mechanisms of exhumation, are not supported. The widespread appearance of intermediate T/P and high T/P metamorphism at the beginning of the Neoarchean, and the subsequent development of a clear bimodality in tectono-thermal environments are interpreted to be evidence of the stabilization of subduction during a transition to a globally linked network of narrow plate boundaries and the emergence of plate tectonics. [ABSTRACT FROM AUTHOR]

As the only known mineral with confirmed ages >4 Ga, zircon is unmatched in the field of early Earth research. In the past two decades, researchers have continued to establish connections between zircon chemistry and the physical/chemical processes that shaped the early crust. This connection has benefited greatly from the application of high-temperature and high-pressure laboratory experiments. This study presents: (1) new zircon U-Pb geochronology and strategies for characterizing and identifying ancient terrestrial material from the Inukjuak Domain in northern Québec, and the Jack Hills, Western Australia; and (2) a blend of new laboratory experiments and measurements of isotope ratios and trace impurities of natural zircon. Research directions in need of future exploration, with emphasis on early Earth studies, are also explored. Topics include Hadean hydrous magmatism and the structural accommodation of “water” into the zircon lattice, Hadean subaerial crust and the identification of peraluminous or metaluminous source melts, methods to characterize the oxidation state of magmas and fluids, and the complementarity of the Si- and O-isotopic systems as proxies for crustal weathering. Finally, the implications of this work are discussed in the context of a possible transition from prebiotic to biotic chemistry on the early Earth. [ABSTRACT FROM AUTHOR]

Observations of discordant ages, meaning that an age given by one mineral geochronometer is different from the age given by another geochronometer from the same rock, began in the early days of geochronology. In the late 1950s and 1960s, discordant U-Pb zircon ages were unquestioningly attributed to Pb diffusion at high temperature. Later, the mineralogical properties and the petrogenesis of the zircon crystals being dated was recognized as a key factor in obtaining concordant U-Pb ages. Advances in analytical methods allowed the analysis of smaller and smaller zircon multigrain fractions, then the analysis of individual grains, and even pieces of grains, with higher degrees of concordancy. Further advances allowed a higher analytical precision, a clearer perception of accuracy, and a better statistical resolution of age discordance. As for understanding the cause(s) of discordance, belief revision followed the coupling of imaging, cathodoluminescence (CL), and backscattered electrons (BSE), to in situ dating by secondary ion mass spectrometry (SIMS) or by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Discordant zircon and other accessory minerals (e.g., monazite, apatite, etc.) often consist of young rims accreted onto/into older cores. Age gradients are sharp, and no Pb diffusion gradients are observed. As U-Pb discordance in crystalline, non-radiation damaged grains is caused by diachronous, heterochemical mineral generations, interpretations of mineral ages, based on the exclusive role of diffusion, are superseded, and closure temperatures of zircon and monazite are irrelevant in geological reality. Other isotopic systems (Rb-Sr, K-Ar) were believed, since the 1960s, to be similarly controlled by the diffusivity of radiogenic daughters. When zircon and monazite discordance were recognized as zone accretion/reaction with sharp boundaries that showed little or no high-temperature diffusive re-equilibration, the other chronometric systems were left behind, and interpretations of mineral ages based on the exclusive role of diffusion survived. The evidence from textural-petrologic imaging (CL, BSE) and element mapping by electron probe microanalyzer (EPMA) or high spatial resolution SIMS or LA-ICP-MS provides the decisive constraints. All microcline and mica geochronometers that have been characterized in detail document patchy textures and evidence for mineral replacement reactions. It is important not to confuse causes and effects; heterochemical microstructures are not the cause of Ar and Sr loss; rather, they follow it. Ar and Sr loss by dissolution of the older mineral generation occurs first, heterochemical textures form later, when the replacive assemblage recrystallizes. Heterochemical mineral generations are identified and dated by their Ca/Cl/K systematics in 39Ar-40Ar. Replacive reactions adding or removing Cl, such as, e.g., sericite overgrowths on K-feldspar, retrograde muscovite intergrowths with phengite, etc. are detected by Cl/K vs. Ar/K isotope correlation diagrams. Ca-poor reaction products, such as, e.g., young biotite intergrown with older amphibole, adularia replacing microcline, etc., can be easily identified by Ca/K vs. Ar/K diagrams supported by EPMA analyses. Mixed mineral generations are observed to be the cause of discordant, staircase-shaped age spectra, while step-heating of crystals with age gradients produces concordant plateaus. Age gradients are therefore unrelated to staircase age spectra. There is a profound analogy between the U-Pb, Rb-Sr, and K-Ar systems. Pb and Ar diffusion rates are both much slower than mineral replacement rates for all T < 750 °C. Patchy retrogression textures are always associated with heterochemical signatures (U/Th ratios, REE patterns, Ca/Cl/K ratios). As a rule, single-generation minerals with low amounts of radiation damage give concordant ages, whereas discordance is caused by mixtures of heterochemical, resolvably diachronous, mineral generations in petrologic disequilibrium. This can also include (sub-)grains that have accumulated significant amounts of radiation damage. For accurate geochronology the petrologic characterization with the appropriate technique(s) of the minerals to be dated, and the petrologic context at large, are as essential as the mass spectrometric analyses. [ABSTRACT FROM AUTHOR]

