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.     

Ostracode carbonate δ18O- and δ13C-signature of hydrological and climatic changes affecting Lake Neuchâtel,Switzerland, since the latest Pleistocene

Floating and grounded peat plateaus were studied in fens in the Yukon Territory (Canada). The peat deposit may be over 4 m thick and consists of a lower bed of aquatic peat overlain by humic fen peat, mesic fen peat and woody peat. Permafrost in the grounded peat plateaus is older than the 1200 year old White River Ash, whereas permafrost in the floating peat plateau is younger.Peat accumulation rates since 1200 years B.P. were greater in the fens (85–100 cm) than on the surface of the peat plateaus (25–55 cm). Where the peat plateau is free-floating, it will persist until the climate changes, causing the icy core to thaw. Where the peat plateau is frozen to the mineral substrate, it slowly drowns since the fen peat accumulates faster than the woody peat. This drowning results in degradation of the landform independently of the climate. Only degradation of floating peat plateaus can be used to identify climatic changes.This publication is the first paper in a series of papers presented at the session on Past Climatic Change and the Development of Peatlands at the ASLO and SWS Meetings in Edmonton, Canada, May 30–June 3, 1993. Dr. P. Kuhry and Dr S. C. Zoltai are serving as Guest Editors.     

Physical and chemical properties of the waters of saline lakes and their importance for deep-water renewal: Lake Issyk-Kul, Kyrgyzstan

The relationships between electrical conductivity, temperature, salinity, and density are studied for brackish Lake Issyk-Kul. These studies are based on a newly determined major ion composition, which for the open lake shows a mean absolute salinity of 6.06 g kg⁻¹. The conductivity-temperature relationship of the lake water was determined experimentally showing that the lake water is about 1.25 times less conductive than seawater diluted to the same absolute salinity as that of the lake water. Based on these results, an algorithm is presented to calculate salinity from in-situ conductivity measurements. Applied to the field data, this shows small but important vertical salinity variations in the lake with a salinity maximum at 200 m and a freshening of the surface water with increasing proximity to the shores. The algorithm we adopt to calculate density agrees well with earlier measurements and shows that at 20°C and 1 atm Lake Issyk-Kul water is about 530 g m⁻³ denser than seawater at the same salinity. The temperature of maximum density at 1 atm is about 0.15°C lower than that for seawater diluted to the same salinity. Despite its small variations, salinity plays an important role, together with temperature changes, in the static stability and in the production of deep-water in this lake. Changes in salinity may have had important consequences on the mixing regime and the fate of inflowing river water over geological time. Uncharged silicic acid is negligible for the stability of the water column except near an ∼15 m thick nepheloid layer observed at the bottom of the deep basin.     

Normal fault growth influenced by basement fabrics: The importance of preferential nucleation from pre‐existing structures

Reactivation of pre‐existing intra‐basement structures can influence the evolution of rift basins, yet the detailed kinematic relationship between these structures and overlying rift‐related faults remains poorly understood. Understanding the kinematic as well as geometric relationship between intra‐basement structures and rift‐related fault networks is important, with the extension direction in many rifted provinces typically thought to lie normal to fault strike. We here investigate this problem using a borehole‐constrained, 3D seismic reflection dataset from the Taranaki Basin, offshore New Zealand. Excellent imaging of intra‐basement structures and a relatively weakly deformed, stratigraphically simple sedimentary cover allow us to: (a) identify a range of interaction styles between intra‐basement structures and overlying, Plio‐Pleistocene rift‐related normal faults; and (b) examine the cover fault kinematics associated with each interaction style. Some of the normal faults parallel and are physically connected to intra‐basement reflections, which are interpreted as mylonitic reverse faults formed during Mesozoic subduction and basement terrane accretion. These geometric relationships indicate pre‐existing intra‐basement structures locally controlled the position and attitude of Plio‐Pleistocene rift‐related normal faults. However, through detailed 3D kinematic analysis of selected normal faults, we show that: (a) normal faults only nucleated above intra‐basement structures that experienced late Miocene compressional reactivation, (b) despite playing an important role during subsequent rifting, intra‐basement structures have not been significantly extensionally reactivated, and (c) preferential nucleation and propagation of normal faults within late Miocene reverse faults and folds appears to be the key genetic relationship between contractionally reactivated intra‐basement structures and rift‐related normal faults. Our analysis shows that km‐scale, intra‐basement structures can control the nucleation and development of newly formed, rift‐related normal faults, most likely due to a local perturbation of the regional stress field. Because of this, simply inverting fault strike for causal extension direction may be incorrect, especially in provinces where pre‐existing, intra‐basement structures occur. We also show that a detailed kinematic analysis is key to deciphering the temporal as well as simply the spatial or geometric relationship between structures developed at multiple structural levels.     

