As critical transition zones between the land and the sea, estuaries are not only hotspots of hydrogeochemical and microbial processes/reactions, but also play a vital role in processing and transferring terrestrial fluxes of metals and nutrients to the sea. This study focused on three estuaries in the Gulf of Bothnia. All of them expe-rience frequent inputs of acidic and Mn/metal-rich creek waters due to flushing of acid sulfate soils that are widespread in the creeks catchments. Analyzing existing long-term water chemistry data revealed a strong sea-sonal variation of Mn loads, with the highest values in spring (after snow melt) and autumn (after heavy rains). We sampled surface waters, suspended particulate matter (SPM), and sediments from the estuarine mixing zones and determined the loads and solid-phase speciation of Mn as well as the composition and metabolic potentials of microbial communities. The results showed that the removal, cycling, and lateral transport of Mn were governed by similar phases and processes in the three estuaries. Manganese X-ray absorption spectroscopy data of the SPM suggested that the removal of Mn was regulated by silicates (e.g., biotite), organically complexed Mn(II), and MnOx (dominated by groutite and phyllomanganates). While the fractional amounts of silicate-bound Mn(II) were overall low and constant throughout the estuaries, MnOx was strongly correlated with the Mn loadings of the SPM and thus the main vector for the removal of Mn in the central and outer parts of the estuaries, along with organically complexed Mn(II). Down estuary, both the fractional amounts and average Mn oxidation state of the MnOx phases increased with (i) the total Mn loads on the SPM samples and (ii) the relative abundances of several potential Mn-oxidizing bacteria (Flavobacterium, Caulobacter, Mycobacterium, and Pedobacter) in the surface waters. These features collectively suggested that the oxidation of Mn, probably mediated by the potential Mn-oxidizing microorganisms, became more extensive and complete towards the central and outer parts of the es-tuaries. At two sites in the central parts of one estuary, abundant phyllomanganates occurred in the surface sediments, but were converted to surface-sorbed Mn(II) phases at deeper layers (>3-4 cm). The occurrence of phyllomanganates may have suppressed the reduction of sulfate in the surface sediments, pushing down the methane sulfate transition zone that is typically shallow in estuarine sediments. At the outermost site in the estuary, deposited MnOx were reduced immediately at the water-sediment interface and converted most likely to Mn carbonate. The mobile Mn species produced by the Mn reduction processes (e.g., aqueous Mn(II) and ligand complexed Mn(III)) could partly diffuse into the overlying waters and, together with the estuarine Mn loads carried by the surface waters, transfer large amounts of reactive Mn into open coastal areas and subsequently contribute to Mn shuttling and inter-linked biogeochemical processes over the seafloor. Given the widespread occurrence of acid sulfate soils and other sulfidic geological materials on many coastal plains worldwide, the identified Mn attenuation and transport mechanisms are relevant for many estuaries globally.

Whole-rock geochemical analysis is a standard method to measure the chemical composition of ores. Analysis of refractory ore metals such as Ta and W typically requires fused bead and acid digestion followed by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled mass spectrometry (ICP-MS). Since these techniques are time-consuming and expensive, there is a demand for methods that can quantitatively measure low elemental concentration of refractory ore metals using a less expensive and simple approach. This paper evaluates preparation and analytical procedures developed to obtain whole-rock element concentrations of ore samples and mineral concentrates. It shows that the production of nano-particulate pressed-powder pellets followed by LA-ICP-MS analysis of W and Ta ores can be used to determine, within the error margin, the concentrations of the refractory metals W, Ta, Nb, and Sn compared to a reference values obtained by solution analysis. The results have implications for developing a commercially viable method for analysis of refractory elements to benefit mineral processing given the simplicity and resource-efficiency of the combined pressed pellet production and laser ablation analytical methodology.

