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The A.M. breccia is part of the Giant Copper porphyry deposit in southern British Columbia. It is the only well-defined zoned tourmaline breccia pipe in the Canadian Cordillera. Tourmaline is a common alteration mineral within the A.M. breccia and is spatially associated with Cu mineralization. Observed changes in tourmaline chemistry range from alkali (schorlitic-dravitic) to calcic (feruvitic-uvitic). Tourmaline subspecies vary based on their spatial location within the A.M. breccia. Tourmaline outside of the pipe contains higher concentrations of Mg, whereas tourmaline preferentially incorporates Fe within the pipe. These chemical variations are indistinguishable in hand specimens. Spectral reflectance data were collected from 587 tourmaline grains to determine if discerning chemical changes in tourmaline can be made field-based and thus more cost-effective. Spectral reflectance differentiates tourmaline associated with mineralization and breccia textures from tourmaline occurring distal to the pipe contact or within barren tourmaline breccia pipes. Fe-rich tourmaline within the A.M. breccia shows spectral characteristics of end-member schorl (Fe-rich) spectra. Tourmaline distal to the A.M. breccia and within barren pipes demonstrates spectra of end-member dravite (Mg-rich). This grouping suggests that tourmaline subspecies can be inferred by spectral reflectance, enhancing the efficiency of tourmaline as a mineral vector. Tourmaline was also identified via airborne spectral surveys. However, the airborne spectral survey did not identify the end-member spectral properties identified by in situ analysis. Airborne spectral surveys can rapidly identify tourmaline breccia pipe exposures and expedite early stages of exploration in ore districts where tourmaline is a known gangue mineral.

The long-standing controversy about the origin of magnetite-(apatite) mineral deposits pertains to how they form. The Pleistocene El Laco deposit in northern Chile is a critical location because the host andesite contains immiscible melt inclusions trapped in plagioclase and clinopyroxene phenocrysts that reveal the involvement of immiscible melts in the evolution of the El Laco Volcanic System hosting the magnetite-(apatite) mineralization. We present results from the first-ever whole-rock and in situ Pb isotope investigation at El Laco, which provides a better understanding of the relationships between immiscible melts preserved in the melt inclusions, the magnetite ore, and the host andesite, and helps identify sources of the ore metals by analyzing potential sources of crustal lead. Our study reveals that the phenocrysts and the melt inclusions contain homogenous Pb isotope compositions that overlap with the host andesite, which confirms that they are coeval and cogenetic. The magnetite ore, however, has significantly more primitive 206Pb/204Pb ratios, which points to Pb isotopic disequilibrium between the magnetite ore and host andesite. Model ages of 367−167 Ma for the magnetite ore suggest that the Pb was inherited from a U−Th-depleted reservoir that could be represented by sedimentary rocks found in the basement of the Andean Cordillera under El Laco, for example, the Palaeozoic P-rich ironstones sequence. These results are consistent with the major role of crustal contamination in the formation of magnetite-(apatite) mineralization elsewhere and suggest that the magnetite ore crystallized from immiscible Fe-rich melts contaminated by the underlying sedimentary sequences.

The Montecristo district, northern Chile, is one of the few places worldwide where there is a direct relationship between magnetite-(apatite) (MtAp) mineralization and iron oxide-copper–gold (IOCG) mineralization. The MtAp mineralization includes Ti-poor magnetite, fluorapatite, and actinolite and is crosscut and partially replaced by a younger IOCG mineralization that includes a second generation of actinolite and magnetite with quartz, chalcopyrite, pyrite, and molybdenite. The MtAp stage at Montecristo is interpreted as the crystallized iron-rich melts that used the pre-existing structures of the Atacama Fault System as conduits. These rocks later acted as a trap for hydrothermal IOCG mineralization. Geochronology data at Montecristo indicate that the host diorite (U–Pb zircon 153.3 ± 1.8 Ma, 2-sigma), MtAp mineralization (40Ar-39Ar in actinolite, 154 ± 2 Ma and 153 ± 4 Ma, 2-sigma), and the IOCG event (Re-Os on molybdenite, 151.8 ± 0.6 Ma, 2-sigma) are coeval within error and took place in a time span of less than 3.4 Ma. The εHfi and εNdi values of the host diorite are + 8.0 to + 9.8 and + 4.3 to + 5.4, respectively. The whole-rock 87Sr/86Sri values of the IOCG mineralization (0.70425 to 0.70442) are in the lower end of those of the MtAp mineralization (0.70426–0.70629). In contrast, εNdi values for the IOCG mineralization (+ 5.4 and + 5.7) fall between those of the MtAp rocks (+ 6.6 to + 7.2) and the host diorite, which suggests that the IOCG event was related to fluids having a more crustal Nd (εNdi < + 5.7) composition than the MtAp mineralization. This likely reflects the mixing of Nd from the MtAp protolith and a deep magmatic-hydrothermal source, very likely an unexposed intrusion equivalent to the host diorite. Sulfur isotope compositions (δ34S, + 0.3 to + 3.4‰) are consistent with a magmatic source., NSERC discovery grant to J.M. Hanchar (RGPIN/004649-2015), RTI2018-099157-A-I00 (MCI/AEI/FEDER, UE) research grant to F. Tornos.

