The behaviour of boron in a peraluminous granite-pegmatite system and associated hydrothermal solutions: a melt and fluid-inclusion study

Detailed analyses of melt and fluid inclusions combined with an electron-microprobe survey of boron-bearing minerals reveal the evolution of boron in a highly evolved peraluminous granite-pegmatite complex and the associated high- and medium-temperature ore-forming hydrothermal fluids (Ehrenfriedersdorf, Erzgebirge, Germany). Melt inclusions in granite represent embryonic pegmatite-forming melts containing about 10 wt% H₂O and 1.8 wt% B₂O₃. These melts are also enriched in F, P, and other incompatible elements such as Be, Sn, Rb, and Cs. Ongoing differentiation and volatile enrichment drove the system into a solvus, where two pegmatite-forming melts coexisted. The critical point is at about 712 °C, 100 MPa, 20 wt% H₂O and 4.1 wt% B₂O₃. Cooling and concomitant fractional crystallisation from 700 to 500 °C induced development of two conjugate melts, an H₂O-poor (A-melt) and an H₂O-rich melt (B-melt) along the opening solvus. Boron is a major element in both melts and is preferentially partitioned into the H₂O-rich melt. Temperature-dependent distribution coefficients D_boron^{B - melt/A - melt} D_{{\rm{boron}}}^{{\rm{B - melt/A - melt}}} are 1.3 at 650 °C, 1.5 at 600 °C, and 1.8 at 500 °C. In both melts, boron concentrations decreased during cooling because of exsolution of a boron-rich hypersaline brine throughout the pegmatitic stage. Boromuscovite containing up to 8.5 wt% was another sink for boron at this stage. The end of the melt-dominated pegmatitic stage was attained at a solidus temperature of around 490 °C. Fluid inclusions of the hydrothermal stage reveal trapping temperatures of 480 to 370 °C, along with varying densities and highly variable B₂O₃ contents ranging from 0.20 to 2.94 wt%. A boiling system evolved, indicating a complex interplay between closed- and open-system behaviour. Pressure switched from lithostatic to hydrostatic and back, generating hydrothermal convection cells where meteoric waters were introduced and mixed with magmatic fluids. Boron-rich solutions originated from magmatic fluids, whereas boron-depleted fluids were mainly of meteoric origin. This highlights the potential of boron for discriminating fluids of different origin. Tin is continuously enriched during the evolution because tin and boron are cross-linked by formation of boron-, fluorine- and tin-fluorine-bearing complexes and is finally deposited within quartz-cassiterite veins during the transition from closed- to open-system behaviour. Boron does not only trace the complex evolution of the Ehrenfriedersdorf complex but exerts, together with H₂O, F and P, an important control on the physical and chemical properties of pegmatite-forming melts, and particularly on the formation of a two-melt solvus at low pressure. We discuss this with respect to experimental results on H₂O solubility and the critical behaviour of the haplogranite-water system which contained variable concentrations of volatiles.     

Compositions of magmatic hydrothermal fluids determined by LA-ICP-MS of fluid inclusions from the porphyry copper–molybdenum deposit at Butte, MT