Fault‐ and fracture‐hosted multi‐stage mineral assemblages that formed by fracture reactivation and fluid migration, constitute archives of the tectonic evolution of Precambrian cratons. Complex intergrowth patterns of these mineral records often hinder absolute dating of mineralization events for geological models. We apply LA‐ICP‐MS/MS in situ Rb‐Sr dating of single crystal growth zones in sub‐mm‐wide vein mineralization assemblages including illite, K‐feldspar, albite, calcite, mica, zeolites, fluorite and/or epidote at three Palaeoproterozoic crystalline bedrock sites over 300 km apart in the Fennoscandian Shield. The dating campaign reveals multiple age clusters between ca. 1757 ± 15 and 355 ± 12 Ma correlating with fluid flow and fracture reactivation events initiated by far‐field orogens and their foreland basin evolution. This new approach for reconstructing geological histories of Precambrian cratons connects micro‐scale age determinations of different mineral growth zones in fractures with regional‐scale crustal dynamic responses to tectonic events.

Apatite is a ubiquitous accessory mineral in various rocks (e.g., igneous, metamorphic and clastic sedimentary rocks). However, precise and accurate U‐Pb LA‐ICP‐MS dating of apatite is often compromised by high common Pb levels. Among the different common Pb correction methods, the main advantage of the 204Pb correction method is that it does not assume U/radiogenic Pb concordance. However, 204Pb is difficult to measure using ICP‐MS instruments because of the isobaric interference of 204Hg on 204Pb. We overcome this limitation by using a reaction cell sandwiched between two quadrupoles within an ICP‐MS, which can allow the online chemical separation of two different elements. Ammonia reacts efficiently (> 98%) with Hg while isotopes of Pb are not affected. The approach was tested on eight apatite reference materials (McClure Mountain, NW‐1, UWA‐1, Otter Lake, Slyudyanka, MK‐1, Durango and Fish Canyon Tuff) for which there are independent constraints on the U‐Pb crystallisation age, by comparing U‐Pb dating results employing different reaction gas mixes (NH3‐N2O and NH3 only) in two laboratories. Based on the U‐Pb data and SEM analyses on each sample, we can exclude apatite inter‐ and intra‐grain U‐Pb age heterogeneity, except for a c. 4% variability of ages in the Otter Lake sample. Our results show that accuracy and precision for U‐Pb dating are not measurably affected by different reaction gases, and we accurately reproduce ages of numerous independently characterised apatites within 4% of the reference ages, and the age reproducibility is typically better than 2%.

Minerals formed in fractures and veins by intermittent fracture reactivation and fluid migration constitute archives of the tectonic evolution of Precambrian cratons. These mineralogical records feature complex intergrowth patterns of fine-grained vein generations and discrete mineral zonations that are difficult to target by bulk dating methods. Instead, absolute ages of mineralization events can be constrained by applying in situ Rb-Sr dating via triple quadrupole laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS/MS) on veins and single fracture crystal growth zones [1, 2]. We utilize in situ Rb-Sr dating of a wide range of coeval K-and Ca-rich mineral assemblages to distinguish discrete vein generations at three Paleoproterozoic crystalline bedrock sites in Sweden, separated by over 300 km. The resulting age clusters link veining and fracturing to tectonic events affecting the Fennoscandian Shield up to a billions years apart. Coupled textural and structural analysis and in situ dating of grain growth zones anchors veins and fracture-hosted mineral precipitation to fluid migration fracture reactivation episodes across the Fennoscandian Shield, enabling reconstruction of far-field orogenic activity and foreland basin evolution. This new approach for resolving geological histories of Precambrian cratons connects micro-scale age determinations of individual grains and veins with regional-scale crustal dynamic responses to tectonic events. Furthermore, the study demonstrates the advancing applicability of the in situ Rb-Sr LA-ICP-MS/MS dating method for tracing hydrothermal systems.

