Formation of solid bituminous matter in pegmatites: Constraints from experimentally formed organic matter on microporous silicate minerals

The formation of solid bituminous matter (SBM) on surfaces of microporous silicates was experimentally studied at pressure and temperature conditions typical of late-stage magmatic and hydrothermal processes. Aliquots of microporous silicate minerals (zorite and kuzmenkoite-Mn, Lovozero Alkaline Massif, Kola Peninsula, Russia) were exposed to solid or liquid organic carbon sources (natural brown coal and liquid 1-hexene for synthesis purposes) in a 0.1 M NaCl-solution for 7 days, at constant pressure (50 MPa), and at three individual temperatures (200, 275, and 300 °C). No thermal decomposition of the solid organic sources happened at 200 °C and only a thin film of brown coal derivatives on the silicates’ surfaces and no formation of SBM were observed at 275 °C and 300 °C. But solid bituminous matter on the surfaces of both microporous silicates were detected in experiments with liquid 1-hexene as organic carbon source and at temperatures of 275 °C and 300 °C with a more pronounced formation of SBM at 300 °C compared to 275 °C. The aromatic and aliphatic hydrocarbons, as well as alcoholic compounds of the experimentally produced SBM are similar, if not even partly identical, with natural SBM occurrences of the Khibiny and Lovozero Massifs, Kola Peninsula, Russia, and from the Viitaniemi granitic pegmatite, Finland, as shown by FT-IR and ¹H NMR spectroscopy. This strengthens the hypothesis of formation of natural solid bituminous matter by catalytic reactions between microporous Ti-, Nb- and Zr-silicates and hydrocarbons at postmagmatic hydrothermal conditions.     

The Blagodatnoe gold-sulfide deposit (Yenisei Ridge,Russia): the nature of geophysical anomalies and the succession and causes of formation of petrophysical zoning

Data on geophysical fields and petrophysical heterogeneity, parageneses and the thermodynamic conditions and age of their formation, and fluid inclusions were used for the genetic reconstruction of petrophysical zoning at the Blagodatnoe gold-sulfide deposit. Petrophysical associations of the preore and ore stages of the deposit formation are clearly reflected in anomalies of the magnetic and natural electric fields and the aureoles of radioactive elements. At the early preore stage (752 Ma), reduced solutions with high activity of K, enriched in U, Th, and, probably, Au, were supplied to intensely foliated tectonic zones. Their interaction with initial metasedimentary rocks gave rise to contiguous zones of quartz–muscovite and chlorite metasomatic rocks. Accompanying graphitization led to a high electrochemical activity of the metasomatic rocks, which generated anomalies of up to –300 mV in the natural electric field; the most intensely carbonized zones became enriched with U (up to 6.5 × 10^–4%) and, probably, Au. The quartz–muscovite metasomatic rocks accumulated Th and K (up to 29 × 10^–4% and 4%, respectively), whereas the chlorite metasomatic rocks accumulated rock-forming elements (particularly Fe), which led to the compaction of these rocks and the acceleration due to gravity in local positive anomalies. The nonmagnetic character of the fresh pre-ore metasomatic rocks suggests the predominantly pyritic composition of early sulfides. At the ore stage (698 Ma), the minerals were deposited from H₂O–CO₂–As–S solutions at 560 to 315 °C. The activity of these solutions caused a redistribution of radioactive elements and a high petrophysical differentiation of the ore-bearing structure. The amplitudes of the anomalies above this structure vary from 500 to 80 nT in the magnetic field and from –130 to + 10 mV in the natural electric field. It has been found that the hydrothermal fluid hardly affected the polarization properties of graphitized rocks at the maximum temperatures but caused an intense removal of U and the development of magnetic pyrrhotite after pyrite. The temperature decrease in the mineral-forming system was favorable for the formation of siderite. Carbonaceous schists which experienced carbonatization lost their electrochemical activity. The binding of carbon dioxide in the solid phase influenced the migration capability of trace elements and their zonal distribution. With this evolution of the solution, Th accumulated at the lower levels of the mineralized zone, whereas the upper levels of the deposit became enriched with U. Productive gold–arsenopyrite–pyrite–pyrrhotite paragenesis with anomalous magnetic susceptibility evolved at the ore stage. The late galena–sphalerite–chalcopyrite paragenesis (365 Ma) was of strictly local occurrence and reduced the magnetic susceptibility of ores.     

