Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.     

Glycol Ethers As Groundwater Contaminants

Ether derivatives of dihydroxy alcohols, which are formed from ethylene or propylene, comprise an important group of groundwater contaminants known as glycol ethers. Compounds in this group are used as solvents, cleaning agents, and emulsifiers in many chemical products and manufacturing operations. Glycol ethers have been associated with a variety of toxic effects, and some compounds in the group are relatively potent teratogens. The limited information available suggests that glycol ethers are contaminants in groundwater, especially in anaerobic plumes emanating from disposal of mixed industrial and household waste. Most methods used to analyze groundwater samples cannot adequately detect 7g/’ (ppb) concentrations of glycol ethers, and the existing methods perform worst for the most widely used and toxic species. A new method capable of analyzing 7g/’ concentrations of glycol ethers was recently developed, and its use is recommended for groundwater samples where glycol ethers are likely to be present. Résumé. Les éthers glycol, polluants des eaux souterraines. Les dérivés d'éther de dihydroxy-alcool, formés à partir de l'éthylène ou du propylène, constituent un important groupe de polluants des eaux souterraines connus sous le nom d'éthers glycol. Les composés de ce groupe sont utilisés comme solvants, comme agents de nettoyage et comme émulsifiants dans de nombreux produits chimiques et dans de nombreux processus de fabrication. Des effets toxiques variés ont été attribués aux éthers glycol et certains des composés sont des agents tératogènes relativement puissants. Les données disponibles, qui sont limitées, indiquent que les éthers glycol sont des polluants communs dans les eaux souterraines, particulièrement dans les panaches anaéorobies émis par les décharges mixtes de déchets industriels et domestiques. La plupart des méthodes d'analyse d'échantillons d'eau souterraine ne sont pas capables de détecter convenablement des concentrations en éthers glycol de l'ordre du 7g/l (ppb); les méthodes actuelles sont médiocres pour doser les espèces toxiques les plus courantes. Une nouvelle méthode permettant de doser des concentrations en éthers glycol de l'ordre du 7 g/l a été récemment mise au point; son utilisation est préconisée pour les échantillons d'eau souterraine contenant des éthers glycol.     

Neoproterozoic chemostratigraphy

Chemostratigraphy has diverse applications to investigating the rock record, such as reconstructing paleoenvironments, determining the tectonic setting of sedimentary basins, indirect dating, and establishing regional or global correlations. Chemostratigraphy is thus an integral component of many investigations of the ancient sedimentary record. In this contribution, we review the principle inorganic geochemical methods that have been applied to the Neoproterozoic sedimentary record. Analysis of the traditional stable and radiogenic isotope systems, such as δ¹³C, δ¹⁸O, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr, is routine, particularly in successions rich in carbonate. These mainstay applications have yielded invaluable data and information bearing on the chronology and evolution of this eventful era in Earth history. Alongside the growing database of traditional data, a series of novel geochemical techniques have given rise to important new models and constraints on Neoproterozoic biogeochemical change. In particular, a range of proxies for water column redox, mainly obtained from black shales, have shed light on the pace and tempo of Neoproterozoic oxygenation and its link to the appearance of early animal evolution. Increased integration of diverse geochemical, sedimentological, and paleontological datasets, and the gradual radiometric calibration of the stratigraphic record promise to bring the details of the evolution of the Neoproterozoic Earth system into ever greater focus.     

象牙海岸Issia地区铌钽砂矿的研究(英文)

在西非的象牙海岸Issia地区分布着许多铌钽矿床,包括原生矿和砂矿。原生矿产在分带很好的伟晶岩中。这个地区发育着许多花岗岩和花岗伟晶岩。伟晶岩可分为:(1)分异不好的伟晶岩,无矿化;(2)含Be伟晶岩,分带较好,见绿柱石;(3)含Be-Nb-Ta的伟晶岩,分带很好,是矿体;(4)Be-Nb-Ta-Li伟晶岩,分带很好,是矿体。除了10多个原生矿外,还有许多砂矿。砂矿有两种类型:一种近原生矿的坡积砂矿,另一种是经河流冲刷搬运后的冲积砂矿。我们选择了Etienne-Meguhe砂矿作为近原生矿的坡积砂矿的代表,Bemadi矿作为河流冲积型的砂矿的代表,对这两种类型的砂矿的风化、搬运、沉积机理进行了比较研究。研究发现不同的搬运距离和搬运模式对铌钽砂矿的主要矿物——铌钽铁矿的化学性质没有什么影响,而其物理形态则发生了变化。坡积型砂矿的铌钽铁矿常与石英、长石等矿物连生,其颗粒大小与原生的Nb-Ta伟晶岩中的铌钽铁矿一致;经河流冲积而形成的砂矿中,铌钽铁矿颗粒变小、轮廓变得圆滑,几乎无连生矿物,但矿体集中,常在河流的冲积扇中分布,易开采。     

The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

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.     