The Pontiac subprovince consists of metaturbidites, plutons and thin ultramafic rock layers of Archean age and lies south of the Cadillac-Larder Lake (C-LL) fault zone which is the boundary between the Pontiac and the extensively mineralized Abitibi Greenstone Belt. The sediments show a Barrovian metamorphic gradient which increases southwards, away from the C-LL fault. The most likely tectonic provenance for the Pontiac sedimentary rocks is that they represent a relic accretionary prism with material derived from both the Abitibi and an older terrane. Zircon U-Pb dating shows that deposition occurred not later than 2685±3 Ma ago and recent, robust Lu-Hf dating of garnets bracketed Pontiac's peak metamorphic conditions at 2658±4 Ma. For this study we used a recently developed LA-ICP-MS/MS method for in-situ Rb-Sr dating of biotite and plagioclase in samples ranging in metamorphic grade (biotite to sillimanite zones) from the Pontiac subprovince. Calibration of the instrument was achieved by repeated ablations on several reference materials (see Hogmalm et al. 2017) which also provided the monitoring of accuracy and precision throughout the analyses. Results show a range in dates between 2550 Ma and 2200 Ma with an average of 2440±50 Ma (2σ). Samples from the staurolite and kyanite zones have a larger range with respect to the other zones, but no significant differences are observed in the data with any method of data handing. These dates are ≈300Ma younger than the peak metamorphism in the area and this is attributed to either overgrowth and re-setting of the Rb-Sr system by a second metamorphic/hydrothermal event, or diffusional resetting with core-rim age variations. Possible influence from the adjacent late syntectonic to post-tectonic monzodiorite-monzonite-granodiorite-syenite (MMGS) plutons dated 2671±4 Ma and the garnet-muscovite-granite series (GMG) dated ≈2650 Ma cannot be ruled out. This study provides insights about the metamorphic history of the sequence and supports previous findings regarding resetting of some isotopic systems with relatively low closure temperatures (≈350-400°C) by later thermal events.

Coarse comminution test-work and modeling are powerful tools in the design and optimization of mineral processing plants and provide information on energy consumption. Additional information on mineral liberation characteristics can be used for assessing the potential of pre-concentration stages or screens in the plant design. In ores of high-value metals (e.g., Ta, W), standard techniques—such as the mineralogical quantification of grain mounts by quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) or chemical analysis by X-ray fluorescence (XRF) can be challenging, due to the low relative abundance of such valuable minerals. The cost of QEMSCAN is also a limiting factor, especially considering the large number of samples required for the optimization of coarse comminution. In this study, we present an extended analytical protocol to a well-established mechanical test of interparticle breakage to improve the assessment of coarse mineral liberation characteristics. The liberation of ore minerals is a function of the rock texture and the difference in size and mechanical properties of the valuable minerals relative to gangue minerals and they may fraction in certain grain sizes if they behave differently during comminution. By analyzing the bulk-chemistry of the different grain size fractions produced after compressional testing, and by generating element by size diagrams, it is possible to understand the liberation characteristics of an ore. We show, based on a case study performed on a tantalum ore deposit, that element distribution can be used to study the influence of mechanical parameters on mineral liberation. This information can direct further mineralogical investigation and test work.

The concentrations, loads and speciation of rare earth elements (REEs) were studied in a 3.5 m thick mud depositional succession from an estuary in the Gulf of Bothnia. The uppermost 182.5 cm of the mud, estimated to have deposited from the early 1970s to 2011 (sampling year), had very high REE concentrations (596-1456 ppm) and accumulation rates (5.2-28 g m(-2) year(-1)). This was explained by large REE export from acid sulfate soils after they became efficiently drained with modern drainage techniques. Geochemical and synchrotron-based spectroscopic (XANES) analyses showed that the REEs in the mud are relatively firmly bound in non-clastic phases, likely adsorbed by clay minerals and also to some extent by iron oxyhydroxides. Below 182.5 cm, the REE concentrations successively decreased down to background values at the base at 3.5 m, reflecting less efficient drainage and leaching of the acid sulfate soils in previous decades and centuries.