The origin of magnetite-(apatite) iron deposits (MtAp) is among the most contentious issue in ore geology with competing models involving purely hydrothermal to magmatic processes. We study here melt inclusions trapped in plagioclase phenocrysts in andesite hosting the emblematic MtAp mineralization at El Laco, Chile. Our high-resolution study reveals that individual melt inclusions preserve complex processes of melt immiscibility including the separation of Si- and Fe-rich melts, the latter hosting other Cu-sulfide, phosphate-rich, and C-O-HFSE-rich residual melts. This assemblage is a small-scale analogue of the ore mineralization and establishes the missing link between silicate and Fe-P-rich melts which subsequently produce extrusive magnetite. These results strongly indicate that El Laco mineralization derives from crystallization of Fe-P-rich melts providing insight into the formation of similar deposits elsewhere.

The origins of Kiruna-type magnetite(-apatite) [Mt(-Ap)] deposits are contentious, with existing models ranging from purely hydrothermal to orthomagmatic end members. Here, we evaluate the compositions of fluids that formed the classic yet enigmatic Mt(-Ap) deposit at El Laco, northern Chile. We report evidence that ore-stage minerals crystallized from an Fe-rich (6–17 wt% Fe) sulfate melt. We suggest that a major component of the liquid was derived from assimilation of evaporite-bearing sedimentary rocks during emplacement of andesitic magma at depth. Hence, we argue that assimilation of evaporite-bearing sedimentary strata played a key role in the formation of El Laco and likely Mt(-Ap) deposits elsewhere.

Laser depth profiling of laboratory-induced helium diffusion profiles in natural zircon confirms that helium diffusivity is crystallographically controlled and significantly anisotropic. Experiments on Mud Tank zircon with low degrees of alpha radiation damage (5.6 × 1016 to 1.3 × 1017 α/g) indicate that c ‖ diffusion is ∼400 to 700 times faster than a ‖ diffusion over the experimental temperature range investigated (400–600 °C). This magnitude of diffusive anisotropy implies that zircon crystals with different crystal morphologies record different helium closure temperatures. Zircon diffusion models commonly used in thermal-kinematic modeling programs do not properly account for diffusive anisotropy, and consequently, are likely to over- or underestimate helium closure temperatures in low-damage zircon. Additional experiments on pieces of a large Sri Lankan zircon crystal with strong radiation damage zoning demonstrate that both c ‖ and a ‖ diffusivity – as well as the magnitude of diffusive anisotropy – decrease with increasing radiation damage over an alpha dose range of ∼4.2 × 1017 to 8.5 × 1017 α/g. Decreases in diffusivity appear to reflect changes in the diffusion coefficient D0 and not the activation energy for diffusion. While we did not design our experiments to explore the effect of trace element geochemistry on helium diffusion in zircon in detail, our results suggest that such an effect may be significant.

The Mesozoic magnetite-(apatite) deposits of the Coastal Cordillera of Chile are interpreted as the product of the crystallization of oxidized iron-rich melts and subsequent hydrothermal alteration produced by related magmatic-hydrothermal systems. These deposits form a regional-scale mineral system controlled by the Atacama Fault System and where the mineralization spans more than 10 km in vertical extent. Individual sub-vertical bodies of massive magnetite coexist with and evolve vertically into pegmatite-, breccia-, and vein-like apatite-actinolite-magnetite/ilmenite rock. The mineralization is always hosted by a hydrothermal aureole of alkali-calcic-iron alteration that includes stockwork-like to disseminated mineralization. The deposits cluster in two groups. Those located in the northern part are mostly vein-like, and are hosted by Jurassic diorite. They have 87Sr/86Sri and eNdi values of 0.7042–0.7062 and + 5.1 to + 7.2, respectively. The southern group includes shallowly emplaced ore lenses in broadly coeval (sub-)volcanic intermediate rocks. They show similar 87Sr/86Sri signatures (0.7033–0.7065, with one value up to 0.7097) and more variable eNdi values (+ 3.9 to + 8.6). As a whole, the Sr-Nd data do not seem to be influenced by the type of crust intruded, but rather, likely track the mixing between a MORB-like reservoir and another source with elevated 87Sr/86Sri (≥ 0.706). The genetic model proposed involves the dehydration of variably altered subducted oceanic crust, the interaction of fluids released from the mantle wedge, the separation of iron-rich melts, and their ascent along transcrustal faults. The broadly coeval intermediate host rocks show a lesser contribution of subducted crust, something that perhaps excludes a genetic relationship between these rocks and the magnetite-(apatite) mineralization.

Iceland exemplifies the potential for generation of abundant silicic magma in the absence of mature island arc or preexisting continental crust. Zircon ages (U-Th and U-Pb) and isotope comp...

Zones of massive to semi-massive Fe-Ti oxide mineralization are present in the Northwest River Anorthosite, a ca. 1625-Ma Paleoproterozoic massif-type anorthosite located in the Grenville Province of south-central Labrador. The oxide mineralization is predominantly composed of coarse to very-coarse grained V-rich magnetite with less abundant coarse granular ilmenite and pleonaste that formed by exsolution from the primary, chemically impure magnetite; all observed oxide minerals have complex and abundant subsolidus reequilibration and exsolution textures. Using petrography, oxide mineral chemistry, whole-rock geochemistry, and oxide-anorthosite field relationships, a three-process model is proposed for the formation of the oxide mineralization: (1) late-stage magmatic crystallization of impure magnetite; (2) concentration of Fe-Ti oxides via solid-state remobilization; and (3) reequilibration during subsequent post-emplacement cooling and Grenvillian metamorphism. These subsolidus processes significantly modified the primary magmatic composition of the magnetite through exsolution and reequilibration. Results from in-situ magnetite EPMA and LA-ICPMS analyses were plotted on magnetite mineral chemical discrimination diagrams. The data display a wide spread and typically do not plot exclusively in the expected anorthosite-hosted Fe-Ti-V magnetite fields. This is most likely due to modification of magnetite chemistry during subsolidus cooling and reequilibration. As such, care must be taken when using magnetite discrimination diagrams for Fe-Ti-V deposits given the complex petrogenetic histories that magnetite within these types of deposits experience.