The field of mineral evolution--a merger of mineralogy and Earth history--coalesced in 2008 with the first of several global syntheses by Robert Hazen and coworkers in the American Mineralogist. They showed that the cumulative abundance of mineral species has a stepwise trend with first appearances tied to various transitions in Earth history such as the end of planetary accretion at ca. 4.55 Ga and the onset of bio-mediated mineralogy at ca. >2.5 Ga. A global age distribution is best established for zircon. Observed abundance of zircon fluctuates through more than an order of magnitude during successive supercontinent cycles. The pulse of the Earth is also recorded, albeit imperfectly, by the 87Sr/86Sr composition of marine biogenic calcite; the Sr-isotopic ratio of this mineral reflects the balance of inputs of primitive strontium at mid-ocean ridges and evolved strontium that drains off the continents. A global mineral evolution database, currently in the works, will greatly facilitate the compilation and analysis of extant data and the expansion of research in mineralogy outside its traditional bounds and into more interdisciplinary realms. [ABSTRACT FROM AUTHOR]

The central Appalachian Piedmont lies in the critical juncture between the northern and southern Appalachians, portions of the orogen with distinct middle to late Paleozoic accretionary histories. Orogen-scale compilation maps link the central and southern Appalachians, but until recently, limited geochronological data prevented robust tectonic comparisons between high-grade metamorphic rocks in different parts of the orogen. We report the results of in situ U-Th-total Pb monazite geochronology that date significant deformation and metamorphism as middle Silurian (~425 Ma) through middle Devonian (~385 Ma) and demonstrate the diachronous nature of orogen development. The Rosemont Shear Zone is identified as a major tectonic boundary in southeastern Pennsylvania and northern Delaware separating the rifted Laurentian margin from younger rock units that formed in a magmatic arc setting. The Laurentian margin rocks occur in a series of nappes in which the metamorphic grade decreases from the structurally highest nappe to the lowest. The in situ monazite ages show that maximum temperature in the lowest nappe may have been attained some 15 million years after maximum temperature in the highest nappe. We interpret this to be the result of successive nappe emplacement, with the warmer overriding sheets contributing heat to lower levels. Combining geochronologic and thermobarometric results with the geometry of deformation results in a new picture of the tectonic development of the central Appalachian Piedmont that further links the evolution of the southern and northern Appalachians. For the Laurentian margin rocks, tectonism resulted from the approach and collision of peri-Gondwanan terranes during the Silurian to early Devonian in a dominantly sinistral, transpressive tectonic regime. This portion of the Pennsylvania-Delaware Piedmont inboard of the Rosemont Shear Zone is contiguous with comparable rocks in the southern Appalachians. In contrast, arc-related rock units outboard of the Rosemont Shear Zone experienced primarily thermal metamorphism in the Silurian, while crustal thickening and associated regional metamorphism is middle Devonian in age and likely the result of the accretion of Avalonia during the Acadian orogeny. These arc-related and younger rocks probably originated to the north of their present location as part of the northern Appalachians. They were ultimately emplaced in a right-lateral transcurrent regime sometime after the middle Devonian. Thus, it is in this portion of the central Appalachian Piedmont that the northern and southern Appalachians are joined. [ABSTRACT FROM AUTHOR]