This study focuses on concentrations and fractionation of rare earth elements (REE) in a variety of minerals and bulk materials of hydrothermal greisen and vein mineralization in Paleoproterozoic monzodiorite to granodiorite related to the intrusion of Mesoproterozoic alkali- and fluorine-rich granite. The greisen consists of coarse-grained quartz, muscovite, and fluorite, whereas the veins mainly contain quartz, calcite, epidote, chlorite, and fluorite in order of abundance. A temporal and thus genetic link between the granite and the greisen/veins is established via high spatial resolution in situ Rb-Sr dating, supported by several other isotopic signatures (δ34S, 87Sr/86Sr, δ18O, and δ13C). Fluid-inclusion microthermometry reveals that multiple pulses of moderately to highly saline aqueous to carbonic solutions caused greisenization and vein formation at temperatures above 200–250°C and up to 430°C at the early hydrothermal stage in the veins. Low calculated ∑REE concentration for bulk vein (15 ppm) compared to greisen (75 ppm), country rocks (173–224 ppm), and the intruding granite (320 ppm) points to overall low REE levels in the hydrothermal fluids emanating from the granite. This is explained by efficient REE retention in the granite via incorporation in accessory phosphates, zircon, and fluorite and unfavorable conditions for REE partitioning in fluids at the magmatic and early hydrothermal stages. A noteworthy feature is substantial heavy REE (HREE) enrichment of calcite in the vein system, in contrast to the relatively flat patterns of greisen calcite. The REE fractionation of the vein calcite is explained mainly by fractional crystallization, where the initially precipitated epidote in the veins preferentially incorporates most of the light REE (LREE) pool, leaving a residual fluid enriched in the HREE from which calcite precipitated. Fluorite occurs throughout the system and displays decreasing REE concentrations from granite towards greisen and veins and different fractionation patterns among all these three materials. Taken together, these features confirm efficient REE retention in the early stages of the system and minor control of the REE uptake by mineral-specific partitioning. REE-fractionation patterns and fluid-inclusion data suggest that chloride complexation dominated REE transport during greisenization, whereas carbonate complexation contributed to the HREE enrichment in vein calcite.

The Akcaabat gold deposit is mainly composed of massive arsenopyrite veins in strongly foliated augen gneisses of the tine Sub-massif in western Turkey. K-bearing minerals from orogenic gold veins were dated by the in situ Rb-Sr method in order to determine the formation age of the Akcaabat gold deposit. Textural relationships between the vein minerals suggest that arsenopyrite, K-feldspar, quartz, and muscovite formed in one paragenetic stage. Native gold, native bismuth, scorodite, and galena were introduced in a later paragenetic stage. The isochron derived from K-feldspar and muscovite occurring in the veins yielded 31.3 +/- 4.7 Ma. In situ Rb-Sr dating of the same assemblage (K-feldspar and muscovite) in the host rock gave an isochron age of 40.8 +/- 3.8 Ma, 10 Ma older than the vein ages, and corresponding to peak metamorphism of the regional main Menderes metamorphism during the Alpine-Himalayan orogenic event. Biotite from the host rock gave an isochron age of 28.1 +/- 2.2 Ma and probably reflects the cooling age. Homogenization temperatures from fluid inclusions in quartz show that quartz formed at 280-390 degrees C but has a dominant mode in the 350-360 degrees C temperature interval. The age of vein formation was successfully distinguished from the age of the Alpine-Himalayan orogenic event associated with main Menderes metamorphism. This study demonstrates that in situ Rb-Sr isotopic study can be applied to resolve absolute dating of orogenic deposits in metamorphic complexes.