Evidence for shear heating,Musgrave Block,central Australia

The phenomenon of shear-heating is generally difficult to recognise from petrologic evidence alone. Establishing that shear zones attain higher temperatures than the surrounding country rocks requires independent evidence for temperature gradients. In the Musgrave Block, central Australia, there is a clear spatial association between shear zones and interpreted elevated temperatures. Eclogite facies shear zones that formed at ∼550 Ma record temperatures of ∼650–700°C. Outside the high-pressure shear zones, minerals with low closure temperatures such as biotite (∼450°C in the ⁴⁰Ar–³⁹Ar and Rb–Sr systems), preserve ages >800 Ma, suggesting that these rocks did not experience temperatures greater than about 450°C at ∼550 Ma for any extended period. Thus, the shear zones record temperatures that are ∼200°C higher than the surrounding country rocks. Simple calculations show that the combination of relatively high shear stresses (∼100 MPa) and high strain rates (∼10⁻¹¹ s⁻¹) for short durations (<1 Ma) can account for the observed apparent temperature variations. The evidence indicates that shear heating is the dominant mechanism for localised temperature increases in the shear zones, while the country rock remained at relatively lower temperatures.     

Metallogeny of the Shilu Fe–Co–Cu deposit,Hainan Island,South China: Constraints from fluid inclusions and stable isotopes

The Shilu deposit is a world-class Fe–Co–Cu orebody located in the Changjiang area of the western part of Hainan Island, South China. The distribution of Fe, Co, and Cu orebodies is controlled by strata of the No. 6 Formation in the Shilu Group and the Beiyi synclinorium. Based on a petrological study of the host rocks and their alteration assemblages, and textural and structural features of the ores, four mineralization stages have been identified: (1) the sedimentary ore-forming period; (2) the metamorphic ore-forming period; (3) the hydrothermal mineralization comprising the skarn and quartz–sulfide stage; and (4) the supergene period. The fluid inclusions in sedimentary quartz and/or chert indicate low temperatures (ca. 160 °C) and low salinities from 0.7 to 3.1 wt.% NaCl_eq, which corresponds to densities of 0.77 to 0.93 g/cm³. CO₂-bearing or carbonic inclusions have been interpreted to result from regional metamorphism. Homogenization temperatures of fluid inclusions for the skarn stage have a wide range from 148 °C to 497 °C and the salinities of the fluid inclusions range from 1.2 to 22.3 wt.% NaCl_eq, which corresponds to densities from 0.56 to 0.94 g/cm³. Fluid inclusions of the quartz–sulfide stage yield homogenization temperatures of 151–356 °C and salinities from 0.9 to 8.1 wt.% NaCl_eq, which equates to fluid densities from 0.63 to 0.96 g/cm³.Sulfur isotopic compositions indicate that sulfur of the sedimentary anhydrite and Co-bearing pyrite, and the quartz–sulfide stage, was derived from seawater sulfate and thermochemical sulfate reduction of dissolved anhydrite at temperatures of 200 °C and 300 °C, respectively. H and O isotopic compositions of the skarn and quartz–sulfide stage demonstrate that the ore-forming fluids were largely derived from magmatic water, with minor inputs from metamorphic or meteoric water. The Shilu iron ore deposit has an exhalative sedimentary origin, but has been overprinted by regional deformation and metamorphism. The Shilu Co–Cu deposit has a hydrothermal origin and is temporally and genetically associated with Indosinian granitoid rocks.     

Predicting pyrogenic organic matter mineralization from its initial properties and implications for carbon management

Predicting pyrogenic carbon (PyC) or biochar stability from its precursor properties is critical for evaluating and managing terrestrial C stocks. Transmission mode Fourier transform infrared spectroscopy (FTIR) spectroscopy was compared with proximate analysis data and H/C and O/C for predicting C mineralization. PyC produced at 7 different temperatures from 6 different feedstocks, in addition to the original feedstock materials, was incubated for 3 yr at 30 °C in a sand matrix. A C debt or credit ratio was calculated by comparing the C remaining in the incubated PyC sample (accounting for the measured C lost during initial PyC production) to the C remaining in the incubated original feedstock. A value > 1 indicates that more C remains in the PyC than in the original feedstock (credit), while a value < 1 indicates a debt. After 3 yr, PyC produced at 300 °C lost significantly more C than higher temperature PyC material, but significant differences in C loss between PyC produced at temperatures ⩾ 350 °C were not detectable. The best predictor of C loss was a multiple linear regression model using the fractional FTIR signals at 816, 1048, 1374, 1424, 1460, 1590, 1700 and 2925 cm⁻¹ as parameters (R² 0.80, p < 0.0001). After 3 yr, the C debt or credit ratio reached values significantly > 1 for all corn PyC samples and some bull, dairy and poultry PyC samples, resulting in net C credit, while all pine and oak PyC samples remained in debt. This C debt or credit ratio reveals that, depending on the timeline of interest, producing relatively low temperature PyC with less initial C loss can result in greater C savings than producing higher temperature PyC, even though the C remaining after exposure to higher pyrolysis temperatures is more stable.     

