Cu- and Mn-bearing tourmalines from Brazil and Mozambique: crystal structures, chemistry and correlations

Cu- and Mn-bearing tourmalines from Brazil and Mozambique were characterised chemically (EMPA and LA-ICP-MS) and by X-ray single-crystal structure refinement. All these samples are rich in Al, Li and F (fluor-elbaite) and contain significant amounts of CuO (up to ~1.8 wt%) and MnO (up to ~3.5 wt%). Structurally investigated samples show a pronounced positive correlation between the <Y-O> distances and the (Li + Mn²⁺ + Cu + Fe²⁺) content (apfu) at this site with R ² = 0.90. An excellent negative correlation exists between the <Y-O> distances and the Al₂O₃ content (R ² = 0.94). The samples at each locality generally show a strong negative correlation between the X-site vacancies and the (MnO + FeO) content. The Mn content in these tourmalines depends on the availability of Mn, on the formation temperature, as well as on stereochemical constraints. Because of a very weak correlation between MnO and CuO we believe that the Cu content in tourmaline is essentially dependent on the availability of Cu and on stereochemical constraints.     

Nucleation and crystallization of otavite, witherite, calcite, strontianite, hydrozincite, and hydrocerussite by CO2 membrane diffusion technique

Otavite, witherite, calcite, strontianite, hydrozincite and hydrocerussite nucleation was induced by CO₂ diffusion through a polyethylene membrane into a metal bearing solution. Nucleation and ongoing precipitation was followed at 25 ± 1 °C by the chemical evolution of the solution and the consumption of sodium hydroxide (pH-stat conditions). X-ray diffraction patterns as well as FT-infrared and Raman spectra confirmed the formation of well crystallized solids, except for less crystalline hydrozincite. In several experiments simonkolleite and laurionite precipitated concurrently with hydrozincite and hydrocerussite. The carbonate end-member minerals, smithsonite and cerussite, however were not formed. Carbonate minerals crystallized as spherical aggregates of thin layered otavite, spherical orientated witherite needles, rhombohedral calcite, pseudo-hexagonal strontianite laths, fibrous lumps of hydrozincite and planar hexagonal hydrocerussite crystals. Crystal and aggregate sizes range between 1 and 100 μm. Nucleation occurred at well defined reaction times and distinct critical supersaturation indices (SI_crit). The time for nucleation at constant pH decreased as the initial metal concentration increased for a given solid. The SI_crit values decreased in the order of hydrocerussite (3.2), otavite (2.5), strontianite (1.6), witherite (0.9) and calcite (0.7).     

Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like ⁸⁷Sr/⁸⁶Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~ 100 °C), and yet its ⁸⁷Sr/⁸⁶Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine–talc fault schists form north of the LHF. These calcites show unradiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.     

Isolation and water-level fluctuations of Lake Kachishayoot, Northern Québec, Canada

This study combines different methods, including grain size, macrofossil, and pollen analyses, to reconstruct paleogeographical and paleoclimatological conditions for periods before, during, and after the isolation of a small lake (Lake Kachishayoot) in northern Québec. After the retreat of the Laurentide Ice Sheet around 8000 ¹⁴C yr B.P., the area was submerged by the Tyrrell Sea. The transition from marine to lacustrine environment occurred about 5400 yr B.P. Two major periods of water-level fluctuations were inferred from organic and mineral sediments: a high water level that occurred after 3200 yr B.P. and a low water level that started before 2200 yr B.P. Our chronological data for the first period are consistent with those from nearby Lac des Pluviers and from other lakes in east central Canada and in the northeastern United States. During the low-water-level period, however, there is no evidence for minor fluctuations, whereas other lakes in northern Québec and east-central Canada underwent several brief lowerings. Long-term changes in atmospheric circulation caused by changing global boundary conditions likely explained long-term water-level fluctuations of Lake Kachishayoot.     