PURPOSE:To investigate the possible mechanisms behind early cup loosening in a metal-on-metal trapeziometacarpal joint replacement. METHODS:The trapezia from 5 female patients were removed as part of a salvage procedure after a median of 22 months (range, 7-43 months) after implantation. Three osteoarthritic patients with symptomatic cup loosening and 2 with instability had a median age of 62 years (range, 59-65 years) at primary surgery. The trapezia with cups in situ were preserved and processed for histomorphometry. Studies with laser ablation inductively coupled plasma mass spectrometry and scanning electron microscopy with energy dispersive x-ray spectroscopy were also performed on 2 of the specimens. RESULTS:In all 5 specimens, osteolytic lesions undermined the cups and were also seen at the cup edges, completely surrounding the loose cups. Large amounts of dark particular material were seen in the periprosthetic tissues, mostly internalized by macrophages. The presence of chrome and cobalt in these regions was confirmed. Four of the 5 cups showed marked or complete loss of hydroxyapatite. CONCLUSIONS:We have found several possible explanations for the poor performance of this cup, including its cannulated design and metal-on-metal bearing. The changes seen are early and advanced, raising serious concerns about the implant and particularly the articulation. TYPE OF STUDY/LEVEL OF EVIDENCE:Therapeutic V.

Conventional dating of molybdenite ( 187 Re- 187 Os) provides one of few options for direct dating of sulfide mineralization. Unfortunately, in situ dating of molybdenite is considered unreliable due to intra-granular decoupling of 187 Re- 187 Os. In this study, we developed a new analytical protocol for studies of micron- to grain scale 187 Re- 187 Os systematics in molybdenite. Online chemical separation using ICP-MS/MS technology enables in situ dating by β-decay systems (e.g., Rb-Sr and K-Ca in micas) using laser ablation. Here, the methodology is extended to the 187 Re- 187 Os system, another β-decay system that cannot be resolved by mass spectrometry. Several reaction gases were evaluated, and production of OsCH 2 by reaction with CH 4 was found to produce strong separation of Os from Re. However, in contrast to the e.g., 87 Rb- 87 Sr system, 1–2% of the parent isotope Re also reacted to ReCH 2 , leaving a significant interference. A mathematical correction of this remaining interference is possible, and 187 Re- 187 Os (mass-shifted) can be measured accurately even for fairly extreme ratios. For laser ablation, standards were developed by pressing particulate pellets of conventionally dated molybdenite (Moly Hill and Merlin), because there are no appropriate reference materials available. Six natural molybdenite samples from a range of geological settings, containing > 10 ppm Re, were analyzed by 70 μm laser ablation spots, and ages were calibrated by analysis of molybdenite pellets. Contrary to our expectation, weighted average ages obtained were in agreement (within 1%) with conventional age determinations, with fairly good precision (from ~ 1 to 5% 2 σ depending on Re concentration), suggesting limited or essentially nonexistent decoupling within crystals. Two important implications of this result are that decoupling Re-Os is not universal, and that our new analytical protocol is useful both for dating and for studies of decoupling. The benefit of in situ dating compared to conventional dating is, apart from lower cost and time consumption, the possibility of targeting smaller molybdenite crystals (≥ 100 μm) in thin sections and epoxy mounts. The youngest sample in the study is 920 Ma, but we see potential of dating significantly younger Re-rich molybdenite.

Weathering caused by interaction between glacial sediments and water in exposed moraines needs to be studied to evaluate their possible effects on the global carbon cycle. In this study, moraine ponds, moraine porewaters, and till samples were collected at a moraine adjacent to the Greenland Ice Sheet at Kangerlussuaq. Scanning electron microscopy (SEM) studies of the till show limited evidence of silicate chemical weathering, but the moraine waters have substantial solute concentrations. δ34SSO4 and δ18OSO4 data indicate that the origin of dissolved sulfate is the oxidation of sulfides, in agreement with the SEM observations. The dissolved HCO3−/SO42− molar ratios indicate an uneven balance between sulfuric and carbonic acid weathering; C-isotope data indicate that some of the CO2 originates from organic carbon mineralization. Ion–ion plots provide evidence of carbonate weathering and of the formation of secondary gypsum and calcite through evaporation and (or) cryoconcentration. The 87Sr/86Sr ratios in the waters correlate with the corresponding till samples, supporting the local origin of the dissolved strontium, which is higher in the waters than in the till due to the selective weathering of biotite. The data evidence a large degree of chemical weathering in moraines promoted by large rock–water ratios and by the hydraulic isolation created by the frozen till. The high PCO2 in the studied moraine waters indicates that they may represent a previously underestimated CO2 source.

