Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δC and ΔC values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ¹³C and Δ¹⁴C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7c, cy17:0, and 18:1ω7c. A PLFA biomarker for type II methanotrophs, 18:1ω8c, comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH₄ as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ¹⁴C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ¹⁴C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH₄ produced by the reduction of DIC. In contrast, δ¹³C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ¹³C_CH4 values (∼−95‰) for each water. The δ¹³C_PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ¹⁴C_PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ¹⁴C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ¹³C_PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H₂. Results of sample storage experiments showed substantial shifts in microbial community composition and δ¹³C_PLFA values (as much as 5‰) during 2-4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ¹³C_PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.     

Modeling CO2 chemistry, δC, and oxidation of organic carbon and methane in sediment porewater: Implications for paleo-proxies in benthic foraminifera

I present a numerical diffusion-advection-reaction model to simulate CO₂ chemistry, δ¹³C, and oxidation of organic carbon and methane in sediment porewater. The model takes into account detailed reaction kinetics of dissolved CO₂ compounds, H₂O, H⁺, OH⁻, boron and sulfide compounds. These reactions are usually assumed to be in local equilibrium, which is shown to be a good approximation in most cases. The model also includes a diffusive boundary layer across which chemical species are transported between bottom water and the sediment-water interface. While chemical concentrations and δ¹³C_TCO2 at these locations are frequently assumed equal, I demonstrate that they can be quite different. In this case, shells of benthic foraminifera do not reflect the desired properties of bottom water, even for species living at the sediment-water interface (z = 0 cm). Environmental conditions recorded in their shells are strongly influenced by processes occurring within the sediment. The model is then applied to settings in the Santa Barbara Basin and at Hydrate Ridge (Cascadia Margin), locations of strong organic carbon and methane oxidation. In contrast to earlier studies, I show that a limited contribution of methane-derived carbon to porewater TCO₂ in the Santa Barbara Basin cannot be ruled out. Simulation of methane venting shows that at oxidation rates greater than , the δ¹³C of porewater TCO₂ at z > 1 cm is depleted by more than 15‰ relative to bottom water. Depletions of this magnitude have not been observed in living benthic foraminifera, even at methane vents with much higher oxidation rates. This suggests that foraminifera at these sites either calcify at very shallow sediment depth or during times when oxidation rates are much lower than ∼50 μmol cm⁻² y⁻¹.     

Riverine carbon fluxes and soil erosion in the Zhujiang(Pearl)River Drainage Basin, South China

This paper deals with the water and suspension in the Zhujiang(Pearl)River and its three tributaries: the Xijiang River, the Beijiang River and the Dongjiang River where samples were collected. The authors calculated the riverine carbon fluxes and measure…     

Chemistry,isotope values (δD, δ18O, δ34SSO4) and temperatures of the water inflows in two Gotthard tunnels,Swiss Alps

Water inflows in the Gotthard Highway Tunnel and in the Gotthard Exploration Tunnel are meteoric waters infiltrating at different elevations, on both sides of an important orographic divide. Limited interaction of meteoric waters with gneissic rocks produces Ca–HCO₃ and Na–Ca–HCO₃ waters, whereas prolonged interaction of meteoric waters with the same rocks generates Na–HCO₃ to Na–SO₄ waters. Waters circulating in Triassic carbonate-evaporite rocks have a Ca–SO₄ composition. Calcium-Na–SO₄ waters are also present. They can be produced through interaction of either Na–HCO₃ waters with anhydrite or Ca–SO₄ waters with a local gneissic rock, as suggested by reaction path modeling. An analogous simulation indicates that Na–HCO₃ waters are generated through interaction of Ca–HCO₃ waters with a local gneissic rock. The two main SO₄-sources present in the Alps are leaching of upper Triassic sulfate minerals and oxidative dissolution of sulfide minerals of crystalline rocks. Values of δ³⁴S_SO4 < ∼+9‰ are due to oxidative dissolution of sulfide minerals, whereas δ³⁴S_SO4 >∼+9‰ are controlled either by bacterial SO₄ reduction or leaching of upper Triassic sulfate minerals. Most waters have temperatures similar to the expected values for a geothermal gradient of 22°C/km and are close to thermal equilibrium with rocks. However relatively large, descending flows of cold waters and ascending flows of warm waters are present in both tunnels and determine substantial cooling and heating, respectively, of the interacting rocks. The most import upflow zone of warm, Na-rich waters is below Guspisbach, in the Gotthard Highway Tunnel, at 6.2–9.0 km from the southern portal. These warm waters have equilibrium temperatures of 65–75°C and therefore constitute an important low-enthalpy geothermal resource.     