The Adamello intrusive suite is a composite batholith in Northern Italy, with an estimated 2000 km3 volume, assembled incrementally over a time span of 10 to 12 million years. The history of crystallization has been studied in detail through laser ablation ICP-MS and SIMS U–Pb geochronology of zircon, which records prolonged crystallization of each of the different intrusive units at mid-crustal levels between 43·47 and 33·16 Ma. The magmas were episodically extracted from this storage area and ascended to the final intrusion level at ∼6 km paleo-depth. Each batch of melt cooled very rapidly down to the ambient temperature of 250°C, evidenced by distinct cooling paths recorded by amphibole, biotite and K-feldspar 40Ar/39Ar dates. The magma source area was moving from SW to NE with time, causing increasing thermal maturity in the mid-crustal reservoir. The resulting temporal trend of higher degrees of crustal assimiliation in the course of the evolution of the magmatic system can be traced through Hf and O isotopes in zircon. Rough estimates of magma emplacement rates (‘magma flux’) yield very low values in the range of 10-4 km3/yr, typical of mid-to-upper crustal plutons and increase with time. Although we cannot discern a decrease of magma flux from our own data, we anticipate that a dramatic decrease of magma flux between 33 and 31 Ma along the northern contact lead to cessation of magma emplacement. ISSN:0022-3530 ISSN:1460-2415

The Earth’s lithosphere changed dramatically in many aspects during the Neoarchean era. In this period, the crust became more felsic and shows significant diversification in the composition of granitoids. Although this change has been noticed for many years, the mechanism that drove the change remains unclear. Here we report a geochemical study of Neoarchean granitoids from the Taihua Complex in the North China Craton. Zircon U-Pb dating reveals two episodes of granitoid magmatisms at ca. 2.65 Ga and ca. 2.55–2.50 Ga. Sodic TTGs at ca. 2.65 Ga are characterized by low K2O/Na2O ratios of

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 back-scattered electrons (BSE), to in situ dating by secondary ion mass spectrometry (SIMS), or by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). 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-ICPMS 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. Argon 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. Calcium-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. Lead 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.

The geology and geochemistry of the El Laco iron oxide deposit (Central Andes, Chile) support a genesis related to the ascent, degassing, and subvolcanic emplacement of an unusual oxidized silica-poor but water-and iron-rich melt that took place during the growth of the host Pliocene-Holocene andesitic volcano. The model proposed in this paper for the evolution of the deposit involves the formation of a shallow telescoped magmatichydrothermal system with complex melt-fluid unmixing in a vertical column of less than 1 km. The dominant mineralization occurs as large stratabound apatite-poor magnetite bodies interfingered with an andesite host and rooted in vertical dikes of magnetite with minor apatite. The stratabound mineralization is crosscut by abundant coeval diatreme-like structures indicative of vigorous degassing. The andesite underlying the mineralization is pervasively replaced by a high-temperature alkali-calcic alteration assemblage (K feldspar-diopside-magnetite-scapolite) that includes coarse-grained diopside-magnetite-anhydrite veins and large subvertical bodies of magmatic-hydrothermal breccias. The host andesite also shows a large strata-bound steam-heated acid alteration that is devoid of any magnetite but has produced the replacement of a significant proportion of the early magnetite by hematite. The El Laco system is rich in anhydrite but poor in sulfides, suggesting that there were persistent oxidizing conditions that inhibited the formation of a sulfide-bearing mineralization. Field evidence, oxygen isotope geothermometry, and thermodynamic constraints suggest that the magnetite mineralization formed close to the surface at temperatures above 800°C. The magnetite textures, similar to those of subaerial low-viscosity basalts, and the presence of melt inclusions in the host andesite recording the presence of immiscible Fe-Mg-Ca-(Si-Ti-P-S) and Si-K-Na-Al melts, suggest that the magnetite ore formed by direct crystallization from an iron-rich melt; its chemistry inhibited the formation of most other magmatic phases except minor apatite, anhydrite, and diopside. The crystallization of the iron-rich melt at shallow depths promoted the separation of large amounts of two immiscible aqueous fluids: a dominant low-density vapor phase and a small volume of hypersaline fluid. Diopside-magnetite-anhydrite veins are interpreted as the product of the crystallization of the residual melts, whereas the interaction of the brine with the host andesite formed the deep alkali-calcic hydrothermal assemblage. The condensation and mixing of the low-density magmatic vapor with meteoric water produced the steam-heated alteration. Isotope data from the host andesite (87Sr/86Sr: 0.7066–0.7074; εNd: −5.5 to −4.1; δ18Owhole rock: 7.2–9.6‰; δ18Omagnetite: 5.1–6.2‰) and an underlying andesite porphyry (87Sr/86Sr: 0.7075–0.7082; εNd: −5.9 to −4.6) reflect the interaction of a primitive mantle melt with Andean crustal rocks. The isotope geochemistry of the magnetite ore (87Sr/86Sr: 0.7083; εNd: −5.4 to −5.1; δ18O 3.5–5.5‰) and the alkali-calcic alteration and related diopside-magnetite-anhydrite veins (87Sr/86Sr: 0.7080–0.7083; εNd: −5.1 to −4.6; δ18Odiopside: 7.2–8.2%c; δ18Omagnetite 4.4–6.3‰) show that the mineralization has a more crustal signature than the host andesite and all the volcanic rocks of the Central Andes. Therefore, ore-forming fluids/melts were not equilibrated with the host volcanic rocks and are interpreted as related to a deep yet undiscovered batch of highly contaminated igneous rocks. Crustal contamination is interpreted as due to major interaction of a juvenile melt with the underlying Late Mesozoic-Tertiary Salta Group, located 1 to 6 km beneath the volcano and which has high 87Sr/86Sr values (0.7140–0.7141).

