Groundwater residence times and flow paths in fractured rock determined using environmental tracers in the Mission Tunnel; Santa Barbara County,California, USA

Multiple geochemical tracers [ion chemistry, stable isotopes of water, chlorofluorocarbons (CFC), tritium] and a 25-year-long record of discharge were used to understand residence times and flow paths of groundwater seeps in the fractured rock aquifer surrounding the Mission Tunnel, Santa Barbara, California. Tritium data from individual seeps indicate that seep waters are a mixture of >45-year-old (recharged prior to the nuclear bomb tests) and young groundwater. CFC data support this interpretation, however, a two-end member mixing model cannot completely explain the age tracer data. Microbial degradation and partial re-equilibration complicate the CFC signal. Spectral analysis of precipitation and groundwater seepage records shows that seepage lags precipitation by 3 months. This delay is related to the advancement of the wetting front and increasing the number of active flow paths. Additionally, the amount of seepage produced by precipitation is less during extended periods of drought than during normal or wet periods, suggesting antecedent conditions strongly affect flow through this fractured rock aquifer.     

Deep to shallow lacustrine evaporites in the Libros Gypsum (southern Teruel Basin, Miocene, NE Spain): an occurrence of pelletal gypsum rhythmites

ABSTRACT A number of non‐marine evaporite units composed of primary gypsum were deposited in saline lakes that developed in the southern Teruel Basin (NE Spain) during the Miocene. In the basin depocentre, a continuum of lacustrine evaporite lithofacies influenced by the activity of organisms is displayed. The Libros Gypsum was deposited in a deep lake, in which water stratification became unstable with progressive shoaling. Rhythmites, composed of laminae of pelletal gypsum and laminae of very fine lenticular gypsum crystals mixed with siliceous microorganisms, formed in addition to gypsum turbidites, intraformational gypsum breccias and slump structures. The pelletal laminae originated from the faecal activity of animals (crustaceans?) ingesting gypsum crystallites in the lake water during episodes of maximum evaporation, whereas the laminae of very fine lenticular gypsum mixed with microorganisms accumulated during episodes of relative dilution. In the wide marginal zones of the basin, the Libros Gypsum unit consists of massive to thin‐bedded bioturbated gypsum and thin‐bedded clotted gypsum, which formed in intermediate to very shallow (palustrine) water depths. The bioturbated gypsum lithofacies were produced by the action of diverse organisms, presumably worms and coleopterans, and chironomid larvae to a lesser extent; the massive lithofacies precipitated in very shallow water; and the thin‐bedded lithofacies formed in shallow to deeper settings. The thin‐bedded clotted gypsum is a relatively deep facies that may have diverse origins (e.g. bioturbation, compaction, disruption of soft sediments and early diagenesis). There is a well‐developed metre‐scale cyclicity in the marginal lake sequences, which is not observed in the inner lake deposits. This suggests a depth control in the various lacustrine subenvironments to record cyclic evaporitic processes. The isotopic composition of the gypsum indicates early sulphate‐reducing bacterial activity in the bottom of the lake and suggests that the sulphate was derived from the chemical recycling of Triassic evaporites of the country rocks.     

Comparison of Cu and Zn cycling in eutrophic lakes with oxic and anoxic hypolimnion

Data on the cycling of Cu and Zn in two eutrophic lakes are presented: Lake Greifen that becomes seasonally anoxic in its hypolimnion and Lake Sempach that is aerated during winter and oxygenated during summer. They suggest that hypolimnetic oxygenation 1) enhances the release of copper from the sediment but 2) also accelerates the entrapment and deposition of Cu and Zn by freshly formed Mn- and Fe-oxides.     

Relationship of Avalonian and Cadomian terranes to Grenville and Pan-African events

Suturing of the supercontinent Rodinia in the Grenville event (˜ 1000 Ma) was followed by rifting in the late Proterozoic (˜ 800-700 Ma), reorganization to Gondwana in the Pan-African (˜ 700-500 Ma) and further accretion to develop Pangea at the end of the Paleozoic. One of the Rodinian rifts followed part of the Grenville suture, it produced the margin of eastern North America and southern Baltica and the contrasting margin of west Gondwana in present South America. The Paleozoic accretionary wedge against the Grenville-age margin of North America and Baltica contains Avalonian/Cadomian terranes that exhibit Pan-African erogenic events ± sediments apparently developed while the terranes were in or near Gondwana. These terranes carry lower-Paleozoic fauna (Acado-Baltic) that are not indigenous to North America and Baltica.U---Pb zircon ages range from 1500-1000 Ma in Grenville terranes and from 800–500 Ma with minor inheritance in Avalonian terranes; they are generally much older in Cadomian terranes, implying very little resetting during Pan-African events. T_DM ages are generally 2000–1200 Ma in Grenville terranes, 1300–600 Ma in Avalonian terranes and 2000–1200 in Cadomian terranes. These summary data show that: (1) the Grenville orogenic event produced almost no juvenile crust; (2) the Avalonian terranes of North America contain crust that evolved primarily in the late Proterozoic, possibly as a mixture of juvenile Pan-African material and Grenville or slightly older material; (3) the Cadomian terranes of Europe consist of old (middle-Proterozoic to Archean) crust with minor juvenile Pan-African material. The Avalonian terranes apparently evolved near, and partly on, the Grenville-age crust now in South America during the intense orogeny associated with rotation of Gondwana away from North America. The Cadomian terranes of Europe, however, appear to be fragments of other parts of Gondwana, probably West Africa.     

