Blue amphibole-albite-chlorite assemblages from Fuscaldo (S Italy) and the role of glaucophane in metamorphism

The Fuscaldo assemblages show that in metabasites suitable for the production of glaucophane at higher pressures, amphibole poor(er) in Gl-molecule + albite + Al-rich chlorite is formed at lower pressure. Blue amphibole formed together with albite, chlorite and a Ca-silicate appears to have a fixed content of the Gl-molecule and of Ca²⁺, apart from the Fe²⁺/ R²⁺ ratio, which varies with host rock chemistry. The constant Gl-content indicates attainment of equilibrium, and is a function of T and especially P, so it may be used as a geobarometer. Glaucophane generally forms at the cost of albite+chlorite. In a P-T diagram the reaction is probably situated somewhat below the reaction albitejadeite+quartz, and has a smaller slope than the latter. The concomitant high-pressure character of glaucophane justifies reintroduction of Eskola's glaucophane-schist facies, of which glaucophane is critical.     

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand

Brothers volcano, of the Kermadec intraoceanic arc, is host to a hydrothermal system unique among seafloor hydrothermal systems known anywhere in the world. It has two distinct vent fields, known as the NW Caldera and Cone sites, whose geology, permeability, vent fluid compositions, mineralogy, and ore-forming conditions are in stark contrast to each other. The NW Caldera site strikes for ??600?m in a SW?CNE direction with chimneys occurring over a ??145-m depth interval, between ??1,690 and 1,545?m. At least 100 dead and active sulfide chimney spires occur in this field and are typically 2?C3?m in height, with some reaching 6?C7?m. Their ages (at time of sampling) fall broadly into three groups: <4, 23, and 35?years old. The chimneys typically occur near the base of individual fault-controlled benches on the caldera wall, striking in lines orthogonal to the slopes. Rarer are massive sulfide crusts 2?C3?m thick. Two main types of chimney predominate: Cu-rich (up to 28.5?wt.% Cu) and, more commonly, Zn-rich (up to 43.8?wt.% Zn). Geochemical results show that Mo, Bi, Co, Se, Sn, and Au (up to 91?ppm) are correlated with the Cu mineralization, whereas Cd, Hg, Sb, Ag, and As are associated with the dominant Zn-rich mineralization. The Cone site comprises the Upper Cone site atop the summit of the recent (main) dacite cone and the Lower Cone site that straddles the summit of an older, smaller, more degraded dacite cone on the NE flank of the main cone. Huge volumes of diffuse venting are seen at the Lower Cone site, in contrast to venting at both the Upper Cone and NW Caldera sites. Individual vents are marked by low-relief (??0.5?m) mounds comprising predominately native sulfur with bacterial mats. Vent fluids of the NW Caldera field are focused, hot (??300°C), acidic (pH????2.8), metal-rich, and gas-poor. Calculated end-member fluids from NW Caldera vents indicate that phase separation has occurred, with Cl values ranging from 93% to 137% of seawater values. By contrast, vent fluids at the Cone site are diffuse, noticeably cooler (??122°C), more acidic (pH?1.9), metal-poor, and gas-rich. Higher-than-seawater values of SO₄ and Mg in the Cone vent fluids show that these ions are being added to the hydrothermal fluid and are not being depleted via normal water/rock interactions. Iron oxide crusts 3?years in age cover the main cone summit and appear to have formed from Fe-rich brines. Evidence for magmatic contributions to the hydrothermal system at Brothers includes: high concentrations of dissolved CO₂ (e.g., 206?mM/kg at the Cone site); high CO₂/³He; negative ??D and ??¹⁸O_H2O for vent fluids; negative ??³⁴S for sulfides (to ?4.6??), sulfur (to ?10.2??), and ??¹⁵N₂ (to ?3.5??); vent fluid pH values to 1.9; and mineral assemblages common to high-sulfidation systems. Changing physicochemical conditions at the Brothers hydrothermal system, and especially the Cone site, occur over periods of months to hundreds of years, as shown by interlayered Cu?+?Au- and Zn-rich zones in chimneys, variable fluid and isotopic compositions, similar shifts in ³He/⁴He values for both Cone and NW Caldera sites, and overprinting of ??magmatic?? mineral assemblages by water/rock-dominated assemblages. Metals, especially Cu and possibly Au, may be entering the hydrothermal system via the dissolution of metal-rich glasses. They are then transported rapidly up into the system via magmatic volatiles utilizing vertical (??2.5?km long), narrow (??300-m diameter) ??pipes,?? consistent with evidence of vent fluids forming at relatively shallow depths. The NW Caldera and Cone sites are considered to represent stages along a continuum between water/rock- and magmatic/hydrothermal-dominated end-members.     