Chemical composition and iron oxidation state of amorphous matrix silicates in the carbonaceous chondrite Acfer 094

Nanoscale amorphous silicates are a major component in primitive carbonaceous chondrite matrices and anhydrous interplanetary dust particles. Owing to their metastability and sensitive response to reactions with water, this material is of particular interest in understanding nebular and parent body processes in the early solar system. Here we investigated the amorphous silicate matrix (ASM) in the ungrouped carbonaceous chondrite Acfer 094 regarding its texture, chemical composition, and Fe oxidation state. We applied transmission electron microscopy techniques on six, focused ion beam technique-prepared, electron-transparent lamellae of Acfer 094 to determine the textures of this material. Furthermore, we used energy-dispersive X-ray analysis and electron energy loss spectroscopy to quantify the Fe content and the Fe oxidation state of the ASM. Textural investigations reveal differences in sulfide content, porosity, and distribution of the ASM among the samples, as well as evidence for rare recrystallization of phyllosilicate fibers. The chemical composition reveals mobilization of Fe. Furthermore, the determined Fe³⁺/ΣFe ratios of the ASM in the six samples display a homogeneously high oxidation state (0.66–0.73). This high and homogeneous Fe oxidation state in the ASM of Acfer 094 disagrees with its formation as a primary phase in a reduced solar gas and must have been induced in a later stage process. Most likely, this process was aqueous alteration on the Acfer 094 parent body, which led to hydration and oxidation of the ASM, which is supported by textural and chemical evidence of aqueous alteration.     

The brecciated texture of polymict eucrites: Petrographic investigations of unequilibrated meteorites from the Antarctic Yamato collection

We report on the petrography and mineralogy of five Yamato polymict eucrites to better constrain the formation and alteration of crustal material on differentiated asteroids. Each sample consists of different lithic clasts that altogether form four dominant textures and therefore appear to originate from closely related petrological areas within Vesta′s crust. The textures range from subophitic to brecciated, porphyritic, and quench‐textured, that differ from section to section. Comparison with literature data for these samples is therefore difficult, which stresses that polymict eucrites are extremely complex in their petrography and investigation of only one thick section may not be representative for the host rock. We also show that sample Y‐793548 consists of more than one lithic unit and must therefore be classified as polymict instead of monomict. The variety and nature of lithic textures in the investigated Yamato meteorites indicate shock events, intense post‐magmatic thermal annealing, and secondary alteration. These postmagmatic features occur in different intensities, varying from clast to clast or among coexisting mineral fragments on a small, local scale. Several clasts within the eucrites studied have been modified by late‐stage alteration processes that caused deposition of Fe‐rich olivine and Fe enrichment along cracks crosscutting pyroxene crystals. However, formation of these secondary phases seems to be independent of the degree of thermal metamorphism observed within every type of clast, which would support a late‐stage metasomatism model for their formation.     

The presolar grain inventory of fine‐grained chondrule rims in the Mighei‐type (CM) chondrites