Computer reconstruction of the physicochemical conditions of sulfide formation for the Krasnov and Ashadze hydrothermal systems (Mid-Atlantic Ridge)

Computer-based reconstruction of the physicochemical conditions of formation of the Krasnov (16° N) and Ashadze (13° N) submarine systems in the Mid-Atlantic Ridge (MAR) has been performed using the equilibrium-thermodynamic approach to study samples from these sites. In the first case, a sphalerite-pyrite-barite association was considered, and in the second case, a sphalerite-pyrite association. In the modeling conducted, the composition of the sphalerite solid solution corresponding to the nonideal mixing of ZnS and FeS was used as a correlation parameter with the total composition of the Fe-Zn-Ba-S-H₂O-NaCl-HCl hydrothermal system depending on temperature (200-300 °C) and a given pressure of 100 bar. The calculation results predict that at an iron content of 0.17-0.36 wt.% in sphalerite, the minimum formation temperatures of the equilibrium sphalerite-pyrite-barite association should correspond to the interval of 280-300 °C (Krasnov site). As the iron content in sphalerite increases to 4.15-13.28 wt.%, the occurrence of barite in the systems studied becomes impossible and the formation temperatures of the sphalerite-pyrite association become equal to or higher than 300 °C (Ashadze site).     

A first step towards identification of tannin-derived black carbon: Conventional pyrolysis (Py–GC–MS) and thermally assisted hydrolysis and methylation (THM–GC–MS) of charred condensed tannins

Tannins account for a significant proportion of plant biomass and are likely to contribute to the residues formed by incomplete biomass combustion (black carbon, BC). Nonetheless, the molecular properties of thermally modified tannins have not been investigated in laboratory charring experiments. We applied conventional analytical pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) and thermally assisted hydrolysis and methylation (THM–GC–MS) to investigate the effects of heat treatment with a muffle furnace on the properties of condensed tannins (CT) from Corsican pine (Pinus nigra) needles. Py–GC–MS showed a decrease in the relative abundance of the 1,2,3-trihydroxybenzenes (pyrogallols) at ⩾300 °C and of the dihydroxybenzenes (mainly catechols) at ⩾350 °C due to dehydroxylation of the CT B ring. Further dehydroxylation led to formation of monohydroxybenzenes (phenols), which showed a strong enrichment between 350 and 400 °C and, at higher temperatures, to a series of monocyclic and polycyclic aromatics [benzene, alkyl benzenes and polycondensed aromatic hydrocarbons (PAHs)]. Degradation of the A ring could not be recognized via Py–GC–MS, probably because of the poor chromatographic behavior of 1,3,5-trihydroxybenzenes (phloroglucinols). The progressive dehydroxylation and eventual polycondensation of the CT B ring was corroborated using THM–GC–MS. In addition, with THM–GC–MS the thermal rearrangement of CT A rings at 300 °C and higher was inferred from the relative abundance of 1,3,5-trimethoxybenzenes (methylated phloroglucinol derivatives). These compounds were observed at moderate/high temperature (up to 450 °C) and can not be produced from THM of lignin, suggesting that they may be markers of CT in natural BC samples.     

Inhibited eclogitization and consequences for geophysical rock properties and delamination models: Constraints from cratonic lower crustal xenoliths

Studies on lower crustal and mantle xenoliths as well as geophysical data provide important information on the cratonic lithosphere. While geothermobarometric calculations of a majority of mantle xenoliths are in agreement with the typically low surface heat flow values of a craton (~ 40 mW/m²), P–T estimates for lower crustal xenoliths deviate significantly from the cratonic geotherms. Independent from the individual cratonic history, the temperatures are ~ 200–300 °C higher than what is expected at the base of the lower crust (~ 500–600 °C at ~ 1.3–1.6 GPa). Possible explanations may be a lack of equilibration to the cratonic geotherm or a relatively recent localized heat input. The presence of granulitic rocks under eclogite-facies conditions which are expected to prevail in the lower cratonic crust has consequences for the interpretation of geophysical rock properties. A mafic granulite which has been preserved under eclogite-facies conditions has densities and P-wave velocities similar to a felsic composition equilibrated to eclogite-facies conditions. Furthermore, phase diagrams calculated from xenolith bulk compositions demonstrate that eclogitization at relatively high temperatures as required for delamination of continental crust can only be triggered at significantly higher pressures than lithostatic at the base of the lower crust. As long as P–T conditions and the rock composition entail the assemblage to be granulitic, the addition of fluid at temperatures above 800 °C will not result in eclogitization, but rather in melt generation. This can also lead to an increase in density of up to 3%, however, this is strongly dependent on the amount of water saturation.     