The ore genesis of the Paleoproterozoic iron oxide apatite deposits in the vicinity of Kiruna in northern Sweden is poorly understood, despite a century-long mining history and 2500 Mt of iron ore with grades of 30 to 70 wt% Fe produced in the region to date. Zircon grains from the ore, recently dated at ca. 1874 Ma, show very different appearances compared to zircon from surrounding host rocks (ca. 1880 Ma) and related intrusions (ca. 1880 and ca. 1874 Ma), particularly an inclusion-rich rim. In contrast, zircon from the host rocks, and a proximal granite intrusion, exhibit typical igneous growth zoning. Electron microprobe results show near stoichiometric composition for Zr, Si, and Hf in the host rock zircon grains. The ore zircon crystals have low analytical totals with significant concentrations of Ca, Fe, Y, and P and infrared spectroscopy showed several weight percent of water. These ore zircon grains further show Fe-rich inclusions, zones and/or veins in elemental X-ray maps, and light rare earth elements (LREE) enrichment. Transmission electron microscopy (TEM) shows that the LREE are not due to micro- or nano-inclusions in the zircon, but are likely hosted as LREE oxides in amorphous regions of the grains. Based on these characteristics, the rims on ore zircon grains are interpreted to be of hydrothermal origin. Uranium-Pb in monazite from the ore, measured by SIMS, suggests a secondary event influencing the area at ca. 1624 Ma, a period of known geologic activity in Fennoscandia. Electron microprobe X-ray mapping of these monazite grains shows no zoning and relatively low U and Th concentrations. Stark contrasts are visible between the ore (depleted mantle influence) and host rocks (crustal influence) in the whole rock Lu-Hf and Sm-Nd data. The depleted mantle signature of the ore could be related to the Kiruna greenstone group as a potential source region for the iron. The Sm-Nd isotopic composition of monazite from the ore shows a crustal influence, and indicates that the younger event has not disturbed the whole rock Sm-Nd signature of the ore. The hydrothermal nature of the ore zircon grains and the isotopic signatures point to a hydrothermal influence on the ore formation, with a high temperature magmatic fluid related to the intrusions as most likely heat and fluid source.

Zircon grains from the Kiruna iron oxide–apatite (IOA) ore bodies in northern Sweden are distinct in their hafnium and oxygen isotopic ratios compared to zircon grains from adjacent metavolcanic host rocks and related intrusions. Here, we combine these two isotopic systems on previously dated zircon grains to improve our understanding of these ore deposits with a long-debated origin. Contrasting theories for the formation of the Kiruna iron ores suggest either (1) emplacement through immiscible silicate–iron oxide melts or (2) transportation and deposition of iron by hydrothermal fluids. Zircon from the metavolcanic host rocks and intrusions have oxygen isotopic ratios (δ 18 O ∼3‰) that lie below typical magmatic compositions, which is evidence that roof rocks altered by meteoric water were digested into the magma. In contrast, the ores show an influence of a fluid that is higher in δ 18 O (∼7‰). Based on these findings, we propose the involvement of episodic magmatic-hydrothermal fluids in the ore genesis of the Kiruna iron ore deposits: (1) the first episode related to a deep-seated magmatism and to regional-scale metasomatic alteration, and (2) a later fluid event related to shallow intrusions and responsible for the ore formation. Distinct differences in the Hf isotopic ratios for host rocks and intrusions (e Hfi = −6 to −10, Archean crust) and ore (e Hfi = −5 to +3, depleted mantle) further allow us to screen possible fluid sources for their involvement in the ore process.

Interpretation of the mineralizing environment of magnetite-apatite deposits remains controversial with theories that include a hydrothermal or magmatic origin or a combination of those two processes. To address this controversy, we have analyzed the trace element content of magnetite from precisely known geographic locations and geologic environments from the Precambrian magnetite-apatite ore and host rocks in Kiruna, Sweden, and the Pliocene-Holocene El Laco volcano in the Atacama desert of Chile. Magnetite samples from Kiruna have low trace element concentrations with little chemical variation between the ore, host, and related intrusive rocks. Magnetite from andesite at El Laco, and dacite from the nearby Lascar volcano, has high trace element concentrations typical of magmatic magnetite. El Laco ore magnetite have low trace element concentrations and displays growth zoning in incompatible elements (Si, Ca, and Ce), compatible elements (Mg, Al, and Mn), large-ion lithophile element (Sr), and high field strength element (Y, Nb, and Th). The El Laco ore magnetite are similar in composition to magnetite that has been previously interpreted to have crystallized from hydrothermal fluids; however, there is a significant difference in the internal zoning patterns. At El Laco, each zoned element is either enriched or depleted in the same layers, suggesting the magnetite crystallized from a volatile-rich, iron-oxide melt. In general, the compositions of magnetite from these two deposits plot in very wide fields that are not restricted to the proposed fields in published discriminant diagrams. This suggests that the use of these diagrams and genetic models based on them should be used with caution.