Crystal nucleation and growth produced by continuous decompression of Pinatubo magma

High-temperature decompression experiments demonstrate that crystal textures preserve a record of the style and rate of magmatic ascent. To reinforce this link, we performed a suite of isothermal decompression experiments using starting material from the climactic 1991 Pinatubo eruption. We decompressed experiments from 220 MPa to final, quench pressures of 75 or 30 MPa using continuous decompression rates of 100, 30, 10, 3, 1, and 0.3 MPa h^?1. Amphibole, clinopyroxene, and plagioclase crystallized during the experiments, with plagioclase microlites dominating the assemblage. Total microlite number densities range from 10^7.6±0.4 up to 10^8.2±0.2 cm^?3, with plagioclase accounting for up to 65% of the total number. Plagioclase microlite area increased systematically from 19?±?8 to 937?±?487 µm² with increasing experiment duration. Our textures provide time-integrated records of crystal kinetics. Average nucleation and areal growth rates of plagioclase are highest in the fastest decompressions (~?10^7.5 cm^?3 h^?1 and 10.1?±?4.1 µm² h^?1, respectively) and more than an order of magnitude lower in the slowest experiments (~?10^5.5 cm^?3 h^?1 and 0.8?±?0.2 µm² h^?1, respectively). Both nucleation and growth rates are highest at high degrees of disequilibrium. We find that peak supersaturation-dependent instantaneous rates are generally more than an order of magnitude faster than average rates. We use those instantaneous nucleation and growth rates to introduce an iterative model to evaluate the effects of different decompression rates, decompression paths (continuous, single-step or multistep), and the presence of phenocrysts on final crystallinity and microlite size distribution.     

Petrogenesis of low-δ<Superscript>18</Superscript>O quartz porphyry dykes,Koegel Fontein complex,South Africa

This paper investigates the origin of low-δ¹⁸O quartz porphyry dykes associated with the 144–133 Ma Koegel Fontein Igneous Complex, which was intruded during the initial phase of breakup of Africa and South America. The 25-km diameter Rietpoort Granite is the largest and youngest phase of activity, and is roofed by a 10-km diameter pendant of gneiss. Quartz porphyry (QP) dykes, up to 15 m in width, strike NW–SE across the complex. The QP dykes that intruded outside the granite have similar quartz phenocryst δ¹⁸O values (average 8.0‰, ± 0.7, n?=?33) to the granite (average 8.3?±?1.0, n?=?7). The QP dykes that intruded the roof pendant have quartz phenocrysts with more variable δ¹⁸O values (average 1.6‰, ± 2.1, n?=?55). In some cases quartz phenocrysts have δ¹⁸O values as low as ? 2.5‰. The variation in δ¹⁸O value within the quartz crystal population of individual dykes is small relative to the overall range, and core and rim material from individual quartz phenocrysts in three samples are identical within error. There is no evidence that quartz phenocryst δ¹⁸O values have been affected by fluid–rock interaction. Based on a ?_quartz?magma value of 0.6‰, magma δ¹⁸O values must have been as low as ? 3.1‰. Samples collected along the length of the two main QP dykes that traverse the roof pendant have quartz phenocryst δ¹⁸O values that range from +?1.1 to +?4.6‰, and ? 2.3 to +?5.6‰, respectively. These δ¹⁸O values correlate negatively (r = ? 0.96) with initial ⁸⁷Sr/⁸⁶Sr, which can be explained by the event that lowered δ¹⁸O values of the source being older than the dykes. We suggest that the QP dykes were fed by magma produced by partial melting of gneiss, which had been variably altered at high temperature by ¹⁸O-depleted meteoric water during global glaciation at ~?550 Ma. The early melts had variable δ¹⁸O value but as melt pockets interconnected during melting, the δ¹⁸O values approached that of average gneiss. Variable quartz phenocryst δ¹⁸O values in the same dyke can be explained by vertical emplacement, at variable rates of ascent along the dyke. The lateral variation in quartz, and hence magma δ¹⁸O value at a particular point along a single dyke would depend on the rate of ascent of magma at that point along the dyke, and the ‘age’ of the particular magma batch.     

Impact of suboxia on sinking particulate organic carbon: Enhanced carbon flux and preferential degradation of amino acids via denitrification

Fluxes of particulate organic carbon (POC) through the oxygen deficient waters in the eastern tropical North Pacific were found to be relatively less attenuated with depth than elsewhere in the eastern North Pacific. The attenuation coefficient (b) for the flux was found to be 0.40 versus the composite value of 0.86 determined by Martin et al. (1987). To examine this further, sinking POC was collected using sediment traps and allowed to degrade in oxic and suboxic experiments. Using a kinetic model, it was found that degradation proceeded at similar rates (roughly 0.8 day⁻¹) under oxic and suboxic conditions, but a greater fraction of bulk POC was resistant to degradation in the suboxic experiments (61% vs. 23%). Amino acids accounted for 37% of POC collected at 75m, but following degradation the value dropped to 17% and 16% in the oxic and suboxic experiments respectively. POC collected from 500m was 10% amino acids. The non-AA component of POC collected at 75m was not degraded under suboxic conditions, while under oxic conditions it was. These results suggest that microbes degrading OC under suboxic conditions via denitrification preferentially utilize nitrogen-rich amino acids. This preferential degradation of amino acids suggests that 9% more nitrogen may be lost via water column denitrification than is accounted for when a more “Redfieldian” stoichiometry for POC is assumed.     

Paraglacial sedimentation and denudation processes in an Alpine valley of Switzerland. An approach to the quantification of sediment budgets

Abstract

As a result of recent drillings in the Walensee Valley (eastern Switzerland) a new facies model for the Quaternary filling of Alpine valleys has been developed. A detailed lithological model and some new radiocarbon dating allowed the calculation of regional sedimentation and denudation rates and their change during the Late- and Postglacial period. It is shown that these changes follow the paraglacial sedimentation model by Church and Ryder [1]. The absolute quantification of the sediment budgets between the Last Glaciation and today points to denudation rates in the order of 1.5 mm y^?1 for the catchment of the Lake of Walenstadt. This is 50 % higher than suggested from current tectonic and isostatic estimates up to now. In that case present day uplift of the Alps would not be in balance with denudation. © Elsevier, Paris