Rutile geochemistry and thermometry of eclogites and associated garnet-mica schists in the Biga Peninsula,NW Turkey

In northwest Turkey, high-pressure metamorphic rocks occur as exotic blocks within the Çetmi mélange located on the south of the Biga Peninsula. Rutile chemistry and rutile thermometry obtained from the eclogite and associated garnet-mica schist in the Çetmi mélange indicate significant trace element behaviour of subducted oceanic crust and source-rock lithology of detrital rutiles. Cr and Nb contents in detrital rutile from garnet-mica schist vary from 355 to 1026 μg/g and 323 and 3319 μg/g, respectively. According to the Cr-Nb discrimination diagram, the results show that 85% of the detrital rutiles derived from metapelitic and 15% from metamafic rocks. Temperatures calculated for detrital rutiles and rutiles in eclogite range from 540 °C to 624 °C with an average of 586 °C and 611 °C to 659 °C with an average of 630 °C at P = 2.3 GPa, respectively. The calculated formation temperatures suggest that detrital rutiles are derived from amphibolite- and eclogite-facies metamorphic rocks. Amphibolite-facies rocks of the Kazdağ Massif could be the primary source rocks for the rutiles in the garnet-mica schist from the Çetmi mélange. Nb/Ta ratios of metapelitic and metamafic rutiles fall between 7–24 and 11–25, respectively. Nb/Ta characteristics in detrital rutiles may reflect a change in source-rock lithology. However, Nb/Ta ratios of rutiles in eclogite vary from 9 to 22. The rutile grains from eclogites are dominated by subchondritic Nb/Ta ratios. It can be noted that subchondritic Nb/Ta may record rutile growth from local sinks of aqueous fluids from metamorphic dehydration.     

Platinum-group elemental chemistry of the Baima and Taihe Fe–Ti oxide bearing gabbroic intrusions of the Emeishan large igneous province,SW China

Nickel-, copper-, and platinum group element (PGE)-enriched sulphide mineralization in large igneous provinces has attracted numerous PGE studies. However, the distribution and behavior of PGEs as well as the history of sulphide saturation are less clear in oxide-dominated mineralization. Platinum group elements of oxide-bearing layered mafic intrusions from the Emeishan large igneous province are examined in this study. Samples collected from the Baima and Taihe oxide-bearing layered gabbroic intrusions reveal contrasting results. The samples from Baima gabbroic rocks have low total PGE abundances (ΣPGE < 4 ppb) whereas the Taihe gabbroic rocks, on average, have more than double the concentration but are variable ranging from ΣPGE < 2 ppb to ΣPGE ∼300 ppb. The Baima gabbro is platinum-subgroup PGE (PPGE = Rh, Pt and Pd) enriched and iridium-subgroup PGE (IPGE = Os, Ir and Ru) depleted, with a distinct positive Ru anomaly on a primitive mantle normalized multi-element plot. The Taihe gabbros are also PPGE enriched but with negative Ru and Pd anomalies on a primitive mantle normalized multi-element plot. The PGE concentrations of Baima rocks are indicative of fractionation of a relatively evolved, mafic, S-undersaturated parental magma that was affected by earlier sulphide segregation. In contrast, the Taihe rocks record evidence of both S-saturated and S-undersaturated conditions and that the parental magma was likely emplaced very close to S-saturation. Comparisons of the platinum group element contents in the Emeishan flood basalts and the Emeishan oxide-bearing intrusions suggest that the PGE budget in a magma is not controlled by magma series (high-Ti vs. low-Ti), but very much by crustal contamination. The unlikelihood of substantial crustal contamination in the Taihe magma allowed the magma to remain S-undersaturated for a longer duration. PGE and sulphide mineralization was not identified in the Taihe intrusion but the presence of one PGE-enriched sample (Pt + Pd = ∼300 ppb) suggests that the parental magma likely did not experience sulphide segregation and is a potential target for further prospecting.     