We analyzed 85 fluid inclusions from seven samples from the porphyry Cu–Mo deposit in Butte, MT, using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The Butte deposit formed at unusually great depth relative to most porphyry deposits, and fluid inclusions in deep veins trapped a low-salinity, CO₂-bearing, magmatically derived, supercritical fluid as a single aqueous phase. This fluid is interpreted to be the parent fluid that cooled, decompressed, unmixed, and reacted with wall rock to form the gigantic porphyry Cu deposit at Butte. Few previous analyses of such fluids exist.Low-salinity, aqueous fluids from the earliest veins at Butte are trapped in deep veins with biotite-rich alteration envelopes (EDM veins). These veins, and the Butte quartz monzonite surrounding them, host much of the Butte porphyry Cu mineralization. Twenty fluid inclusions in one EDM quartz vein are dominated by Na, K, Fe (from 0.1 to 1 wt.%) and contain up to 1.3 wt.% Cu. These inclusions contain only small amounts (tens of ppm) of Pb, Zn, and Mn, and typically contain Li, B, Ca, As, Mo, Ag, Sn, Sb, Ba, and W in less than detectable quantities. The abundance of Cu in early fluids indicates that a low-salinity, Cu-rich, aqueous ore fluid can be directly produced by aqueous fluid separation from a granitic magma. Similar inclusions (eight) in an early deep quartz–molybdenite vein with a K-feldspar selvage have similar compositions but contain significantly less Cu than most inclusions in the biotite-altered vein. Analyzed inclusions in both veins contain less than detectable concentrations of Mo even though one is molybdenite-bearing.Low-salinity, CO₂-bearing aqueous fluids are also trapped in pyrite–quartz veins with sericitic selvages. These veins cut both of the above vein types and contain inclusions that were trapped at lower pressure and temperature. Thirty-nine inclusions in two such veins have compositions similar to early fluids, but are enriched by up to a factor of 10 in Mn, Pb, and Zn relative to early fluids, and are slightly depleted in Fe. Many of these inclusions contain as much or more Cu than early fluids, although little chalcopyrite is found in or around pyrite–quartz veins.Eighteen halite-bearing inclusions from three veins from both chalcopyrite-bearing and barren veins with both K-silicate and sericitic selvages were analyzed as well. Halite-saturated inclusions are dominated by Na, K, Fe, and in some inclusions Ca. Whereas these inclusions are significantly enriched in Ca, Mn, Fe, Zn, and Pb, fluids in all three veins contain significantly less Cu than early, high temperature, low-salinity inclusions.Analyses of all inclusion types show that whereas bulk-salinity of the hydrothermal fluid must be largely controlled by the magma, fluid–rock interactions have a significant role in controlling fluid compositions and metal ratios. Cu concentrations range over an order of magnitude, more than any other element, in all four samples containing low-salinity inclusions. We infer that variations are the result of fluid trapping after different amounts of fluid–rock reaction and chalcopyrite precipitation. Enrichment, relative to early fluids, of Mn, Pb, and Zn in fluids related to sericitic alteration is also likely the result of fluid–rock reaction, whereby these elements are released from biotite and feldspars as they alter to sericite. In halite-bearing inclusions, concentrations of Sr, Ca, Pb, and Ba are elevated in inclusions from the pyrite–quartz vein with sericitic alteration relative to halite-bearing inclusions from unaltered and potassically altered samples. Such enrichment is likely caused by the breakdown of plagioclase and K-feldspar in the alteration envelope, releasing Sr, Ca, Pb, and Ba.     

Accurate quantification of melt inclusion chemistry by LA-ICPMS: a comparison with EMP and SIMS and advantages and possible limitations of these methods

Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) has recently emerged as a powerful in situ microanalytical technique for major to trace elements in heterogeneous samples such as fluid and melt inclusions. Here, a rigorous comparison of melt inclusion (MI) data acquired by electron microprobe (EMP), ion microprobe (the secondary ion mass spectrometry, SIMS) and LA-ICPMS is used to evaluate the applicability and advantages/drawbacks of these approaches. We are specifically interested in determining if LA-ICPMS data on entire, unexposed, crystallized MI that cannot be homogenized in the lab are accurate and of a useful precision.

Quantification of LA-ICPMS MI signals requires the use of an internal standard, i.e., the concentration of one element, or an element ratio, at the time of MI entrapment must be known independently, in order to derive the pure MI composition from the MI plus host mixed signal. Analysis of plagioclase-hosted glassy MI of a mid-ocean ridge basalt (MORB) sample from the East Pacific Rise illustrates that melt inclusion chemistry can be accurately quantified by LA-ICPMS, including the correction for postentrapment sidewall crystallisation of the host mineral without prior reheating in the lab.

The LA-ICPMS data obtained on crystallized MI demonstrate agreement with the EMP and SIMS data on exposed glassy MI at the 1 standard deviation uncertainty level except for a few elements close to their limits of detection. LA-ICPMS data reduction schemes include the quantification of analytical uncertainty on each element of single MI. Therefore, weighted average element concentrations can be obtained for MI assemblages, at precisions that compare well with those of average element concentrations obtained by EMP and SIMS.