To constrain the origin of komatiites from the Barberton Greenstone Belt, South Africa, we measured 147Sm-143Nd and 176Lu-176Hf compositions for 18 komatiites from core obtained during the International Continental Drilling Program in the Komati Formation of the Barberton Belt, as well as 33 komatiites from surface outcrops of the Komati, Hooggenoeg, and Weltevreden Formations, these latter for purposes of comparison between core and surface samples. Magmatic clinopyroxene from surface samples near the drill site was also analyzed. For the Lu-Hf isotope system, the Komati Formation core and surface samples including the clinopyroxene define a linear array whose slope corresponds to an age of 3426 ± 16 Ma (MSWD = 118; εHf(T) = +2.2), which is slightly younger than the accepted age of the rocks (3.48 Ga). The Sm-Nd isotope data for the same set of samples likewise fall along a linear array also yielding a younger age of 3339 ± 12 Ma (MSWD = 42; εNd(T) = +2.8). The high MSWD for both isotope systems indicate substantial scatter at variance with normal magmatic processes, likely implying element mobility disturbing even these relatively robust isotopic systems shortly after eruption of the lavas. The average initial εNd and εHf of the core samples at 3.48 Ga are +0.45 and +1.4, respectively, in overall accordance with the positive errorchron intercepts and a depleted mantle source at 3.5 Ga. In contrast, the clinopyroxene and their host rocks have strongly positive εHf(T) of about +5 and negative εNd(T) of about -2. Given the overall scatter of the whole-rock data, the most robust constraint on the composition of the komatiite source comes from the clinopyroxene. Their positive εHf(T) is in line with, though somewhat higher than other results from komatiites from the Komati Formation, but their negative εNd(T) is unexpected in that it indicates a source with long-term low Sm/Nd, which is at odds with its long-term high Lu/Hf. This signature is also found in the trace element compositions of some of the komatiites, such as moderately enriched LREE, negative Hf anomalies, and low Hf/Sm ratios. The origin of these features is uncertain but one possibility is that the discordance between the Hf and Nd isotope systems reflects the presence of deep-sea sediments in the source of some of the Barberton komatiites. The possible presence of a surface component in an ancient deep mantle source has wide-ranging implications for mantle-crust interaction and dynamics in the early Earth and for constraining a minimum age for the onset of plate tectonics. [ABSTRACT FROM AUTHOR]

Baddeleyite is a frequently found accessory mineral in silica undersaturated lavas. Because it is typically enriched in uranium, while having low initial lead, baddeleyite has long been a prime target for U-Pb geochronology of mafic rocks. The difficulties in retrieving small baddeleyite grains from volcanic samples and the lack of a detailed understanding of baddeleyite occurrence, however, have limited baddeleyite chronology largely to coarse-grained mafic intrusive rocks. Here, the development of U-Th in situ baddeleyite analysis using secondary ionization mass spectrometry (SIMS) is presented together with an assessment of baddeleyite occurrence in Quaternary silica-undersaturated lavas from Campi Flegrei (Naples, Italy). Samples studied comprise the pre- and post Campanian Ignimbrite (ca. 40 ka) lava domes of Cuma and Punta Marmolite, and Astroni and Accademia, respectively. The in situ sample preparation required initial identification of baddeleyite crystals from sawed and polished rock billets using scanning electron microscope (SEM) backscatter imaging and energy-dispersive X-ray analysis. U-Th baddeleyite isochron ages for intra-caldera Astroni and Accademia lava domes are 5.01+2.61-2.55 ka (MSWD = 2.0; n = 17) and 4.36+1.13-1.12 ka (MSWD = 2.9; n = 24), respectively. The ages for Punta Marmolite (62.4+3.9-3.8 ka; MSWD = 1.2; n = 11) and Cuma (45.9+3.6-3.5 ka; MSWD = 2.2; n = 11) predate the Campanian Ignimbrite. Rapid baddeleyite crystallization at the time of emplacement is supported by petrologic observations that >50% of the baddeleyite crystals documented in this study occur either in vesicles or in vesicle-rich regions of the host lavas whose textures developed over timescales of a few years to a few decades based on microlite crystal size distribution (CSD) analysis. Radiometric U-Th baddeleyite ages are mostly in agreement with previously determined K-Ar eruption ages, except for the Punta Marmolite lava dome whose U-Th baddeleyite age predates the K-Ar age by ca. 15 ka. Baddeleyite thus records eruptive emplacement with little evidence for significant pre-eruptive crystal residence, and has potential as an eruption chronometer for Quaternary silica-undersaturated volcanic rocks. [ABSTRACT FROM AUTHOR]