On the rheology of partially molten synthetic granite

In an attempt to obviate some of the difficulties inherent in using natural rocks to study experimentally the rheology of partially-molten granitic rocks, we report some preliminary experiments using hot-pressed synthetic aggregates, with quartz as the solid phase and a quartz–albite glass to form the melt phase. Undrained constant displacement rate and stress relaxation experiments were performed at 1100 °C and 300 MPa total confining pressure using nominally 16 and 28 wt% anhydrous melt, and at 980 °C with 12 wt% of water-saturated melt. Strain rate varies non-linearly with stress, corresponding to a stress exponent of 3.6 for the anhydrous melt tests, and 1.9 with the wet melt. Strain rate is enhanced about 160-fold through doubling the melt fraction from 16 wt%. Intracrystalline plasticity appears to contribute insignificantly to the observed deformation, and the preservation of relatively equant grains implies a granular flow process. Microcracking occurs during isostatic hot-pressing, and also contributes to subsequent non-isostatic deformation at high stresses and strain rates. Models of flow of partially molten rock that assume diffusive transfer accommodation of granular flow predict linear viscosity but only at lower strain rates than accessed experimentally. It is suggested that the non-linear granular flow observed in these experiments involved the episodic unsticking of sintered contacts between grains by a rate-dependent cracking and/or dislocation accommodation process.     

P-T evolution of metapelites from the Bajgan complex in the Makran accretionary prism,south eastern Iran

The Bajgan Complex, one of the basement constituents of the arc massif in Iranian Makran forms a rugged, deeply incised terrain. The complex consists of pelitic schists with minor psammitic and basic schists, calc silicate rocks, amphibolites, marbles, metavolcanosediments, mafic and felsic intrusives as well as ultramafic rocks. Metapelitic rocks show an amphibolite facies regional metamorphism and contain garnet, biotite, white mica, quartz, albite ± rutile ± apatite. Thermobarometry of garnet schist yields pressure of more than 9 kbar and temperatures between 560 and 675 °C. The geothermal gradient obtained for the peak of regional metamorphism is 19 °C/km, corresponding to a depth of ca. 31 km. Replacement of garnet by chlorite and epidote suggest greenschist facies metamorphism due to a decrease in temperature and pressure through exhumation and retrograde metamorphism (370–450 °C and 3–6 kbar). The metapelitic rocks followed a ‘clockwise’ P–T path during metamorphism, consistent with thermal decline following tectonic thickening. The formation of medium-pressure metamorphic rocks is related to presence of active subduction of the Neotethys Oceanic lithosphere beneath Eurasia in the Makran.     

Quartzose–mafic spectral feature space model: A methodology for extracting felsic rocks with ASTER thermal infrared radiance data

The original spectral features of felsic rocks are often intermingled with other surface objects, which results in difficulty of detecting felsic rocks using remote sensing techniques. Few felsic rock indices were proposed and visual interpretation with RGB false color composition is widely used to detect felsic rocks. This paper aims to construct a two-dimensional spectral feature space model to extract felsic rocks using ASTER thermal infrared radiance data. The study area is located in northern Qinghai Province, western China with average altitude of approximately 4200 m. A large number of training pixels of mafic–ultramafic rock, quartz-rich rock, felsic rock, carbonate rock and vegetation were selected from the ASTER images as samples of these surface objects. Then we used a quartz-rich rock index (QI, QI = band14 − 0.844 × band12 − 1.897) and a mafic–ultramafic rock index (MI, MI = 0.915 × band10 − band13 + 1.437) to generate a two-dimensional scatter plot. The plot was named after quartzose–mafic spectral feature space (QMFS). The samples show an approximate triangular shape in the QMFS. Mafic–ultramafic rock, quartz-rich rock and carbonate rock are located in separate locations in the three vertex regions, respectively, while felsic rock is located in the central region of the triangle. Next, we calculated a linear belt of silicate rocks in which silicate rocks vary regularly by using a linear regression analysis in the QMFS. Statistical characteristics of the felsic rock samples are analyzed. Afterwards, a polygon which delineates the distribution of felsic rock samples was constructed from the linear belt of silicate rocks. Then we generated a system of inequalities based on the equations of the edges of the polygon. The application of the inequalities to the ASER images shows a good performance of the QMFS for extracting felsic rocks.     

High-temperature,high-pressure granulites (retrogressed eclogites) in the central region of the Lewisian,NW Scotland: Crustal-scale subduction in the Neoarchaean