The Kenya Rift Valley contains many ochre sources that are currently used by indigenous peoples for adornment, rituals, and art. Ochre pigments occur in rock art and archaeological sites spanning over 250,000 years. Chemical analysis for provenience of geological sources is the first step in the process of reconstructing provenance of archaeological artifacts for cultural heritage, archaeological, and paleoanthropological research. Development of an ochre source chemical composition database can facilitate reconstruction of social interaction networks and cultural heritage conservation efforts in this region. Techniques such as Laser Ablation-Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) and Instrumental Neutron Activation Analysis (INAA) are often used for compositional analysis and sourcing of ferruginous mineral pigments. Sourcing has proven challenging due to the diverse range of rocks and minerals that are classified as red and yellow ochres, and the diverse processes that induce variation in composition, including modes of formation, sedimentary transport of parent materials, and diagenesis. Attribution of samples to specific sources is possible only when variation within sources is less than differences between sources (the Provenience Postulate). Here we present the results of a study using LA-ICPMS to determine inter- and intra-source geochemical variations for ten ochre sources associated with three large volcanic centers in the central Rift Valley of Kenya. Our results show that differences in chemical composition among sources are greater than variation within sources, both at the scale of large volcanic centers and of individual ochre outcrops within these centers. Clear differentiation of source chemical fingerprints at local and regional scales satisfies the Provenience Postulate, and suggests that provenance studies of ochre artifacts, residues, and rock art in Kenya will be feasible.

Mapping the age and trace element and Sm-Nd isotope compositions of monazite grains from a peraluminous Cretaceous granite using laser ablation–split stream analysis reveals a wide range in Nd isotope and rare earth element (REE) compositions within and between single grains. These data corroborate isotopic variability indicated by Hf isotope analysis of zircon in the same granite sample. The REE variations indicate that monazite grew during fractional crystallization. Hf and Nd isotopes indicate that the granitic magma was generated from at least two distinct Proterozoic sources of approximately the same age: one component that had highly radiogenic initial 176Hf/177Hf and 143Nd/144Nd and a second component that was notably less radiogenic. This study highlights the utility of in situ REE and Sm-Nd isotope data in monazite in magmatic systems. Further, it refines the zircon-based constraints on magmatic processes because of sensitivity of light REEs to fractional crystallization, lower probability of complications owing to inheritance, and smaller analytical volumes required.

Detrital zircon U-Pb age and Hf isotope studies are useful for identifying the chemical evolution of the continental crust. Zircon, however, is typically a magmatic mineral and thus often fails to document the timing of low-grade metamorphism, and its survival through multiple sedimentary cycles potentially biases the crustal evolution record toward older events. In contrast, monazite typically records metamorphic events and is less likely to survive sedimentary recycling processes, thus providing information not available by zircon. Here, we demonstrate that monazite apparently faithfully records the Sm-Nd isotope composition of the bulk rock and can therefore track the record of crustal evolution and growth, similar to Hf isotopes in zircon. We examine the utility of detrital zircon and monazite for studies of crustal evolution through a comparison of age and tracer isotope information using sediments from two large rivers draining the South China block (SCB). Monazite and zircon grains yield mostly Mesozoic and Paleozoic U-Pb ages and depleted mantle model age peaks at ca. 1900–1300 Ma, indicating that both minerals preserve similar, yet critical, information on the crustal evolution of the catchment area. In contrast, zircon yields abundant Neoproterozoic and older U-Pb ages with a very large spread of model ages, preserving a history strongly skewed to older ages. Based on the lack of known rocks of this age in the catchments, ancient zircon was likely sourced from sedimentary rocks within the catchment area. This combined data set presents a more complete history of crustal evolution and growth in the SCB and demonstrates the advantages of an integrated approach that includes both detrital monazite and zircon.