Trace elements in organic- and iron-rich surficial fluids of the boreal zone: Assessing colloidal forms via dialysis and ultrafiltration

On-site size fractionation of about 40 major and trace elements (TE) was performed on waters from boreal small rivers and their estuaries in the Karelia region of North-West Russia around the “Vetreny Belt” mountain range and in Paanajärvi National Park (Northern Karelia). Samples were filtered in the field using a progressively decreasing pore size (5 μm, 2.5 (3) μm, 0.22 (0.45) μm, 100 kDa, 10 and 1 kDa) by means of frontal filtration and ultrafiltration (UF) techniques and employing in-situ dialysis with 10 and 1 kDa membranes followed by ICP-MS analysis. For most samples, dialysis yields a systematically higher (factor of 2-3) proportion of colloidal forms compared to UF. Nevertheless, dialysis is able to provide a fast and artefact-free in-situ separation of colloidal and dissolved components.Similar to previous studies in European subarctic zones, poor correlation of iron concentration with that of organic carbon (OC) in (ultra)filtrates and dialysates reflect the presence of two pools of colloids composed of organic-rich and Fe-rich particles. All major anions and silica are present as dissolved species (or solutes) passing through the 1-kDa membrane. Size-separation ultrafiltration experiments show the existence of larger or smaller pools of colloidal particles different for each of the considered elements.The effect of rock lithology (acidic versus basic) on the colloidal speciation of TE is seen solely in the increase of Fe and some accompanying TE concentrations in catchment areas dominated by basic rocks compared to granitic catchments. Neither the ultrafiltration pattern nor the relative proportions of colloidal versus truly dissolved TE are affected by the lithology of the underlying rocks: within ±10% uncertainty, the two colloidal (10 kDa-0.22 μm and 1-10 kDa) and the truly dissolved (<1 kDa) pools show no difference in percentage of TE distribution between two types of bedrock lithology. The same conclusion is held for organic- and Fe-rich waters. In contrast, landscape context analysis demonstrated slight dominance, for most TE affected by UF, of large-size colloids (10 kDa-0.22 μm) in rivers and streams and small-size colloids and truly dissolved fractions in swamp stagnant surface waters. This supports the existence of two pathways of colloids formation: during the plant litter degradation in wetland zones and at the redox front in river riparian zone.     

Sulfur isotope fractionation during growth of sulfate-reducing bacteria on various carbon sources

Stable sulfur isotope fractionation during microbial sulfate reduction is a potential tool to estimate sulfate reduction rates at field sites. However, little is known about the influence of the utilized carbon source on the magnitude of sulfur isotope fractionation. To investigate this effect, both a pure culture (strain PRTOL1) and enrichment cultures from a petroleum hydrocarbon (PHC)-contaminated aquifer were used and grown in batch cultures on various carbon sources with an initial sulfate concentration of 1 mmol/L. As sole carbon sources the PHC components naphthalene, 1,3,5-trimethylbenzene, and heating oil (enrichment culture) and the organic acids acetate, pyruvate, benzoate, and 3-phenylpropionate (enrichment culture and PRTOL1) were used. Sulfate reduction rates of all cultures ranged from 6 ± 1 nmol cm⁻³ d⁻¹ (enrichment culture grown on 1,3,5-trimethylbenzene) to 280 ± 6 nmol cm⁻³ d⁻¹ (enrichment culture grown on pyruvate). Cell-specific sulfate reduction rates ranged from 1.1 × 10⁻¹⁴ mol cell⁻¹ d⁻¹ (PRTOL1 grown on pyruvate) to 1.5 × 10⁻¹³ mol cell⁻¹ d⁻¹ (PRTOL1 grown on acetate). Sulfur isotope enrichment factors (ε) for the enrichment culture ranged from 16.1‰ (3-phenylpropionate) to 34.5‰ (1,3,5-trimethylbenzene) and for PRTOL1 from 30.0‰ (benzoate) to 36.0‰ (pyruvate). Cultures of PRTOL1 always showed higher ε values than the enrichment culture when grown on the same carbon source due to culture-specific properties. Higher ε values were obtained when the enrichment culture was grown on PHC components than on organic acids. No relationship between ε values and cell-specific sulfate reduction rate existed when all data were combined. When comparing the magnitude of ε values determined in this laboratory study with ε values measured at contaminated and uncontaminated field sites, it becomes evident that a multitude of factors influences ε values at field sites and complicates their interpretation. The results of this study help us assess some of the general parameters that govern the magnitude of ε in sulfate-reducing environments.     