Eclogites and associated high-pressure (HP) rocks in collisional and accretionary orogenic belts preserve a record of subduction and exhumation, and provide a key constraint on the tectonic evolution of the continents. Most eclogites that formed at high pressures but low temperatures at > 10–11 kbar and 450–650 °C can be interpreted as a result of subduction of cold oceanic lithosphere. A new class of high-temperature (HT) eclogites that formed above 900 °C and at 14 to 30 kbar occurs in the deep continental crust, but their geodynamic significance and processes of formation are poorly understood. Here we show that Neoarchaean mafic–ultramafic complexes in the central granulite facies region of the Lewisian in NW Scotland contain HP/HT garnet-bearing granulites (retrogressed eclogites), gabbros, lherzolites, and websterites, and that the HP granulites have garnets that contain inclusions of omphacite. From thermodynamic modeling and compositional isopleths we calculate that peak eclogite-facies metamorphism took place at 24–22 kbar and 1060–1040 °C. The geochemical signature of one (G-21) of the samples shows a strong depletion of Eu indicating magma fractionation at a crustal level. The Sm–Nd isochron ages of HP phases record different cooling ages of ca. 2480 and 2330 Ma. We suggest that the layered mafic–ultramafic complexes, which may have formed in an oceanic environment, were subducted to eclogite depths, and exhumed as HP garnet-bearing orogenic peridotites. The layered complexes were engulfed by widespread orthogneisses of tonalite–trondhjemite–granodiorite (TTG) composition with granulite facies assemblages. We propose two possible tectonic models: (1) the fact that the relicts of eclogitic complexes are so widespread in the Scourian can be taken as evidence that a > 90 km × 40 km-size slab of continental crust containing mafic–ultramafic complexes was subducted to at least 70 km depth in the late Archaean. During exhumation the gneiss protoliths were retrogressed to granulite facies assemblages, but the mafic–ultramafic rocks resisted retrogression. (2) The layered complexes of mafic and ultramafic rocks were subducted to eclogite-facies depths and during exhumation under crustal conditions they were intruded by the orthogneiss protoliths (TTG) that were metamorphosed in the granulite facies. Apart from poorly defined UHP metamorphic rocks in Norway, the retrogressed eclogites in the central granulite/retrogressed eclogite facies Lewisian region, NW Scotland have the highest crustal pressures so far reported for Archaean rocks, and demonstrate that lithospheric subduction was transporting crustal rocks to HP depths in the Neoarchaean.     

Thermobaric structure of the Himalayan Metamorphic Belt in Kaghan Valley,Pakistan

The thermobaric structure of the Himalayan Metamorphic Belt (HMB) has been constructed along the Kaghan Valley transect, Pakistan. The HMB in this valley represents mainly the Lesser Himalayan Sequence (LHS) and Higher Himalayan Crystallines (HHC). Mineral parageneses of 474 samples, from an approximately, 80-km traverse from southwest to northeast, were examined. Microprobe analyses were carried out to quantify the mineral composition. To determine the pressure–temperature (P–T) conditions, 65 thin sections (7 pelites from LHS and 25 pelites, 9 mafic rocks/amphibolites and 19 eclogites from HHC) were selected. Based on field observations and mineral paragenesis, low-grade to high-grade metapelites, show Barrovian-type progressive metamorphic sequence, with chlorite, biotite, garnet and staurolite zones in LHS and staurolite, kyanite and sillimanite zones in HHC. By using well-calibrated geothermobarometers, P–T conditions for pelitic and mafic rocks are estimated. P–T estimates for pelitic rocks from the garnet zone indicate a condition of 534 ± 17 °C at 7.6 ± 1.2 kbar. P–T estimates for rocks from the staurolite and kyanite zones indicate average conditions of 526 ± 17 °C at 9.4 ± 1.2 kbar and 657 ± 54 °C at 10 ± 1.6 kbar, respectively. P–T conditions for mafic rocks (amphibolites) and eclogites from HHC are estimated as 645 ± 54 °C at 10.3 ± 2 kbar and 746 ± 59 °C at 15.5 ± 2.1 kbar, respectively. The coesite-bearing ultrahigh-pressure (UHP) eclogites record a peak P–T condition of 757–786 °C at 28.6 ± 0.4 kbar and retrograde P–T conditions of 825 ± 59 °C at 18.1 ± 1.7 kbar.These results suggest that HMB show a gradual increase in metamorphic grade from southwest to northeast. The P–T conditions from Pelitic and adjacent mafic rocks having identical peak conditions in the same metamorphic zone, while the structural middle in HHC reached the highest P–T condition upto the UHP grade.     

Naturally occurring arsenic: Mobilization at a landfill in Maine and implications for remediation

Elevated levels of dissolved arsenic (∼300 μg L⁻¹) have been detected beneath and in groundwater plumes extending away from a closed landfill in southern Maine. This study sought to determine the source of arsenic to the aquifer, the processes responsible for arsenic mobilization, and to evaluate the effectiveness of remediation efforts that have occurred at this site. The As appears to originate in the natural (glacial) aquifer solids, which contain ∼5 mg kg⁻¹ As on a dry weight basis. This conclusion is supported by the relatively uniform distribution of As in sediment samples, results of laboratory batch incubation experiments, and comparisons with groundwaters in nearby wetlands, which also have high levels of dissolved As that do not appear to originate within the landfill. The As is mobilized in the subsurface by strongly reducing conditions beneath the landfill and in nearby wetlands. In the aquifer beneath the landfill, the average oxidation–reduction potential (ORP) is −95 mV (Eh + 105 mV), and these reducing conditions were primarily induced by landfill leachate. Remediation efforts at this site have included installation of a low permeability clay cap; groundwater extraction, oxidation, and re-injection; and subsurface oxidation by injection of magnesium peroxide. The natural source of arsenic within the aquifer solids, coupled with widespread reducing conditions, has severely limited the effectiveness of these interventions on groundwater arsenic concentrations.     