Ar / Ar dating of high-pressure rocks from the Ligurian Alps: Evidence for a continuous subduction–exhumation cycle

We present ³⁹Ar–⁴⁰Ar dating of phengite, muscovite and paragonite from a set of mafic and metasedimentary rocks sampled from the high-pressure (HP) metaophiolites of the Voltri Group (Western Alps) and from clasts in the basal layer conglomerates from the Tertiary molasse which overlie the high-pressure basement. The white mica-bearing rocks display peak eclogitic and blueschist-facies parageneses, locally showing complex greenschist-facies replacement textures. The internal discordance of age spectra is proportional to the chemical complexity of the micas. High-Si phengites from eclogite clasts record a ³⁹Ar–⁴⁰Ar age of ca. 49 Ma for the eclogite stage and ca. 43 Ma for the blueschist retrogression; phengites from a blueschist basement sample yield an age of ca. 40 Ma; low-Si muscovite from a metasediment dates the formation of the greenschist paragenesis at ca. 33 Ma. Our data indicate that the analyzed samples reached high-pressure conditions at different times over a time-span of c.a. 10 Ma. Subduction was continuing during exhumation and blueschist retrograde re-equilibration of higher-pressure, eclogite-facies rocks. This process kept the isotherms depressed, allowing the older HP-rocks to escape thermal re-equilibration. Our results, added to literature data, fit a tectonic model of a subduction–exhumation cycle, with different tectonic slices subducted at different times from Early Eocene until the Eocene–Oligocene boundary.     

Production of a molybdophore during metal-targeted dissolution of silicates by soil bacteria

Although many bioessential metals are scarce in natural water and rock systems, microbial secretion of high-affinity ligands for metal extraction from solid phases has only been documented for Fe. However, we have discovered that Mo is extracted from a silicate by a high-affinity ligand (a possible “molybdophore”) secreted by an N₂-fixing soil bacterium. The putative molybdophore, aminochelin, is secreted as a siderophore under Fe-depleted conditions, but is also secreted under Fe-sufficient, Mo-depleted conditions. Presumably, molybdophore production facilitates uptake of Mo for use in Mo enzymes. In contrast, an Fe-requiring soil bacterium without a special Mo requirement only enhances the release of Fe from the silicate. Fractionation of Mo stable isotopes during uptake to cells may provide a “fingerprint” for the importance of chelating ligands in such systems. Many such metal-specific ligands secreted by prokaryotes for extraction of bioessential metals, their effects on Earth materials, and their possible utility in the recovery of economic metals remain to be discovered.     

Adsorption of Copper, Nickel, and Cadmium on Goethite in the Presence of Organic Ligands

Adsorption of copper, cadmium and nickel at low concentrations on goethite was studied in the presence of the simple organic ligands oxalate, salicylate, and pyromellitate. The experimental metal adsorption behavior was compared to calculations with a surface complexation model to evaluate the most important interactions. Oxalate mostly decreased Cu and Ni adsorption at high pH-values by competition between solution and surface complexation but had no effect on Cd adsorption. Cu adsorption in the presence of oxalate below pH 6 could best be described by defining a ternary complex of type A (surface-metal-ligand). Salicylate had only minor effects on metal adsorption. The adsorption of Cu in the presence of salicylate above pH 5 could be explained by a ternary complex of type A. Pyromellitate increased the adsorption of Cu and Cd in the acidic pH-range, likely by formation of ternary surface complexes of type B (surface-ligand-metal).     

Eclogite relics in the Variscan orogenic belt of Bulgaria (SE Europe)

Eclogitic rocks were sampled from two zones in the basement of the Sredna Gora terrane (central western Bulgaria): (1) partially retrogressed eclogites and amphibolites embedded in sillimanite-bearing garnet-micaschists with kyanite relics and migmatites and (2) banded amphibolites associated with muscovite-bearing metagranites within two-mica paragneisses. Rutile relics and oligoclase + green hornblende + epidote ± biotite pseudomorphs after garnet suggest an eclogite facies event. A tholeiitic, transitional affinity was determined for the protoliths, suggesting a continental rift environment, consistent with several eclogite-bearing complexes in the eastern segments of the Variscan belt that arose from the Cambro-Ordovician Gondwana break-up. Decreasing pressure after the eclogite overprint was demonstrated by (a) diopside-albite symplectite, and (b) plagioclase + red–brown to green amphibole kelyphite. The early static re-equilibration, dated to 398 ± 5.2 Ma by ⁴⁰Ar–³⁹Ar technique, was followed by an amphibolite facies foliation, which was pervasive in amphibolites, gneisses and micaschists, and poorly developed in eclogites. The lithospheric PT paths corresponding to higher and lower metamorphic gradients reflect the juxtaposition of crustal and lithospheric mantle units, respectively. In the build-up of the basement of the Balkan orogen, the physical properties of the lithological complexes might have influenced the collisional pattern of involved microplates.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.