Atom-probe tomography (APT) and secondary ion mass spectrometry (SIMS) provide complementary in situ element and isotope data in minerals such as zircon. SIMS measures isotope ratios and trace elements from 1-20 µm spots with excellent accuracy and precision. APT identifies mass/ charge and three-dimensional position of individual atoms (±0.3 nm) in 100 nm-scale samples, volumes up to one million times smaller than SIMS. APT data provide unique information for understanding element and isotope distribution; crystallization and thermal history; and mechanisms of mineral reaction and exchange. This atomistic view enables evaluation of the fidelity of geochemical data for zircon because it provides new understanding of radiation damage, and can test for intracrystalline element mobility. Nano-geochronology is one application of APT in which Pb isotope ratios from sub-micrometer domains of zircon provide model ages of crystallization and identify later magmatic and metamorphic reheating. Based on SEM imaging and SIMS analysis, 11 needle-shaped specimens ~100 nm in diameter were sampled from one Archean and two Hadean zircons by focused ion-beam milling and analyzed with APT. The three-dimensional distribution of Pb and nominally incompatible elements (Y, REEs) differs at the atomic scale in each zircon. Zircon JH4.0 (4.007 Ga, Jack Hills, Western Australia) is homogeneous in Pb, Y, and REEs. In contrast, Pb and Y and REEs are clustered in sub-equant ~10 nm diameter domains, spaced 10-40 nm apart in zircons ARG2.5 (2.542 Ga, Grouse Creek Mountains, Utah) and JH4.4 (4.374 Ga, Jack Hills). Most clusters are flattened parallel to (100) or (010). U and Th are not collocated with Pb in clusters and appear to be homogeneously distributed in all three zircons. The analyzed domains experienced 4 to 8 x 1015 α-decay events/mg due to U and Th decay and yet all zircons yield U-Pb ages by SIMS that are better than 97% concordant, consistent with annealing of most radiation damage. The 207Pb/206Pb ratios for the 100 nm-scale specimens measured by APT average 0.17 for ARG2.5, 0.42 for the JH4.0, and 0.52 for JH4.4. These ratios are less precise (±10-18% 2σ) due to the ultra-small sample size, but in excellent agreement with values measured by SIMS (0.1684, 0.4269, and 0.5472, respectively) and the crystallization ages of the zircons. Thus Pb in these clusters is radiogenic, but unsupported, meaning that the Pb is not spatially associated with its parent isotopes of U and Th. For the domain outside of clusters in JH4.4, the 207Pb/206Pb ratio is 0.3, consistent with the SIMS value of 0.2867 for the zircon overgrowth rim and an age of 3.4 Ga. In ARG2.5, all Pb is concentrated in clusters and there is no detectable Pb remaining outside of the clusters. The Pb-Y-REE-rich clusters and lack of correlation with U in ARG2.5 and JH4.4 are best explained by diffusion of Pb and other elements into ~10 nm amorphous domains formed by α-recoil. Diffusion distances of ~20 nm for these elements in crystalline zircon are consistent with heating at temperatures of 800 °C for ~2 m.y. Such later reheating events are identified and dated by APT from 207Pb/206Pb model ages of clusters in JH4.4 and by the absence of detectable Pb outside of clusters in ARG2.5. SIMS dates for the zircon rims independently confirm reheating of ARG2.5 and JH4.4, which were xenocrysts in younger magmas when rims formed. It is proposed that most domains damaged by α-recoil were annealed at ambient temperatures above 200-300 °C before reheating and only a small number of domains were amorphous and available to concentrate Pb at the time of reheating. The size, shapes, and orientations of clusters were altered by annealing after formation. The absence of enriched clusters in JH4.0 shows that this zircon was not similarly reheated. Thus APT data provide thermochronologic information about crustal reworking even for zircons where no overgrowth is recognized. The clusters in JH4.4 document Pb mobility at the sub-50 nm scale, but show that the much larger 20 µm-scale domains analyzed by SIMS were closed systems. The reliability of oxygen isotope ratios and other geochemical data from zircon can be evaluated by these means. These results verify the age of this zircon and support previous proposals that differentiated crust existed by 4.4 Ga and that the surface of Earth was relatively cool with habitable oceans before 4.3 Ga. These analytical techniques are of general applicability to minerals of all ages and open many new research opportunities. [ABSTRACT FROM AUTHOR]