Simple sample preparation minimizing inclusion loss through polishing combined with the analytical efficiency of 50 inclusions plus neighbouring host mineral at up to 40 elements per day enable the collection of statistically relevant datasets by LA-ICPMS. These allow to recognize nonrepresentative MI (e.g., heterogeneous entrapment). Application to individual clinopyroxene crystals from the AD79 pumice horizon of Mt. Somma-Vesuvius reveals chemical variability that exceeds the analytical precision on single melt inclusions. This variability was not obvious from the limited data set obtained by SIMS and EMP.

The largest source of nonquantifiable error for EMP and SIMS data stems from the requirement of reheating the melt inclusions in the lab in order to reverse postentrapment crystallisation onto inclusion walls or growth of crystallites. For LA-ICPMS analysis of unexposed MI, the reliability with which the internal standard (IS) element concentration is known determines the quality of the data. LA-ICPMS, however, cannot analyse H₂O, F, S and Cl reliably, has higher limits of detection (LODs) than SIMS for some elements for MI below 25 μm, has lower spatial resolution than both EMP and SIMS and consumes much more sample per analysis. Therefore, EMP, SIMS and LA-ICPMS are complementary in MI research, and the type of application will determine the analytical method or methods of choice.     

Neuere Veröffentlichungen

Ohne Zusammenfassung     

Bathymetrie und Geomorphologie des NOAMP-Gebietes,Westeuropäisches Becken (17° W bis 22° W, 46° N bis 49° N)

Zusammenfassung Im Westeuropäischen Becken wurden bathymetrische Vermessungen und geomorphologische Untersuchungen zur Unterstützung eines ozeanographischen Meßprogramms (NOAMP) des Deutschen Hydrographischen Instituts durchgeführt. Für das zentrale Arbeitsgebiet wurde mit dem SEA BEAM-System eine sehr exakte Tiefenkarte erstellt. Die Karte der weiteren Umgebung ergab sich aus den NBS-Lotungen während der Profilfahrten des hydrographischen Meßprogramms.Die bathymetrischen Karten zeigen Wassertiefen zwischen 3500 und 4900 m an. Das Relief ist damit deutlich rauher, als es aus bisherigen Vermessungen zu erwarten war. Es herrschen NNE-SSW-streichende Strukturen vor, die parallel zum Mittelatlantischen Rücken verlaufen. Ab und zu werden diese durch breite, E-W-verlaufende Senken geschnitten. Bei diesen Senken handelt es sich vermutlich um derzeit inaktive ozeanische Bruchzonen.Die basaltische Kruste hat im Zentralgebiet ein paläozänes bis eozänes Alter (Magnetanomalie 26 bis 21). Die basaltischen Rücken tragen eine ca. 30 m mächtige Sedimentdecke, die das schroffe Krustenrelief noch nicht geglättet hat. Tiefergelegene Rinnen und Senken besitzen durch Sedimentumlagerung und (nördlich 47° N) durch Turbiditzufuhr aus dem Maury-Channel-System südlich von Island eine mehr als 150 m mächtige Sedimentfüllung.

---

Bathymetric and physiographic charting in the NOAMP area, West European Basin (17° W to 22° W, 46° N to 49° N)

Summary The Deutsches Hydrographisches Institut (DHI), Hamburg, is carrying out an oceanographic measurement programme in the NE Atlantik (NOAMP) in order to compute the transportation paths of dissolved and particulate substances from the ocean bottom up to surface layers. One of the main tasks, to resolve the movements of the bottom currents, required detailed knowledge of the structure of the ocean floor. Therefore, the oceanographic data collection was accompanied by bathymetric charting and a geophysical site survey (continuous profiling of reflection seismic, gravity, and orientation of magnetism) of the central area of investigation. The mapping of the central NOAMP area was carried out with the SEA BEAM system (RV Polarstern, RV Sonne). NBS soundings, recorded during the hydrographic cruises, were evaluated for a map of the outer vicinity.As the most important result, the mapping revealed a much more sophisticated relief than was expected from known charts. The water depth range between 3500 and 4900 m. A system of ridges and furrows, with a mean crest-to-crest distance of 10 nautical miles, trends parallel to the Mid-Atlantic Ridge (NNE to SSW). This system is cut each 50 nautical miles by broad E-W striking valleys. The ridges climb about 300 to 400 m above the bottom of the furrows. Some peaks sitting on top of the ridges rise up to the shallowest depths of 3500 m.The internal cores of the ridges consist of basaltic ocean crust, as can be seen by the relative increases of the Bouguer gravity. In the central NOAMP area, the age of the crust is Paleocene to Eocene (magnetic anomalies 26 to 21). The E-W striking valley at 47° 30 N is interpreted as a fossil fracture zone, due to the Z-like bending of the magnetic anomalies.The sediment cover is rather thin on elevations (about 30 m). Therefore, the rough microtopography of the basaltic crust is not yet buried. Downslope mass transport of sediment by currnets and submarine slides raised the sediment thickness in the deeper furrows to more than 100 m, and smoothed out the floor. North of 47° N, there is an additional supply of sediment by turbidity currents from the depositional Maury Channel system south of Iceland.