We investigated the inventory of presolar silicate, oxide, and silicon carbide (SiC) grains of fine‐grained chondrule rims in six Mighei‐type (CM) carbonaceous chondrites (Banten, Jbilet Winselwan, Maribo, Murchison, Murray and Yamato 791198), and the CM‐related carbonaceous chondrite Sutter's Mill. Sixteen O‐anomalous grains (nine silicates, six oxides) were detected, corresponding to a combined matrix‐normalized abundance of ~18 ppm, together with 21 presolar SiC grains (~42 ppm). Twelve of the O‐rich grains are enriched in ¹⁷O, and could originate from low‐mass asymptotic giant branch stars. One grain is enriched in ¹⁷O and significantly depleted in ¹⁸O, indicative of additional cool bottom processing or hot bottom burning in its stellar parent, and three grains are of likely core‐collapse supernova origin showing enhanced ¹⁸O/¹⁶O ratios relative to the solar system ratio. We find a presolar silicate/oxide ratio of 1.5, significantly lower than the ratios typically observed for chondritic meteorites. This may indicate a higher degree of aqueous alteration in the studied meteorites, or hint at a heterogeneous distribution of presolar silicates and oxides in the solar nebula. Nevertheless, the low O‐anomalous grain abundance is consistent with aqueous alteration occurring in the protosolar nebula and/or on the respective parent bodies. Six O‐rich presolar grains were studied by Auger Electron Spectroscopy, revealing two Fe‐rich silicates, one forsterite‐like Mg‐rich silicate, two Al‐oxides with spinel‐like compositions, and one Fe‐(Mg‐)oxide. Scanning electron and transmission electron microscopic investigation of a relatively large silicate grain (490 nm × 735 nm) revealed that it was crystalline åkermanite (Ca₂Mg[Si₂O₇]) or a an åkermanite‐diopside (MgCaSi₂O₆) intergrowth.     

Products and Mechanism of the Gas Phase Reaction of Ozone with β-Pinene

Gas phase ozonolysis of -pinene was performedin a 570 l static reactor at 730 Torr and 296 K insynthetic air and the products were analysed by acombination of gas phase FTIR spectroscopy, HPLC andIC analyses of gas phase and aerosol samples,respectively. The reaction mechanism was investigatedby adding HCHO, HCOOH and H₂O as Criegeeintermediate scavenger and cyclohexane as OH radicalscavenger. Main identified products (yields inparentheses) in the presence of cyclohexane as OHradical scavenger were HCHO (0.65 ± 0.04),nopinone (0.16 ± 0.04), 3-hydroxy-nopinone (0.15± 0.05), CO₂ (0.20 ± 0.04), CO (0.030± 0.002), HCOOH (0.020 ± 0.002), the secondaryozonide of -pinene (0.16 ± 0.05), andcis-pinic acid (0.02 ± 0.01). The decompositionof the primary ozonide was found to yieldpredominantly the excited C₉-Criegee intermediateand HCHO (0.84 ± 0.04) and to a minor extent theexcited CH₂OO intermediate and nopinone (0.16± 0.04). Roughly 40% of the excitedC₉-Criegee intermediate becomes stabilised andcould be shown to react with HCHO, HCOOH and H₂O. The atmospherically important reaction of thestabilised C₉-Criegee intermediate with H₂Owas found to result in a nopinone increase of (0.35± 0.05) and in the formation of H₂O₂(0.24 ± 0.03). Based on the observed products,the unimolecular decomposition/isomerisationchannels of the C₉-Criegee intermediate arediscussed in terms of the hydroperoxide and esterchannels. Subsequent reactions of the nopinonylradical, formed in the hydroperoxide channel, lead tomajor products like 3-hydroxy-nopinone but also tominor products like cis-pinic acid. A mechanismfor the formation of this dicarboxylic acid isproposed and its possible role in aerosol formationprocesses discussed.     

Lead isotopic composition of the potassic rocks from Roccamonfina (South Italy)

Pb isotope data are presented for the potassic rocks from Roccamonfina and some other Campanian volcanoes. Pb isotope variations for Roccamonfina fall within the previously found range of values for the Italian potassic volcanism and form similar shallow regression lines in the Pb-Pb diagrams. Their interpretation as two-component mixing lines is well supported by other geochemical evidence. The relation of the mixing processes deduced for Roccamonfina and for the wider regional volcanism is discussed. The enriched and anomalous mantle under Italy is proposed to be a result of various degrees of metasomatism of a range of “Atlantic island” type mantle compositions by an LIL-element-enriched mantle “fluid”. The mantel “fluid” may either derive its isotope and trace element characteristics from an old LIL-element-enriched mantle source or from continental crust which has to some extend retained its geochemical identity in the upper mantle.     

Methane and sulfide fluxes in permanent anoxia: In situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m⁻² d⁻¹. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m⁻² d⁻¹) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 10⁷ mol yr⁻¹. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m⁻² d⁻¹. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.