The 40Ar/39Ar and Rb–Sr chronology of the Precambrian Aksu blueschists in western China

Three metapelite samples from the Aksu blueschist terrane, Xinjiang, China, were dated by the ⁴⁰Ar/³⁹Ar method on separated phengite grains, obtaining plateau ages in the range of 741−757 Ma. In contrast, the measured Rb and Sr isotope data for the three samples yielded isochron ages ranging from 630 Ma to 900 Ma, suggesting large heterogeneity in the blueschist protolith and suppression of diffusional exchange owing to the low-temperature metamorphic conditions. Because the protolith of Aksu blueschist is composed of oceanic materials that formed ⁴⁰Ar-free phengite during HP and UHP metamorphism and the apparent ⁴⁰Ar/³⁹Ar plateaus ages in this study are similar to previous K–Ar and Rb–Sr ages, the existence of excess argon in these rocks is considered to be insignificant. As a result, the ⁴⁰Ar/³⁹Ar plateau ages in this study (ca. 750 Ma) likely represent the approximate time for peak metamorphism, given the low peak metamorphic temperatures for the Aksu blueschist terrane (300−400 °C). This strongly implies that modern style, cold subduction tectonics operated along the margin of the Aksu terrane no later than 750 Ma, in Neoproterozoic time.     

Fluid elemental and stable isotope composition of the Nibelungen hydrothermal field (8°18′S,Mid-Atlantic Ridge): Constraints on fluid–rock interaction in heterogeneous lithosphere

Depending on the geological setting, the interaction of submarine hydrothermal fluids with the host rock leads to distinct energy and mass transfers between the lithosphere and the hydrosphere. The Nibelungen hydrothermal field is located at 8°18′S, about 9 km off-axis of the Mid-Atlantic Ridge (MAR). At 3000 m water depth, 372 °C hot, acidic fluids emanate directly from the bottom, without visible sulfide chimney formation. Hydrothermal fluids obtained in 2009 are characterized by low H₂S concentrations (1.1 mM), a depletion of B (192 μM) relative to seawater, lower Si (13.7 mM) and Li (391 μM) concentrations relative to basaltic-hosted hydrothermal systems and a large positive Eu anomaly, and display a distinct stable isotope signature of hydrogen (?²H_H2O = 7.6–8.7‰) and of oxygen (?¹⁸O_H2O = 2.2–2.4‰).The heavy hydrogen isotopic signature of the Nibelungen fluids is a specific feature of ultramafic-hosted hydrothermal systems and is mainly controlled by the formation of OH-bearing alteration minerals like serpentine, brucite, and tremolite during pervasive serpentinization. New isotopic data obtained for the ultramafic-hosted Logatchev I field at 14°45′N, MAR (?²H_H2O = 3.8–4.2‰) display a similar trend, being clearly distinguished from other, mafic-hosted hydrothermal systems at the MAR.The fluid geochemistry at Nibelungen kept stable since the first sampling campaign in 2006 and is evident for a hybrid alteration of mafic and ultramafic rocks in the subseafloor. Whereas the ultramafic-fingerprint parameters Si, Li, B, Eu anomaly and ?²H_H2O distinguish the Nibelungen field from other hydrothermal systems venting in basaltic settings at similar physico-chemical conditions and are related to the interaction with mantle rocks, the relatively high concentrations of trace alkali elements, Pb, and Tl can only be attributed to the alteration of melt-derived gabbroic rocks. The elemental and isotopic composition of the fluid suggest a multi-step alteration sequence: (1) low- to medium-temperature alteration of gabbroic rocks, (2) pervasive serpentinization at moderate to high temperatures, and (3) limited high-temperature interaction with basaltic rocks during final ascent of the fluid. The integrated water/rock ratio for the Nibelungen hydrothermal system is about 0.5.The fluid compositional fingerprint at Nibelungen is similar to the ultramafic-hosted Logatchev I fluids with respect to key parameters. Some compositional differences can be ascribed to different alteration temperatures and other fluid pathways involving a variety of source rocks, higher water/rock ratios, and sulfide precipitation in the sub-seafloor at Logatchev I.     