The Pliocene El Laco volcano (northern Chile) hosts a large iron oxide deposit that occurs as stratiform bodies with underlying feeder zones (dykes) hosted by hydrothermally altered andesite lava flows. Phenocrysts in the andesite hosting the mineralization have abundant melt inclusions displaying strong evidence for melt immiscibility. Most of the pyroxene and the plagioclase phenocrysts contain abundant Fe-rich melt inclusions with low-Ti magnetite, pyroxene, apatite, and minor anhydrite. The glassy groundmass of these melt inclusions is chemically similar to sub-alkaline rhyolitic rocks (e.g., > 70% SiO 2 ; Si-Al-K-Na-rich). Large resorbed plagioclase phenocrysts also host another group of melt inclusions with a similar silica-rich groundmass but hosting evenly distributed immiscible and complex Fe-rich spheroidal globules that are enriched in Ti, P, Mg, Ca, and S. These immiscible globules and the Ti-poor magnetite daughter crystals in the melt inclusions in pyroxene phenocrysts are thought to be the parental iron oxide-melt liquid, after which their coalescence leads to the formation of magnetite melts, from which the magnetite that formed the El Laco iron oxide deposits crystallized and were emplaced. The mineralogy and chemistry of these melt inclusions tracks the chemical evolution of the Fe-Ox melts and supports a magmatic origin for the El Laco magnetite. This is mainly recognized by the continuum of compositions between volcanic, separate immiscible Fe-oxide melts, and magnetite ores. The trace element composition of the Fe-rich melt inclusions and of the magnetite in the host andesite and the ore bodies reveals a systematic depletion in most of the elements that are compatible in magnetite. The Ti content of the magnetite also records the separation and crystallization of the iron-rich melt. Typically, the magnetite in the orebodies and the melt inclusions is Ti-poor compared with titanomagnetite found in the andesite groundmass and that hosted by the hydrothermally-altered andesite; that is interpreted as being attributed to its crystallization under oxidizing and sulfur-rich conditions. The cause of this unusual chemical behaviour is probably due to the mechanism(s) governing the crystallization of the iron-rich melt, including the temperature, changes in chemistry prior to eruption, and an increase in the redox conditions of the silicate melt. Magma oxidation facilitates the prevalence of ferric iron and formation of Ti-poor magnetite, preventing the incorporation of Ti in the exsolving iron-rich melt. The likely reason for the formation of these large Ti-poor magnetite deposits is likely the contamination of the parental andesitic magma by oxidized crustal rocks and concomitant crystallization of magnetite under oxidizing conditions, something that had a significant impact on the elemental distribution.

Magnetite-apatite deposits are important sources of iron and other metals. A prominent example are the magnetite lavas at the El Laco volcano, Northern Chile. Their formation processes remain debated. Here, we test the genetic hypothesis that an Fe-rich melt separated from silicate magma and ascended along collapse-related fractures. We complement recent analyses with thermodynamic modelling to corroborate Fe-Si liquid immiscibility evident in melt inclusions at El Laco and present viscometry of Fe- and Si-rich melts to assess the time and length scales of immiscible liquid separation. Using a rock deformation model, we demonstrate that volcano collapse can form failure zones extending towards the edifice flanks along which the ore liquid ascends towards extrusion driven by vapour exsolution despite its high density. Our results support the proposed magmatic genesis for the El Laco deposits. Geochemical and textural similarities indicate magnetite-apatite deposits elsewhere form by similar processes.

Trabajo presentado en el AGU (American Geophysical Union) Fall Meeting: Advancing Earth and Space Science, celebrado en Washington D.C. (Estados Unidos), del 10 al 14 de diciembre de 2018, The origin of Kiruna-type magnetite-apatite deposits, which are thought to form by magmatic and/or hydrothermal processes, has recently come under renewed scrutiny. Geological and geochemical studies of volcanic-hosted magnetite deposits that include magnetite lava flows and ash layers at El Laco, a volcano in the Central Volcanic Zone, northern Chile, suggest a formation by eruptive emplacement of an iron oxide-rich melt. The generation of such exotic high density, low viscosity melts by dissociation from an andesitic host magma contaminated by shallow crustal sediments has only recently been shown experimentally. The dynamics of volcanic emplacement have remained enigmatic, because the high density of iron-rich melts seems to negate their eruption potential. Yet, observations of ubiquitous vesiculation, degassing structures, and steam-heated alteration provide important clues that volatiles had a pivotal role in the volcanic emplacement. Here, we posit a scenario in which an iron-rich immiscible liquid gravitationally separates from its andesitic parent magma in a shallow magma reservoir and subsequently rises as a bubbly suspension along volcano-tectonic faults extending to the flanks of the edifice. We test this hypothesis through numerical models that capture both the deformation of the volcanic edifice as well as the melt transport within. Preliminary results indicate that separation of a low-viscosity, iron- and volatile-rich melt from a silicic magma within reasonable time is possible only if an interconnected melt drainage networks forms at the granular scale. Results further suggest that magma reservoir deflation and/or minor local extension combined with the topographic load of the edifice may explain normal faults connecting the magma reservoir with magnetite flow locations on the volcano flanks. Finally, our models show that hydrostatically driven flow of iron-rich melts into these faults at depth may trigger volatile exsolution and bubble expansion to provide sufficient driving force for an eruptive emplacement. Although the case for such magmatic ore formation is perhaps strongest at El Laco, evidence from other localities suggests that similar processes have been at work. The new insights derived from our models may therefore apply more generally to Kiruna-type deposits elsewhere.

This study aims to improve our understanding of the current limitations to high-precision U–Pb analysis of zircon by LA-ICP-MS by investigating the underlying causes of variation in ablation behaviour between different zircon matrices. Multiple factors such as: the degree of accumulated radiation damage; trace element composition; crystal colour; and crystallographic orientation are all systematically investigated. Due to the marked decrease in elastic moduli of natural zircon crystals with increasing radiation damage, the accumulation of this damage is the dominant factor controlling the rate of ablation for partially damaged to highly metamict zircon samples. There are slight differences, however, in ablation behaviour between highly crystalline matrices that cannot be attributed solely to differences in the degree of accumulated radiation damage. These differences are associated with structural weakening (i.e., decrease in elastic moduli and overall lower mechanical resistance) caused by an increasing degree of cation substitution in some of the zircon samples. Effects of crystallographic orientation and of crystal opacity (i.e., colour) on ablation behaviour are negligible compared to the combined influences of accumulated radiation damage and trace element substitution into the zircon structure. Experiments performed on natural and annealed zircon grains reveal that the reduction in ablation rates observed for the treated samples compared to the untreated grains is proportional to the degree of structural reconstitution achieved after annealing. Thermal annealing of natural zircon at temperatures > 1000 °C results in much more uniform ablation characteristics. This ‘homogenisation’ of ablation behaviour between zircon matrices produces a decrease in the laser-induced matrix effects and subsequent improvement in the accuracy of 206 Pb/ 238 U ratio determinations by LA-ICP-MS.