An Equation of State for Hypersaline Water in Great Salt Lake,Utah, USA

Great Salt Lake (GSL) is one of the largest and most saline lakes in the world. In order to accurately model limnological processes in GSL, hydrodynamic calculations require the precise estimation of water density (ρ) under a variety of environmental conditions. An equation of state was developed with water samples collected from GSL to estimate density as a function of salinity and water temperature. The ρ of water samples from the south arm of GSL was measured as a function of temperature ranging from 278 to 323 degrees Kelvin (^oK) and conductivity salinities ranging from 23 to 182 g L⁻¹ using an Anton Paar density meter. These results have been used to develop the following equation of state for GSL (σ = ± 0.32 kg m⁻³):

Phytoreduction and volatilization of mercury by ascorbate in Arabidopsis thaliana, European beech and Norway spruce

Mercury vapor (Hg⁰) emission from plants contributes to the atmospheric Hg cycle. Young barley (Hordeum vulgare L.) plants grown on a hydroponic cultivation medium containing Hg(II) have previously been shown to increase their Hg⁰ emission significantly by reduction of Hg(II) with endogenous ascorbic acid. Regarding the potential contribution to the Hg cycle from the vast forest-covered areas, it was important to investigate this mechanism in trees. The increase in Hg⁰ emission from young European beech plants cultivated on a HgCl₂ medium exceeded that from controls by ca. tenfold and was proportional to the Hg(II) concentration. From these experiments, a flux of 12.8 μg Hg⁰/h/m² was estimated at an exposure of the roots to 20 μM Hg(II). Mercury vapor release from homogenates of Norway spruce needles exceeded that from European beech leaves by a factor of 2.3–4, i.e. in proportion to the reported AA concentrations; the reduction was maximal at alkaline pH which is typical for AA. The 8.4-fold difference in Hg⁰ release between homogenates from wild-type Arabidopsis thaliana and from its AA-deficient mutant vtc 1-1 also paralleled the reported difference in AA levels of both species. It is concluded that the phytoreduction and vaporization of Hg by AA is an important mechanism as much for Hg detoxification in trees as for Hg emission to the atmosphere. The efficiency of this process seems to result from the optimal coordination of transfer and biochemical transformation of mercuric ions and Hg vapor. There is no evidence for a relevant difference in the mechanisms of biogenic Hg(II) reduction between grass plants and trees.     

Salt kinematics and regional tectonics across a Permian gas field: a case study from East Frisia, NW Germany

This study presents a reconstruction of the tectonic history of an Upper Rotliegend tight gas field in Northern Germany. Tectonism of the greater study area was influenced by multiple phases of salt movement, which produced a variety of salt-related structural features such as salt walls, salt diapirs as well as salt glaciers (namakiers). A sequential 2D retro-deformation and stratal backstripping methodology was used to differentiate mechanisms inducing salt movement and to discuss their relation to regional tectonics. The quantitative geometric restoration included sedimentary balancing, decompaction, fault-related deformation, salt movement, thermal subsidence, and isostasy to unravel the post-depositional tectonic overprint of the Rotliegend reservoir rock. The results of this study indicate that reactive salt diapirism started during an Early Triassic interval of thin-skinned extensional tectonics, followed by an active diapirism stage with an overburden salt piercement in the Late Triassic, and finally a period of intensive salt surface extrusion and the formation of salt glaciers (namakiers) in Late Triassic and Jurassic times. Since the Early Cretaceous, salt in the study area has been rising by passive diapirism.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄ ^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄ ^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄ ^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄ ^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃ ^- in the solutions. An increase in the concentration of HCO₃ ^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃ ^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.     

