The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750–850 °C as a function of oxygen fugacity (Ni–NiO or Re–ReO₂ buffer), melt composition (Al/(Na?+?K) ratio), and fluid composition (NaCl and CO₂ content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under “reducing conditions” (Ni–NiO buffer), D^fluid/melt is nearly one order of magnitude larger (323?±?14 for a metaluminous melt) than under “oxidizing conditions” (Re–ReO₂ buffer; 74?±?5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H₂S and HS^? under reducing conditions and of SO₄^2? and HSO₄^? under oxidizing conditions, while SO₂ is undetectable. The latter observation suggests that already at the Re–ReO₂ buffer, sulfur in the fluid is almost completely in the S⁶⁺ state and, therefore, more oxidized than expected according to current models. CO₂ in the fluid (up to x_CO2?=?0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D^fluid/melt is independent of x_NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H₂S to NaSH as dominant sulfur species in the fluid. A decrease of D^fluid/melt with alkali content in the melt is observed over the entire compositional range under reducing conditions, while it is prominent only between the peraluminous and metaluminous composition in oxidizing experiments. Overall, the experimental results suggest that for typical oxidized, silicic to intermediate subduction zone magmas, the degassing of sulfur is not influenced by the presence of other volatiles, while under reducing conditions, strong interactions with chlorine are observed. If the sulfur oxidation state is preserved during an explosive eruption, a large fraction of the sulfur released from oxidized magmas may be in the S⁶⁺ state and may remain undetected by conventional methods that only measure SO₂. Accordingly, the sulfur yield and the possible climatic impact of some eruptions may be severely underestimated.     

Late Holocene hydrologic changes in northern New Zealand inferred from stable isotope values of aquatic cellulose in sediments from Lake Pupuke

Isotopic records of aquatic cellulose are becoming increasingly important for palaeohydrological reconstructions, but widespread application of this climate proxy is hampered by minerogenic contamination that affects oxygen isotope measures in cellulose. Few records of isotopes in aquatic cellulose are available from palaeoclimate archives in the Southern Hemisphere. In this study, we used a new bulk cellulose extraction method and determined the oxygen (δ¹⁸O) and carbon (δ¹³C) isotope values in cellulose from a Holocene lake sediment core segment (7.2–1.1 cal ka BP) from Lake Pupuke, Auckland, New Zealand. Isotope values from modern, potential sources of sedimentary cellulose revealed the aquatic origin of the cellulose extracted from the core, and hence enabled inference of past lake water δ¹⁸O values from the δ¹⁸O of measured cellulose in the core. A shift to a more positive water balance in the lake was identified around 2.8 cal ka BP by a decrease in inferred lake water δ¹⁸O values. At that time, greater epilimnetic primary productivity is indicated by the higher δ¹³C values of sedimentary cellulose. Greater divergence between the δ¹³C values of cellulose and bulk organic matter suggests stronger stratification of the lake, likely caused by greater freshwater input. We discuss a possible link to a solar minimum that occurred at that time.     

Deglaciation chronology,sea-level changes and environmental changes from Holocene lake sediments of Germania Havn Sø, Sabine Ø, northeast Greenland

Germania Havn Sø is located at the outermost coast of northeastern Greenland. According to radiocarbon dating, the lake basin was deglaciated in the early Holocene, around 11,000 cal yr BP. At that time the lake was a marine bay, but the lake was isolated soon after deglaciation at ~ 10,600 cal yr BP. The marine fauna was species-poor, indicating harsh conditions with a high sedimentation rate and lowered salinity due to glacial meltwater supply. The pioneer vegetation around the lake was dominated by mosses and herbs. Deposition of relatively coarse sediments during the early Holocene indicates erosion of the newly deglaciated terrain. Remains of the first woody plant (Salix herbacea) appear at 7600 cal yr BP and remains of other woody plants (Salix arctica, Dryas octopetala, Cassiope tetragona and Empetrum nigrum) appear around one millennium later. Declining concentrations of D. octopetala and the caddis fly Apatania zonella in the late Holocene probably imply falling summer temperatures. Only moderate changes in the granulometric and geochemical record during the Holocene indicate relatively stable environmental settings in the lake, which can probably be explained by its location at the outer coast and the buffering effect of the neighboring ocean.     

Monazite stability,composition and geochronology as tracers of Paleoproterozoic events at the eastern margin of the East European Craton (Taratash complex,Middle Urals)