High spatial resolution zircon U-Pb geochronological data obtained directly on the Kiirunavaara iron oxide-apatite (IOA) deposit, related orebodies, and host rocks provide new constraints on the timing of mineralization in these deposits. These data raise new arguments in the debate of a magmatic versus hydrothermal/metasomatic genesis of these major (2,500 Mt, 30–70 wt % Fe) Paleoproterozoic deposits. The main orebody at Kiirunavaara contains Ti-poor magnetite and minor (0.05–5 wt % P) apatite, located between a trachyandesite footwall and a rhyodacite hanging wall, which also hosts smaller orebodies (Nukutus, Rektorn, and Tuolluvaara). The pervasive Na and K metasomatism in the host rock is documented by whole-rock geochemical data and cathodoluminescence (CL) microscopy. Zircon U-Pb data for the metavolcanic rocks in the footwall and hanging wall cluster between 1884 ± 4 and 1880 ± 3 Ma. In the footwall, a syenite-aplite system yields ages of 1880 ± 7 and 1881 ± 4 Ma; a granite pluton exposed underground has an age of 1874 ± 4 Ma. Zircons in two ore samples, never directly dated before this study, yield ages of 1877 ± 4 and 1874 ± 7 Ma. Brecciation at the contacts between the ore and host rocks, the tight age at ca. 1880 Ma for most volcanic and plutonic rocks in the footwall and hanging wall, and the marginally younger age for ore at ca. 1877 to 74 Ma, matching the age of the spatially related granite pluton, suggest a magmatic-hydrothermal emplacement model for the Kiruna area IOA ores.

Characterization of diffusion behavior in minerals is key to providing quantitative constraints on the ages and thermal histories of Earth and planetary materials. Laboratory experiments are a vital source of the needed diffusion measurements, but these can pose challenges because the length scales of diffusion achievable in a laboratory time are commonly less than 1 μm. An effective strategy for dealing with this challenge is to conduct experiments involving inward diffusion of the element of interest from a surface source, followed by quantification of the resulting diffusive-uptake profile using a high-resolution depth-profiling technique such as Rutherford backscattering spectroscopy (RBS), nuclear reaction analysis (NRA), or ion microprobe (SIMS). The value of data from such experiments is crucially dependent on the assumption that diffusion in the near-surface of the sample is representative of diffusion in the bulk material. Historical arguments suggest that the very process of preparing a polished surface for diffusion studies introduces defects—in the form of dislocations and cracks—in the outermost micrometer of the sample that make this region fundamentally different from the bulk crystal in terms of its diffusion properties. Extensive indirect evidence suggests that, in fact, the near-surface region of carefully prepared samples is no different from the bulk crystal in terms of its diffusion properties. A direct confirmation of this conclusion is nevertheless clearly important. Here we use transmission electron microscopy to confirm that the near-surface regions of olivine, quartz and feldspar crystals prepared using careful polishing protocols contain no features that could plausibly affect diffusion. This finding does not preclude damage to the mineral structure from other techniques used in diffusion studies (e.g., ion implantation), but even in this case the role of possible structural damage can be objectively assessed and controlled. While all evidence points to the reliability of diffusivities obtained from in-diffusion experiments, we do not recommend experiments of this type using a powder source as a means of obtaining diffusant solubility or partitioning information for the mineral of interest.

We propose an integrated model that explains the magmatic and hydrothermal features of the unique El Laco iron deposit that is located in a Pliocene–Pleistocene volcano of the Chilean Andes. (Sub)volcanic crystallization of an iron-rich melt as massive magnetite promoted the exsolution of a small volume of a hydrosaline melt and of large amounts of vapor that led to the formation of an alkali-calcic hydrothermal assemblage replacing the host andesite; this assemblage is capped and overprinted by a large zone of acid-sulfate steam-heated alteration forming as a whole a protracted shallow-level magmatic-hydrothermal system. Oxygen isotopic data for the massive magnetite (δ18O: 4.3‰–5.0‰) and the alkali-calcic altered rock (diopside δ18O: 7.2‰–8.7‰; magnetite δ18O: 4.4‰–6.7‰) suggest that these rocks are genetically related to the host andesite (δ18O: 7.4‰–9.6‰). The estimated temperature of the mineral assemblage (>∼900 °C) may be the highest recorded in hydrothermal systems, is attributed to exsolution of fluids from the crystallizing iron-rich melts, and is considered unlikely to reflect the convection of surficial fluids.

The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid–rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nb and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 °C and pressures 2 O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at ∼300 °C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 °C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log D Zr ∼10 −25 m 2 /s at 650 °C and ∼10 −30 m 2 /s at 250 °C) with diffusion length-scales of − concentration, and the 3rd to 4th power of the F − concentration. These new data are consistent with observations from field studies of exhumed terranes that indicate that rutile is soluble in complex aqueous fluids, and that fluid composition is the primary control on rutile solubility and HFSE mobility.