This study investigated interfacial reactions between aqueous Ce(III) and two synthetic nanosized Mn (hydr-) oxides (manganite: gamma-MnOOH, and vernadite: delta-MnO2) in the absence and presence of Nordic Lake fulvic acid (NLFA) at circumneutral pH by batch experiments and cryogenic X-ray photoelectron spectroscopy (XPS). The surfaces of manganite and vernadite were negatively charged (XPS-derived loadings of (Na+ K)/Cl > 1) and loaded with 0.42-4.33 Ce ions nm(-2). Manganite stabilized Ce-oxidation states almost identical to those for vernadite (approximately 75% Ce(IV) and 25% Ce(III)), providing the first experimental evidence that also a Mn (III) phase (manganite) can act as an important scavenger for Ce(IV) and thus, contribute to the decoupling of Ce from its neighboring rare earth elements and the development of Ce anomaly. In contrast, when exposed to Ce (III)-NLFA complexes, the oxidation of Ce by these two Mn (hydr-) oxides was strongly suppressed, suggesting that the formation of Ce(III) complexes with fulvic acid can stabilize Ce(III) even in the presence of oxidative Mn-oxide surfaces. The experiments also showed that Ce(III) complexed with excess NLFA was nearly completely removed, pointing to a strong preferential sorption of Ce(III)-complexed NLFA over free NLFA. This finding suggests that the Ce(III)-NLFA complexes were most likely sorbed by their cation side, i.e. Ce(III) bridging between oxide groups on the Mn (hydr-) oxides and negatively-charged functional groups in NLFA. Hence, Ce(III) was in direct contact with the oxidative manganite and vernadite but despite that not oxidized. An implication is that in organic-rich environments there may be an absence of Ce(IV) and Ce anomaly despite otherwise favorable conditions for Ce(III) oxidation.

In the deep biosphere, microbial sulfate reduction (MSR) is exploited for energy. Here, we show that, in fractured continental crystalline bedrock in three areas in Sweden, this process produced sulfide that reacted with iron to form pyrite extremely enriched in 34S relative to 32S. As documented by secondary ion mass spectrometry (SIMS) microanalyses, the δ34Spyrite values are up to +132‰V‐CDT and with a total range of 186‰. The lightest δ34Spyrite values (−54‰) suggest very large fractionation during MSR from an initial sulfate with δ34S values (δ34Ssulfate,0) of +14 to +28‰. Fractionation of this magnitude requires a slow MSR rate, a feature we attribute to nutrient and electron donor shortage as well as initial sulfate abundance. The superheavy δ34Spyrite values were produced by Rayleigh fractionation effects in a diminishing sulfate pool. Large volumes of pyrite with superheavy values (+120 ± 15‰) within single fracture intercepts in the boreholes, associated heavy average values up to +75‰ and heavy minimum δ34Spyrite values, suggest isolation of significant amounts of isotopically light sulfide in other parts of the fracture system. Large fracture‐specific δ34Spyrite variability and overall average δ34Spyrite values (+11 to +16‰) lower than the anticipated δ34Ssulfate,0 support this hypothesis. The superheavy pyrite found locally in the borehole intercepts thus represents a late stage in a much larger fracture system undergoing Rayleigh fractionation. Microscale Rb–Sr dating and U/Th–He dating of cogenetic minerals reveal that most pyrite formed in the early Paleozoic era, but crystal overgrowths may be significantly younger. The δ13C values in cogenetic calcite suggest that the superheavy δ34Spyrite values are related to organotrophic MSR, in contrast to findings from marine sediments where superheavy pyrite has been proposed to be linked to anaerobic oxidation of methane. The findings provide new insights into MSR‐related S‐isotope systematics, particularly regarding formation of large fractions of 34S‐rich pyrite.