Coupling hydrogeological with surface runoff model in a Poltva case study in Western Ukraine

This paper presents the hydrological coupling of the software framework OpenGeoSys (OGS) with the EPA Storm Water Management Model (SWMM). Conceptual models include the Saint Venant equation for river flow, the 2D Darcy equations for confined and unconfined groundwater flow, a two-way hydrological coupling flux in a compartment coupling approach (conductance concept), and Lagrangian particles for solute transport in the river course. A SWMM river–OGS aquifer inter-compartment coupling flux is examined for discharging groundwater in a systematic parameter sensitivity analysis. The parameter study involves a small perturbation (first-order) sensitivity analysis and is performed for a synthetic test example base-by-base through a comprehensive range of aquifer parametrizations. Through parametrization, the test cases enables to determine the leakance parameter for simulating streambed clogging and non-ocillatory river-aquifer water exchange rates with the sequential (partitioned) coupling scheme. The implementation is further tested with a hypothetical but realistic 1D river–2D aquifer model of the Poltva catchment, where discharging groundwater in the upland area affects the river–aquifer coupling fluxes downstream in the river course (propagating feedbacks). Groundwater contribution in the moving river water is numerically determined with Lagrangian particles. A numerical experiment demonstrates that the integrated river–aquifer model is a serviceable and realistic constituent in a complete compartment model of the Poltva catchment.     

A new technique for precise uranium-series dating of travertine micro-samples

Secondary carbonate formations, such as travertine and calcareous tufa deposits, are important archives for quaternary continental climate studies and archaeology. The extremely complex growth mechanisms result in some serious problems for precise mass spectrometric uranium-series dating. Often, detrital and organic particles contaminate the carbonate and large pore volumes yield a great potential for open system behavior. We utilized microscopic, mineralogical and geochemical methods prior to sample selection to determine the abundance of primary calcite, i.e. micrite and spar. Furthermore, the state of alteration was characterized by cathodoluminescence and trace-element analysis. We conclude that travertine and calcareous tufa are appropriate for precise U-series age determination if a) micrite and/or spar are the dominant phases; b) cathodoluminescence of both phases is weak or absent; c) Fe and Al levels are low; and d) Sr concentrations are close to the average of the studied site. We mapped and sampled solely areas of major micrite/spar abundance having minor alteration for accurate U-series dating. When this new method was applied, travertines located in eastern Germany (sites Bad Langensalza, Burgtonna and Weimar-Ehringsdorf) gave single ²³⁰Th/²³⁸U-ages consistent with the lithological growth sequence and greatly improved compared to previously published chronologies. In addition, we determined ²³⁰Th/U isochron ages on bulk samples that confirm our single ages. In contrast to primary calcite, pore cements are homogeneously distributed throughout the travertine fabric and reflect early diagenetic processes and/or weathering.     

The early Caledonian (Finnmarkian) event reassessed in Finnmark: Ar/Ar cleavage age data from NW Varangerhalvøya, N. Norway

The relative significance of early (Finnmarkian) and late (Scandian) Caledonian deformation in N. Norway is uncertain. Early studies suggested pervasive Finnmarkian deformation whilst later results indicated a restricted Finnmarkian domain. The present work suggests it was more widespread than accepted and that inter Finnmarkian–Scandian deformation occurred. ⁴⁰Ar/³⁹Ar dating of 2–6 and 6–11 μm pelitic fractions from the lower to mid-greenschist facies Tanahorn Nappe (five samples; base Middle Allochthon) and the epizone Løkvikfjellet and Barents Sea Groups (three samples; North Varanger Region) in the north Scandinavian Caledonides show slightly discordant spectra. Most spectra from the Tanahorn Nappe preserve possible evidence of an early Caledonian event in the high temperature steps, with recoil/excess Ar effects in the low temperature steps; no pre-Caledonian relict component has been recorded. The results indicate Finnmarkian deformation continued to 460 Ma, with Scandian reactivation at 425–415 Ma. From the North Varanger Region, a strongly crenulated sample yielded plateau ages (444–442 Ma); means of combined young steps from weakly to uncrenulated samples gave 470–450 Ma, suggesting penetrative strike-slip deformation occurred in the late Finnmarkian to inter-Finnmarkian–Scandian period. No Scandian ages were recorded in the North Varanger Region. Reassessment of published data from the Laksefjord Nappe and Gaissa Thrust Belt suggests they were affected by Finnmarkian deformation.