The diopside-allanite veins and apatite breccia veins of the Hoidas Lake LREE deposit cross-cut the deformed Archaean and Paleoproterozoic granitoid gneisses of the Rae Subprovince, in northern Saskatchewan, Canada. The timing and source of this unusual and complex REE deposit are not well-constrained. Here we report on the results of LA-ICP-MS U-Pb geochronology of zircon and titanite from diopside-allanite veins and green apatite and monazite from apatite breccia veins, Hf isotopic data for zircon, and Sm-Nd isotopic data for titanite, apatite and monazite, in an attempt to constrain the age and duration of crystallization of REE-bearing phases, and provide implications on the source of the mineralization. Geological relationships and in situ U-Pb data indicate that the REE veins formed after peak metamorphism at ca. 1.9 Ga. However, there are zircon crystals in the diopside-allanite veins with concordant U-Pb dates as old as ~2350 Ma, the oldest of which may have been inherited from Arrowsmith Orogen granitoids. Zircon rims show a concordant cluster of U-Pb dates around 1911 Ma, which are interpreted to represent new zircon growth, based on textural features and their distinct initial ɛHf values (26.9 and 34.3), compared to the inherited zircon cores, which range from −9.5 to −2.0. Younger U- Pb Concordia ages of titanite (ca. 1860 Ma and 1830 Ma) and monazite (ca. 1843 Ma), and discordant apatite 207Pb/206Pb dates (ca. 1840 Ma), are considered to be the best constraints on the initiation of REE mineralization. The initial ɛNd values of titanite, green apatite and monazite (−15.2 to −10.7) are comparable to, but lower than the ɛNd values for the Martin Group alkali basalts (Beaverlodge Domain) and the ultrapotassic rocks of the Christopher Island Formation (Baker Lake Basin), both of which also yielded similar U-Pb dates to those of the youngest Hoidas Lake REE-bearing minerals. These regionally occurring alkali units originated from a similar source, most probably an ancient enriched lithospheric mantle reservoir. The melts and fluids, from which the Hoidas Lake deposit formed, then interacted with Rae craton crust as they utilized structures while they were transported from the source region to the depositional site.

Recent research has demonstrated the importance of understanding alpha radiation damage in zircon in order to effectively interpret the thermochronologic significance of (U-Th)/He dates and to appropriately select laser ablation U/Pb reference standards. Direct measurements of alpha radiation damage in zircon are most easily done by using Raman spectral response as a proxy. Current Raman microscopes provide the opportunity to quantify not just a crystal's bulk radiation damage, but to map intracrystalline variations in radiation damage related to radionuclide zoning. Here we illustrate the procedure through a detailed study of zoned Proterozoic zircon crystals from the Adirondack Mountains of New York state. Although previous Raman studies have focused on the response of the v3(SiO4) stretching band (1008 cm−1) to radiation damage, we demonstrate that the internal v2(SiO4) bending band (439 cm−1) and the external Eg band (357 cm−1) are in some cases more useful – and in the case of the Eg band more responsive – proxies. We present curves that permit α dose estimates to be made from Eg and v2 band widths over a range of ~2 × 1017 to 1.8 × 1018 α/g. We then illustrate how these radiation damage maps can be used to visualize and interrogate intracrystalline variations in any damage-dependent material property in zircon, using helium diffusivity as an example, and discuss the implications for (U-Th)/He and U/Pb chronology of ancient, zoned zircon.

Continued improvements in both ICPMS (inductively-coupled plasma mass spectrometry) and laser ablation technologies are fueling advancements in accessory mineral investigations and their related isotope systems of interest, and are now being applied to a wide range of geological applications. In this contribution we present an updated methodology for laser ablation split-stream (LASS) analysis of the light rare earth element (LREE) enriched minerals monazite, titanite, and apatite for simultaneous analysis of the U-Th-Pb age (or trace element content) and the Sm-Nd isotope system. The data were collected with the current generation of high-sensitivity ICPMS and laser systems (ThermoFinnigan NeptunePlus MC-ICPMS and Element XR SF-ICPMS- coupled to a RESOlution 193 nm ArF excimer laser system). The increased sensitivity of these ICPMS instruments allows for improved spatial resolution and the ability to target minerals which previously contained insufficient concentrations of elements of interest (e.g., Sm-Nd in apatite), making their analysis difficult, if not impossible, using less sensitive instruments. Furthermore, the higher sensitivity allows less aggressive ablation parameters that facilitate thin section sampling and reduces inter-element and isotopic fractionation. To assess and improve the accuracy, precision, and efficiency of the technique, three new potential LASS reference materials (RMs) are evaluated for dual U-Pb and Sm-Nd analysis (Tory Hill apatite, Tory Hill titanite, and Steenskralkamp monazite). The homogeneity of these materials was first assessed using reconnaissance laser ablation analyses, with final characterization of U-Pb age and Sm-Nd isotope composition using isotope-dilution thermal ionization mass spectrometry (ID-TIMS). The precision and accuracy of the LASS method is explored using secondary mineral reference materials of known age and Sm-Nd isotope composition. The utility of the technique is evaluated with a case study of monazite and apatite from the Eoarchean Uivak Gneiss complex of Labrador, Canada. Finally, we suggest that there is a wide variety of geological applications for this methodology, such as multi-mineral detrital provenance, crustal growth, and petrogenic studies.