---

Relevés bathymétriques et physiographiques dans la zone NOAMP, bassin européen Ouest (17° W à 22° W, 46° N à 49° N)

Résumé Le Deutsches Hydrographisches Institut (DHI) de Hamburg, est en train d'exécuter un programme de mesures océanographiques dans l'Atlantique Nord-Est (NOAMP), dans le but de déterminer le cheminement du transport des substances dissoutes et particulaires du fond de l'océan vers les couches de surface. L'une des principales tâches, étant la détermination des déplacements des courants de fond, elle exigeait une connaissance détaillée de la structure du fond de l'océan. En conséquence, la collecte des données océanograhiques fut accompagnée de relevés bathymétriques et d'un levé géophysique sur le site (profils continus de réflexion sismique, gravité, orientation du champ magnétique) de la zone centrale d'investigation. La cartographie de la zone centrale NOAMP a été réalisée à l'aide du sondeur «SEA BEAM» (RV «Polarstern», RV «Sonne»). Les sondages NBS enregistrés au cours des campagnes hydrographiques, étaient évalués pour une carte du voisinage extérieur.Le résultat le plus important, révélé par la cartographie, était un relief beaucoup plus complexe que celui auquel on pouvait s'attendre à la lecture des cartes existantes. La profondeur était comprise entre 3500 et 4900 m. Un système de dorsales et de sillons, avec une distance moyenne de crête à crête de 10 milles marins, s'étire parallèlement à la dorsale médiane de l'Atlantique (du NNE au SSW). Ce système est interrompu tous les 50 milles marins par de larges vallées de direction Est-Ouest. Les dorsales culminent de 300 à 400 m au-dessus du fond des sillons. Quelques pics situés au sommet des dorsales remontent vers les profondeurs les plus faibles qui sont de 3500 m.La structure interne des dorsales consiste en une croûte de basalte océanique comme cela peut être observé par l'augmentation relative de l'anomalie de Bouguer. Dans la partie centrale de la zone NOAMP, l'âge de la croûte s'étale du paléocène à l'éocène (les anomalies magnétiques de 26 à 21). La vallée de direction Est-Ouest située en 47° 30 N, est interprétée comme une zone de fracture fossile, attribuable à la sinuosité, en forme de Z, des anomalies magnétiques.La couverture sédimentaire est plutôt mince sur les hauteurs (de l'ordre de 30 m). C'est pourpuoi, la microtopographie grossière de la croûte basaltique n'est pas encore enfouie. Le transport en masse des sédiments suivant la pente descendante du aux courants et aux glissements sous-marins ont augmenté l'épaisseur du sédiment dans les sillons les plus profonds jusqu'à plus de 100 m et ont «lissé» le fond. Il existe au Nord de 47° N, un apport supplémentaire de sédiments amené par des courants de turbidité provenant du dépôt de Maury Channel au Sud de l'Islande.

     

Experimental investigation of the mechanism of the reaction: 1 tremolite+11 dolomite ⇌ 8 forsterite+13 calcite+9 CO2+1H2O

Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO₂-H₂O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO₂ produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO₂ concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO₂-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO₂-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:

1. Dissolution of the reactants tremolite and dolomite.
2. Diffusion of the dissolved constituents in the fluid.
3. Heterogeneous nucleation of the product minerals.
4. Growth of forsterite and calcite from the fluid.