Significant improvements to the analytics and calibration of in situ Rb–Sr dating; extending the concept to in situ K–Ca dating.

A great deal of research has been devoted to the characterization of metal exposure due to the consumption of vegetables from urban or industrialized areas. It may seem comforting that concentrations in crops, as well as estimated exposure levels, are often found to be below permissible limits. However, we show that even a moderate increase in metal accumulation in crops may result in a significant increase in exposure. We also highlight the importance of assessing exposure levels in relation to a regional baseline. We have analyzed metal (Pb, Cd, As) concentrations in nearly 700 samples from 23 different vegetables, fruits, berries and mushrooms, collected near 21 highly contaminated industrial sites and from reference sites. Metal concentrations generally complied with permissible levels in commercial food and only Pb showed overall higher concentrations around the contaminated sites. Nevertheless, probabilistic exposure assessments revealed that the exposure to all three metals was significantly higher in the population residing around the contaminated sites, for both low-, median- and high consumers. The exposure was about twice as high for Pb and Cd, and four to six times as high for As. Since vegetable consumption alone did not result in exposure above tolerable intakes, it would have been easy to conclude that there is no risk associated with consuming vegetables grown near the contaminated sites. However, when the increase in exposure is quantified, its potential significance is harder to dismiss - especially when considering that exposure via other routes may be elevated in a similar way.

Direct mineral dating is critical for thorough understanding of the genesis of hydrothermal mineralizations, ore forming processes and events of fracturing and related fluid-rock interaction. Since minerals of suitable type and sample volume for conventional techniques can be rare, development of high-precision in situ Rb-Sr dating of common rock-forming minerals such as micas, feldspars and calcite offers possibilities to gain temporal constraints of a wide variety of geological features with detailed spatial and depth resolution. This technique separates 87Sr from 87Rb by introducing a reaction gas between two quadropoles in a LA-ICP-MS system. In this study, in situ Rb-Sr geochronology distinguishes the timing of several different fracture-controlled hydrothermal events: 1 and 2) greisen mineralizations and associated far-field hydrothermal veins adjacent to a granite intrusion, 3) reactivation events within a mylonite shear zone and 4) low-temperature precipitation from saline organic-rich brines in thin veinlets. We demonstrate that in situ Rb-Sr dating is feasible for a broad range of mineral assemblages, textures, temperatures and ages, emphasizing the impending use of this new method in ore deposit exploration and many other research fields.

The local geology at Kloxasen is characterised by ejecta deposits from the 458 Ma Lockne marine impact. The Kloxasen ejecta are located on a Caledonian parautochthonous unit, approximately 7 km from the centre of the 7.5-km-wide Lockne crater structure. The ejecta were deposited on the seafloor and were covered with seawater immediately after the impact event. Of special interest is a mafic impact breccia within the ejecta, which before the impact was angstrom sby dolerite that belongs to the Jamtland suite of the 1.25 Ga Central Scandinavian Dolerite Group. The mafic impact breccia occurs mainly as a coherent thin domain within a larger block of granitic breccia, which we interpret as a result of the in situ brecciation of a dolerite sill within granitic bedrock. Shock pressure in the doleritic breccia was low, in the order of 0.4 GPa, constrained by the presence of mechanically twinned clinopyroxene. Low shock pressure and brecciation corresponds well to the spall zone of an impact crater, where ejecta originate from. Whereas spalled ejecta can also show signs of having been exposed to high shock pressures, including shocked quartz, evidence for this was not found in the Kloxasen ejecta. The breccia has been hydrothermally altered, but the ejecta are too far removed from the crater to have been affected by hydrothermal circulation in relation to Lockne's impact event. Fluid inclusion analyses suggest that most of the alteration happened later, during the Caledonian orogeny. Geochemical analyses reflect observed mineral alterations well, such as serpentinisation of olivine.