The Precambrian Taratash complex (Middle Urals) is one of the rare windows into the Palaeoproterozoic and earlier history of the eastern margin of the East European Craton. Monazite from intensively deformed rocks within a major amphibolite-facies shear zone in the Taratash complex has been investigated by means of electron-probe microanalysis and laser-ablation SF-ICP-MS.Metamorphic and magmatic cores of monazite from metasedimentary and metagranitoid rocks yield U–Pb ages of 2244 ± 19 and 2230 ± 22 Ma (± 2 σ) and record a previously unknown pre-deformational HT-metamorphic event in the Taratash complex. Subsequent dissolution–reprecipitation of monazite, during shear zone formation under amphibolite-facies conditions, caused patchy zonation and chemical alteration of the recrystallised monazite domains, leading to higher cheralite and huttonite components. This process, which was mediated by a probable (alkali + OH)-bearing metamorphic fluid also caused a total resetting of the U–Pb-system. The patchy domains yield concordant U–Pb-ages between 2052 ± 16 and 2066 ± 22 Ma, interpreted as the age of the shear zone. In line with previously published ages of high grade metamorphism and migmatisation, the data may point to a Palaeoproterozoic orogenic event at the eastern margin of the East European Craton.Post-deformational fluid-induced greenschist-facies retrogression caused partial to complete breakdown of monazite to fluorapatite, REE + Y-rich epidote, allanite and Th-orthosilicate.The retrograde assemblages either form coronas around monazite, or occur as dispersed reaction zones, indicating that the REE, Y, and Th were mobile at least on the thin section scale. The greenschist-facies metamorphic fluid was aqueous and rich in Ca. Monazite affected by advanced breakdown responded to the retrogression by incorporating the cheralite or huttonite components during a fluid-induced dissolution–reprecipitation process. This event did not reset the U–Pb-system but caused partial Pb loss reflected by discordant U–Pb-dates.     

Günterblassite, (K,Ca)3 − x Fe[(Si,Al)13O25(OH,O)4] · 7H2O, a new mineral: the first phyllosilicate with triple tetrahedral layer

A new mineral, günterblassite, has been found in the basaltic quarry at Mount Rother Kopf near Gerolstein, Rheinland-Pfalz, Germany as a constituent of the late assemblage of nepheline, leucite, augite, phlogopite, åkermanite, magnetite, perovskite, a lamprophyllite-group mineral, götzenite, chabazite-K, chabazite-Ca, phillipsite-K, and calcite. Günterblassite occurs as colorless lamellar crystals up to 0.2 × 1 × 1.5 mm in size and their clusters. The mineral is brittle, with perfect cleavage parallel to (001) and less perfect cleavage parallel to (100) and (010). The Mohs hardness is 4. The calculated and measured density is 2.17 and 2.18(1) g/cm³, respectively. The IR spectrum is given. The new mineral is optically biaxial and positive as follows: α = 1.488(2), β = 1.490(2), γ = 1.493(2), 2V _meas = 80(5)°. The chemical composition (electron microprobe, average of seven point analyses, H₂O is determined by gas chromatography, wt %) is as follows: 0.40 Na₂O, 5.18 K₂O, 0.58 MgO, 3.58 CaO, 4.08 BaO, 3.06 FeO, 13.98 Al₂O₃, 52.94 SiO₂, 15.2 H₂O, and the total is 98.99. The empirical formula is Na_0.15K_1.24Ba_0.30Ca_0.72Mg_0.16F _0.48 ²⁺ [Si_9.91Al_3.09O_25.25(OH)_3.75] · 7.29H₂O. The crystal structure has been determined from a single crystal, R = 0.049. Günterblassite is orthorhombic, space group Pnm2₁; the unit-cell dimensions are a = 6.528(1), b = 6.970(1), c = 37.216(5) Å, V = 1693.3(4) ų, Z = 2. Günterblassite is a member of a new structural type; its structure is based on three-layer block [Si₁₃O₂₅(OH,O)₄]. The strong reflections in the X-ray powder diffraction pattern [d Å (I, %) are as follows: 6.532 (100), 6.263 (67), 3.244 (49), 3.062 (91), 2.996 (66), 2.955 (63), and 2.763 (60). The mineral was named in honor of Günter Blass (born in 1943), a well-known amateur mineralogist and specialist in electron microprobe and X-ray diffraction. The type specimen of günterblassite is deposited in the collections of the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, Russia, with the registration number 4107/1.     

Experimental reactions between olivine and orthopyroxene with phonolite melt: implications for the origins of hydrous amphibole + phlogopite + diopside bearing metasomatic veins

Amphibole + phlogopite + diopside bearing veins are observed in a large number of upper mantle xenoliths, but the composition of the melt that forms them is poorly constrained. Recent data from the Heldburg Phonolite, Central Germany, has shown that phonolite melt will react with olivine and orthopyroxene xenocrysts to form reaction rims of amphibole + phlogopite + diopside at mid-lower crustal pressures. This is the first example of where a melt has reacted with peridotite to form the mineralogy of the metasomatic veins. It is therefore necessary to explore whether a phonolite melt could be the parent melt that forms amphibole + phlogopite + diopside metasomatic veins. Experimental reactions between single crystals of olivine and orthopyroxene with phonolite melt were conducted at upper mantle conditions of 1.0–1.5 GPa and 900–1,000 °C. Melt water contents were varied from anhydrous to >12 wt. H₂O. Olivine reacts to form phlogopite reaction rims with overgrowths of diopside <1,000 °C or rims of secondary olivine >1,000 °C. Orthopyroxene reacts to form amphibole with epitaxial diopside overgrowths <1,000 °C. No reaction rims form when the bulk melt H₂O is lower than ~3.8 wt%. Pressure has little effect over the small range tested. These experiments reproduce reaction rims on olivine and orthopyroxene observed in the Heldburg Phonolite, Central Germany, and suggest that a relatively narrow range of temperatures and melt water contents is required for rim formation. The compositions of rim amphibole, phlogopite and diopside from the experiments have very similar compositions to those from Heldburg but do not match those from metasomatic veins. Phenocrysts from Heldburg are similar to the metasomatic veins, suggesting that a phonolite could potentially form the veins if vein formation is dominated by crystallization rather than reaction and replacement of wall rock phases.     