Subduction of rocks into the mantle results in high-pressure metamorphism and the formation of eclogites from basaltic precursor rocks. In general, many kilometers of oceanic lithosphere are ultimately consumed prior to the subsequent continental slab subduction and collision. The exposure of the eclogites derived from oceanic subduction and continental subduction at the surface of Earth today record provide different P-T-t records of the subduction process. The Huwan shear zone in the Hong'an orogenic belt, marking a former ocean-continent transition zone, has been the focus of many studies on subduction-related high-pressure metamorphism. In this study, Lu-Hf garnet, U-Pb zircon, and Ar-Ar mica ages are combined with geochemical data to understand the origin of two coexisting eclogite bodies exposed along the Xuehe River in the Huwan Shear zone. In total, the results indicate that the two eclogites have different protoliths but experienced a similar metamorphic history. This observation requires new tectonic model for the coupled subduction of oceanic and continental crust in subduction zones. Combined geochemistry and zircon U-Pb geochronology suggest distinct oceanic and continental affinities for the eclogite protoliths. The Lu-Hf dates of 261.5 ± 2.4 Ma of the continental-type eclogite and 262.7 ± 1.7 Ma of the oceanic-type eclogite reflect garnet growth and are interpreted to closely approximate the age of eclogite-facies metamorphism. Therefore, both the geochemically oceanic- and continental-type eclogites underwent the same episode of Permian eclogite-facies metamorphism. The Permian Lu-Hf ages of ca. 262 Ma and the obtained Triassic Ar-Ar ages (~240 Ma) of the oceanic-type and continental-type eclogites imply coupled subduction and exhumation of oceanic and continental crustal materials in the Hong'an orogenic belt during the Permian and the Triassic. Though limited, the geochemical and geochronological results of this study, together with the discrepant Carboniferous dates for the nearby eclogites of previous studies, apparently suggest that the Huwan shear zone was not always a single coherent unit but instead comprises different tectonic slices that were metamorphosed at different times before final assembly. Some slices of the oceanic and continental crust underwent two subduction cycles during the Carboniferous and the Permian, whereas some eclogites registered only a single subduction-exhumation loop during the convergence between the South China Block and the North China Block in the Huwan shear zone. The consistent ages of the oceanic- and continental-type eclogites disfavor the traditional mélange model that high-pressure rocks are dismembered fragments that have been assembled and intercalated with rocks devoid of any high-pressure history at shallow crustal levels, forming a tectonic mélange. [ABSTRACT FROM AUTHOR]

Analysis of radiation damage in natural mineral analogs such as zircon is important for the evaluation of the long-term behavior of nuclear waste forms and for geochronology. Here we present results of experiments to determine the partitioning of radiation damage due to the heavy nuclear recoil of uranium and thorium daughters and the a-particles ejected in an a-decay event in zircon. Synthetic polycrystalline zircon ceramics were doped with 10B and irradiated in a slow neutron flux for 1, 10, and 28 days to achieve the reaction 10B + n → 7Li + a (+2.79 MeV), creating an a event without a heavy nuclear recoil. The 7Li atoms produced in the nuclear reaction were directly detected by NMR "spin-counting", providing a precise measurement of the a-dose applied to each sample. The amount of damage (number fraction and volume fraction) created by each a-event (one a-event being a 7Li + a-particle) has been quantified using radiological nuclear magnetic resonance and X-ray diffraction data. The number of permanently displaced atoms in the amorphous fraction was determined by 29Si NMR to be 252 ± 24 atoms for the 10B(n,a) event when the heavy recoil is absent, which is broadly in agreement with ballistic Monte Carlo calculations. The unit-cell swelling of the crystalline fraction, determined by X-ray diffraction, is small and anisotropic. The anisotropy is similar to that observed in ancient natural samples and implies an initial anisotropic swelling mechanism rather than an anisotropic recovery mechanism occurring over geological timescales. The small unit-cell volume swelling is only ~6% of the expansion frequently attributed to a-particles associated with an actinide a-decay event. The lattice parameters indicate a volume increase as a function of a dose of 0.21 A3/1018 a-events/g, which is significantly less than the increase of 3.55 A3/1018 a-events/g seen in Pu-doped zircon and 2.18 A3/1018 a-events/g seen in natural zircon. It is concluded that the heavy recoil plays a more important role in unit-cell swelling than previously predicted. The likely mechanism for such an effect is the rapid, and thus defect-rich, recrystallization of material initially displaced by the heavy recoil. [ABSTRACT FROM AUTHOR]

The article presents information on a study which assessed the temporal behavior of most of the American Cordilleran arc by leveraging the uranium-lead zircon geochronological database from arc bedrocks and detrital samples from adjacent basins.

In-situ U-Th dating is among the most challenging analytical techniques, requiring extreme sensitivity to quantify the low-abundance 230Th. Consequently, not all mineral phases are suitable for this technique. In this issue, Wu et al. have demonstrated that baddeleyite in basic rocks can provide meaningful U-Th ages when analyzed using secondary ionization mass spectrometry. [ABSTRACT FROM AUTHOR]