Refined relationship between the position of the fundamental OH stretching and the first overtones for clays

The aim of this paper is to determine a relationship between the wavenumbers of the first OH-stretching overtones (W_2OH) and the wavenumbers of the OH-stretching fundamentals (W_OH) to help to interpret the near-infrared (NIR) spectra. The first overtone (2OH) bands appear at wavenumbers less than twice those of the fundamental bands (OH), due to the anharmonic character of vibrations, X = W_2OH/2 - W_OH, with X being the anharmonicity constant. Talc samples with various crystal chemistries are used to solve the equation and the experimental data are well fitted with X = –85.6 cm^–1. As far as the authors are aware, it is the first time that the anharmonicity constant for the OH-stretching vibrations is determined for phyllosilicates. The anharmonicity constant remains almost unchanged for several types of clay samples. Therefore the relation, established from talc samples because their absorption bands are narrow and their wavenumber range of OH vibrations is wide, can be used for any other clay minerals.     

EUV Full-Sun Imaging and Pointing Calibration of the SOHO Coronal Diagnostic Spectrometer

Although the field of view of the Normal Incidence Spectrometer (NIS) of the Coronal Diagnostic Spectrometer (CDS) is 4×4 arc min, it is possible to observe the full solar disk by forming a mosaic of images taken in succession. This paper describes just such a study which has been used to collect images of the Sun simultaneously in six wavelengths between 304 Ú and 630 Ú, and with a temperature coverage between 5×10⁴ K and 2.5×10⁶ K. A representative sample of the resulting images is presented. These data can be used to explore the origin of solar EUV variability, and examine large-scale solar features. Another use of these data is to calibrate the pointing of the CDS Offset Pointing System (OPS), by comparing them against the SOHO Extreme ultraviolet Imaging Telescope (EIT) full-disk images taken at the same time. Many joint observations are made with CDS and other SOHO instruments, and calibration of the pointing is crucial to the co-pointing of the instruments, and to the analyses of these data. Coalignment is done by fitting to a cross-correlation function, using an IDL procedure which can be applied to any CDS/NIS data set. The accuracy of an individual coalignment can be demonstrated to be in the range 1–2 arc sec. The overall accuracy of the OPS calibration is ±5 arc sec, mainly attributable to measurement error in the actuator positions. An onboard Spartan Intermediate Sun Sensor of the Lockheed design, which was intended to provide greater pointing accuracy, exhibits a time-varying calibration, possibly due to a gradual loss of sensitivity.     

Study of the post-flare loops on 29 July 1973

Bright and dark curvilinear structures observed between the two major chromospheric ribbons during the flare of 29 July 1973 on films from the Big Bear Solar Observatory are interpreted as a typical system of coronal loops joining the inner boundaries of the separating flare ribbons. These observations, made through a 0.25 Å H filter, only show small segments of the loops having Doppler shifts within approximately ± 22 km s^–1 relative to the filter passband centered at H, H -0.5 Å or H +0.5 Å. However, from our knowledge of the typical behavior of such loop systems observed at the limb in H and at 5303 Å, it has been possible to reconstruct an appoximate model of the probable development of the loops of the 29 July flare as they would have been viewed at the limb relative to the position of a prominence which began to erupt a few minutes before the start of the flare. It is seen that the loops ascended through the space previously occupied by the filament. On the assumption that H fine structures parallel the magnetic field, we can conclude that a dramatic reorientation of the direction of the magnetic field in the corona occurred early in the flare, subsequent to the start of the eruption of the filament and prior to the time that the H loops ascended through the space previously occupied by the filament.     

Detection of new hydrocarbons in Uranus' atmosphere by infrared spectroscopy

Ethane (C₂H₆), methylacetylene (CH₃C₂H or C₃H₄) and diacetylene (C₄H₂) have been discovered in Spitzer 10-20 μm spectra of Uranus, with 0.1-mbar volume mixing ratios of (1.0±0.1)×¹⁰⁻⁸, (2.5±0.3)×¹⁰⁻¹⁰, and (1.6±0.2)×¹⁰⁻¹⁰, respectively. These hydrocarbons complement previously detected methane (CH₄) and acetylene (C₂H₂). Carbon dioxide (CO₂) was also detected at the 7-σ level with a 0.1-mbar volume mixing ratio of (4±0.5)×¹⁰⁻¹¹. Although the reactions producing hydrocarbons in the atmospheres of giant planets start from radicals, the methyl radical (CH₃) was not found in the spectra, implying much lower abundances than in the atmospheres of Saturn or Neptune where it has been detected. This finding underlines the fact that Uranus' atmosphere occupies a special position among the giant planets, and our results shed light on the chemical reactions happening in the absence of a substantial internal energy source.