Characterization and sources of extractable organic matter from sediment cores of an urban lake (Tasik Perdana), Kuala Lumpur,Malaysia

The extractable organic matter of sediment samples from six sampling sites in Lake Perdana, Kuala Lumpur, was analyzed to characterize the source inputs. The analysis of aliphatic homologous series indicated that terrestrial higher plant waxes can be assigned as the major sources of the identified aliphatic components in the lake sediments. The presence of an unresolved complex mixture of branched and cyclic compounds and a series of hopanes ranging from C₂₇ to C₃₅ reflected the contamination by petroleum residues from urban vehicular emissions brought in by runoff and fallout. The steroids present included stenols and stanols and showed an input of organic matter from higher plants. The detected pentacyclic triterpenoids comprised oleanane, ursane, lupane and friedelane skeletons including unsaturated oxygenated, mono-, di- and triaromatic counterparts. They are recognized as biomarkers for angiosperms. The presence of des-A-triterpenoids and their aromatized derivatives as the major diagenetic products of triterpenoids reflected the degradation of natural organic matter in the sediments occurring under mainly anoxic conditions. In addition, the presence of tetrahymanol and ββ-bishomohopan-32-ol indicated a minor algal/plankton and bacterial input to the sediments.     

Web-based 4D visualization of marine geo-data using WebGL

For marine logistics and maintenance of extensive and expensive marine engineering projects in the coastal zone, it is essential that institutions provide the public with relevant information in an easily understandable yet comprehensive manner over the web. A perennial challenge, however, has been the development of spatio-temporal (four-dimensional (4D)) geo-visualization algorithms to enable the integration of time-varying geo-information in map-based visualizations on the Internet. In this paper, we address the challenge of visualizing marine spatial data in web-based applications through a 4D visualization concept, focusing on usability criteria, performance parameters, the required implementation effort, and delivering a breath of spatial information that supports decision-making on multiple levels. We used Web Graphic Library (WebGL) to validate our concept through a prototypical implementation. In our technology evaluation, WebGL proved highly suitable for the development of interactive, responsive, efficient, and mobile web-based Geographic Information applications, including 2D, 3D, and 4D (spatiotemporal) content. During our research, we identified a number of open research questions, including mapping graphic variables to thematic expressivity, representation of the time dimension in 4D systems, generic temporal generalization, and integration of (pseudo-)photorealistic illustrations in web-based geo-visualization systems.     

2D and 3D Polar Plume Analysis from the Three Vantage Positions of STEREO/EUVI A, B, and SOHO/EIT

Polar plumes appear as elongated objects starting at the solar polar regions. Here we analyze these objects from a sequence of images taken simultaneously by the three spacecraft telescopes STEREO/EUVI A and B, and SOHO/EIT. We establish a method capable of automatically identifying plumes in solar EUV images close to the limb at 1.01?–?1.39?R _⊙ in order to study their temporal evolution. This plume-identification method is based on a multiscale Hough-wavelet analysis. Then two methods to determine the 3D localization and structure of the plumes are discussed: first, tomography using filtered back-projection and including the differential rotation of the Sun and, second, conventional stereoscopic triangulation. We show that tomography and stereoscopy are complementary for studying polar plumes. We also show that this systematic 2D identification and the proposed methods of 3D reconstruction are well suited to identify plumes individually and also to analyze the distribution of plumes and inter-plume regions. Finally, the results are discussed, focusing on plume position and cross-sectional area.     

Temperature dependence of the OH-stretching frequencies in topaz-OH

Hydrogen bonding in topaz-OH, Al₂SiO₄(OH)₂, was investigated by IR spectroscopic analysis of the temperature dependence of the OH-stretching frequencies. Low-temperature spectra ranging from −196 to −160°C prove the existence of four non-equivalent H-positions in the crystal structure from the occurrence of four different OH-bands. With increasing temperature, these bands merge first, above −160°C, into two OH-bands and then above 400°C into one asymmetric broad band. Shifting of the OH-bands is caused by thermally induced hydrogen order–disorder. Low temperature fixes the protons in their positions; increasing temperature induces proton movement and allows switching between the different positions. Autocorrelation analysis of the IR spectra reveals two phase transitions, one at about −155°C from P1 to Pbn2 ₁ characterized as static–dynamic change and the second at about 380°C from Pbn2 ₁ to Pbnm caused by disordering of the protons. The increasing symmetry with temperature is due to advanced proton movement and dynamical averages over the proton distribution densities.