Zircon captures exhumation of an ultrahigh-pressure terrane,North-East Greenland Caledonides

Zircon from the North-East Greenland ultrahigh-pressure (UHP) terrane formed over a 45 million year period from peak UHP conditions through the amphibolite facies. Our study utilizes sensitive high resolution ion microprobe-reverse geometry (SHRIMP-RG) mass spectrometry to assess the multiple ages and trace element patterns preserved in zircon from samples chosen to capture the exhumation history of these rocks. Peak UHP conditions from 365 to 350 Ma are derived from coesite-bearing samples, while a suite of progressively retrogressed quartzofeldspathic host gneisses and late-stage, leucocratic melts emplaced into the gneisses track exhumation. Melting occurred during all stages of exhumation, beginning with H₂O-absent dehydration melting of phengite on the decompression path. A garnet-bearing leucosome in the neck of a kyanite-eclogite boudin that gives an age of 347 Ma is taken as the beginning of phengite melting. Leucosomes formed in HP granulite to amphibolite facies gneisses between 350 and 340 Ma, and fluid assisted melting continued until 320 Ma in the form of late, cross cutting pegmatites. Changes in the zircon trace element patterns are linked to decreasing temperature, and show that significant new zircon grew during melting on the exhumation path. Zircon cores recording protolith ages generally preserve magmatic temperatures (700 °C) and typical igneous REE patterns (Yb/Gd = 10). UHP/HP eclogite-facies zircon records higher T (900 °C) and flat HREE patterns (Yb/Gd = 1). Granulite to amphibolite facies zircon in quartzofeldspathic gneisses records both flat (Yb/Gd = 1) and steep (Yb/Gd = 100) HREE patterns at ca 700 °C suggesting the variable effects of garnet during decompression. Amphibolite facies pegmatites and leucosomes document a transition from moderate HREE (Yb/Gd = 10) at 700 °C to steep HREE (Yb/Gd = 100–1000) patterns at 600 °C. The pronounced steepening of the HREE patterns is attributed to garnet breakdown during amphibolite-facies metamorphism. The 30–50 million year spread of ages observed in individual samples records multiple periods of zircon growth and is interpreted as a characteristic signature of slowly exhumed UHP terranes. The data show that zircon ages combined with trace element and textural characterization of zircon from a broad suite of samples can successfully define the exhumation history of UHP terranes.     

Anatomy of a world-class epizonal orogenic-gold system: A holistic thermochronological analysis of the Xincheng gold deposit,Jiaodong Peninsula,eastern China

Xincheng is a world-class orogenic-gold deposit hosted by the Early Cretaceous Guojialing granitoid in the Jiaodong Peninsula, eastern China. A zircon U–Pb age of 126 ± 1.4 Ma, together with previous data, constrain the emplacement of the Guojialing intrusion to 132–123 Ma. The granitoid underwent subsolidus ductile deformation at >500 °C following its intrusion. The small difference in age between the youngest zircon U–Pb age of unaltered granitoid (~123 Ma) and the ca. 120 Ma ⁴⁰Ar/³⁹Ar ages of sericite, associated with breccias and gold mineralization within it indicate initial rapid cooling from magmatic temperatures to those prevalent during brittle deformation and associated gold mineralization at ~220–300 °C. Evidence of a direct association between granitic magmatism and gold mineralization, such as at least localized near-magmatic depositional temperatures and metal zoning evident in undoubted intrusion-related gold deposits, is absent. The ⁴⁰Ar/³⁹Ar age of ~120 Ma coincides with the mineralization age of many other orogenic-gold deposits along the Jiaojia Fault. Sixteen zircon fission-track (ZFT) ages across the ore and alteration zones range from 112.9 ± 3.4 to 99.1 ± 2.7 Ma. The long period of cooling to the ~100 Ma ZFT closure temperatures recorded here suggests that ambient temperatures for hydrothermal alteration systems lasted to ~100 Ma, possibly because of their focus at Xincheng within the young Guojialing granitoid as it cooled more slowly below approximately 300 °C to 220 °C. However, the restricted number of auriferous ore stages, combined with the presence of cross-cutting gold-free quartz-carbonate veins, indicate that gold itself was only deposited over a restricted time interval at ~120 Ma, consistent with studies of orogenic gold deposits elsewhere. This highlights the complex interplay between magmatism, deformation and the longevity of hydrothermal systems that cause genetic controversies. Based on apatite fission-track (AFT) ages, the Xincheng gold deposit was then uplifted and exhumed to near the surface of the crust at 15 Ma, probably due to movement on the crustal-scale Tan-Lu Fault. Recognition of such exhumation histories along gold belts has conceptual exploration significance in terms of the probability of discovery of additional exposed or sub-surface gold ore bodies as discovery is as much a function of preservation as formation of the deposits.