Two possible explanations are discussed for the development of the amoured texture at \(X_{{\text{CO}}_{\text{2}} }\) above 0.4. The first is based upon the assumption that dolomite has a lower rate of dissolution than tremolite at high \(X_{{\text{CO}}_{\text{2}} }\) values resulting in preferential calcite and forsterite nucleation and growth on the dolomite surface. An alternative explanation is the formation of a raised CO₂ concentration around the dolomite grains at high \(X_{{\text{CO}}_{\text{2}} }\) values, leading to product precipitation on the dolomite crystals.     

The partitioning of copper and molybdenum between silicate melts and aqueous fluids

The partitioning of copper and molybdenum between silicate melts and aqueous fluids has been determined at 750°C, and 1.4 Kb. The experiments were conducted in a $\text{1}\text{2}$ inch ID, rapid quench, cold seal pressure vessel. The aqueous and glass phase run products were analyzed by atomic absorption spectrophotometry and ion microprobe, respectively. The vapor/melt partition coefficient for copper, $\text{D}{}^{\mathrm{<mtext>v</mtext><mtext>l</mtext>}}{}_{\mathrm{Cu}}$, defined as the ratio of the concentrations of copper in the vapor to copper in the melt was found to be $\text{D}{}^{\mathrm{<mtext>v</mtext><mtext>l</mtext>}}{}_{\mathrm{Cu}}\text{= (9.1 ± 2.5)m}{}^{\mathrm{v}}{}_{\mathrm{Cl}}$ at NNO up to at least 4.5 moles of chlorine per kg of solution. The partition coefficient for molybdenum is equal to 2.5 ± 1.6 at NNO and QFM; its value is independent of the fluorine concentration of the melt up to at least 1.7 wt. percent fluorine, and of the chlorine concentration up to at least 4.5 moles of chlorine per kg of solution. Copper is probably present in the univalent state in both the silicate melt and in the associated aqueous phase at NNO; the most important aqueous complex of copper is probably CuCl⁰. Molybdenum is probably present in the aqueous phase as one or more molybdate species.     

Potential Flank-Collapse of Soufrière Volcano, Guadeloupe, Lesser Antilles? Numerical Simulation and Hazards

The past history of recurrent flank collapses of la Soufrière volcano of Guadeloupe, its structure, its well-developed hydrothermal system and the current activity constitute factors that could promote a future flank collapse, particularly in the case of a significant increase of activity, with or without shallow magmatic input. To address the hazards associated with such a collapse, we model the emplacement of the debris avalanche generated by a flank-collapse event in 1,250 BC (3,100 years B.P.). We use a finite-difference grain-flow model solving mass and momentum conservation equations that are depth-averaged over the slide thickness, and a Coulomb-type friction law with a variable basal (minimum) friction angle. Using the parameter values determined from this simulation, we then simulate the debris avalanche which could be generated by a potential collapse of the present lava dome. We then discuss the region which could be affected by such a future collapse, and additional associated hazards of concern.     

Evidence for Holocene environmental changes in the northern Fertile Crescent provided by pedogenic carbonate coatings

Holocene environmental changes in the northern Fertile Crescent remain poorly understood because of the scarcity of local proxy records in the region. In this study we investigated pedogenic (soil-formed) carbonate coatings on stones at the Pre-Pottery Neolithic site Göbekli Tepe as an indicator of local early-mid Holocene environmental changes. The ¹⁴C ages and stable isotopic composition of carbon and oxygen in thin (0.2–0.3 mm thick) pedogenic carbonate lamina indicate two main periods of coating formation: the early-Holocene (ca. 10000–6000 cal yr BP) and the mid-Holocene (ca. 6000–4000 cal yr BP). During the first period, there was an inverse relationship between δ¹³C and δ¹⁸O curves: a decrease in δ¹³C values coincide with an increase in δ¹⁸O values. For this period a trend towards higher temperatures is suggested. In the mid-Holocene, the mean rate of coating growth was 2–3 times higher than in the early Holocene. Both δ¹³C and δ¹⁸O reached their maximum values during this time and the direction of changes of the δ¹³C and δ¹⁸O curves became similar. The combination of data suggests that this period was the most humid in the Holocene and on average warmer than the early Holocene. At ca. 4000 cal yr BP secondary accumulation of carbonate ceased, presumably reflecting a shift to a more arid climate.     

Forensic view on two Raspberry Shake burglargrams

Journal of Seismology - A steadily increasing number of citizen seismological stations, often located in populated areas, record a plethora of man-made events. These events are especially of...