Li, Be, B concentrations and δ7Li values in plagioclase phenocrysts of dacites from Nea Kameni (Santorini, Greece)

Li, Be, B and δ⁷Li SIMS analyses of plagioclase phenocrysts from the 1040–1941 Niki dacite lava (Nea Kameni, Santorini, Greece) exhibit varied processes. From their anorthite contents alone, the crystals may be segregated into four main types: type-N shows the normal decline in An during crystallisation (An_62–40); type-O has only oscillatory zoning accompanied by resorption surfaces (An_58–39); type-C is complex with high-An cores (subtype C1: An_64–58, subtype C2: An_88–73) and normal rims (An_55–42). Type-A plagioclase with high An content (An_92–82) is found within mafic enclaves. On the basis of their Li concentrations, type-O crystals may be subdivided into subtype O1 with flat Li concentration profiles and subtype O2 with decreasing Li concentration from core to rim. The concentrations of Be and B of all four types show a negative correlation with anorthite content (An), but Li concentration profiles differ amongst the different plagioclase types. Types N and O1, and the cores of type-C, are equilibrated in Li concentration. Types O2 and A, and the mantles of type-C display an initial enrichment in Li, probably from volatile influx into the melt. Consistent with the propensity towards equilibrium with the melt, these crystals display dramatic rim-ward declines in Li concentration. All analysed plagioclase crystals, except for the xenocrystic type-A, have nearly the same Li, Be and B concentrations at their rims. These coincide with the composition of plagioclase microlites in the groundmass, thereby affording estimates of plagioclase-melt partitioning for the light elements: K _Li = 0.19–0.28, K _Be = 0.24–0.38 and K _B = 0.007–0.009. δ⁷Li profiles in type-O2 and type-A phenocrysts manifest an unmistakable inverse relation to Li concentration, with variations of up to ~39 ‰, revealing preferential kinetic diffusion. This may have been driven by Li loss from the melt, most likely through degassing during decompression, perhaps in the course of magma ascent to subsequent eruption. Considering the rapid diffusion of Li in plagioclase, in situ phenocryst analyses may yield useful information about processes leading up to, or even causing, eruptions.     

Phytoplankton,protozooplankton and nutrient dynamics in the Bornholm Basin (Baltic Sea) in 2002–2003 during the German GLOBEC Project

From March 2002 to until April 2003 we investigated the seasonal nutrient and phytoplankton dynamics in the central Bornholm Basin (Baltic Sea) within the framework of the German GLOBEC Project. We choose a nested approach consisting of vertical fluorescence profiles, phytoplankton counts and nutrient analyses. The Fluoroprobe (MultiProbe, BBE Moldaenke) is capable of distinguishing four algal groups (Cryptophyceae, Cyanophyceae, Chlorophyceae, Bacillariophyceae + Dinophyceae). Winter nutrient concentrations were about 5 μM NO₃ and 0.5 μM PO₄ in the central Basin. The spring phytoplankton bloom was dominated by the diatom Skeletonema sp. and reached a maximum of about 270 μg C/l before the onset of the seasonal stratification. Protozooplankton was dominated by the Mesodinium rubrum (a phototrophic ciliate = Myrionecta rubra) and reached a maximum biomass of about 200–300 μg C/l about 2 weeks after the demise of the diatom spring bloom. During summer, the water column was stratified and a subsurface maximum developed near the thermocline consisting of Bacillariophyceae, Cryptophycea and other phototrophic flagellates. Phytoplankton and protozooplankton biomass was generally low. Nutrient concentrations point towards a nitrogen limitation during this period. The stratification period ended during September and surface nutrient concentrations increased again. Protozooplankton reached a second maximum during September. With the Fluoroprobe small scale structures in the plankton community could be detected like a subsurface Cryptophyceae maximum near the thermocline that however, could not be confirmed by cell counts. The chlorophyll a estimate of the Fluoroprobe was in good agreement with the phytoplankton biomass estimated from counts. We conclude that only by combining modern sensing technology with microscopy, the small-scale dynamics and taxonomic spectrum of the plankton can be fully captured.     

Geology,mineralogy and geochemistry of the Kekem dyke swarm (Western Cameroon): Insights into Paleozoic–Mesozoic magmatism and geodynamic implications

The broadly N70°–90°E-trending dykes swarm at Kekem cut across the Paleoproterozoic-to-Achean terranes of West Cameroon remobilized during the Pan-African orogeny. They are picrite basalts and basalts with tholeiitic/transitional affinity, as shown by mineralogical and geochemical data, with variable major and trace element contents, MgO ranges from 7.3 to 12.4 wt.%, Cr from 190 to 411 ppm, Ni from 15 to 234 ppm. All the dykes are light REE enriched with La_N/Yb_N values of 5.3–8.1, suggesting a co-magmatic origin. They originated from a 2.8% partial melting of a spinel-mantle source with no or little crustal input. The geochemical features of Kekem dykes are similar to those of Paleozoic and Mesozoic dykes recorded in North and Central Africa, suggesting multiple reactivations of pre-existing fractures that resulted in the fragmentation of western Gondwana and the opening of Central and South Atlantic Oceans.     

How continuous and precise is the record of P–T paths? Insights from combined thermobarometry and thermodynamic modelling into subduction dynamics (Schistes Lustrés,W. Alps)

Pressure–temperature (P–T) paths as complete as possible and with a precision on the km‐scale or less are needed to further improve the knowledge of deformation, re‐equilibration processes and element/fluid transfer, in particular along subduction zones. This contribution attempts to (i) critically evaluate the precision and continuity with which metamorphic P–T histories are retrieved today and (ii) discuss implications for regional‐scale accretionary processes in subduction zones, through application to the Schistes Lustrés complex (Haute Maurienne, W. Alps). P–T estimates are compared and combined using several independent approaches: (i) from minerals assumed to be in textural equilibrium; (ii) from electron microprobe compositional maps; and (iii) from pseudosection modelling predictions. Multi‐equilibrium calculations were performed with tweequ and thermocalc, and pseudosections were built with Perple_X and Theriak/Domino. These P–T estimates were also compared with maximum temperatures (T_max) deduced from the Raman spectroscopy of carbonaceous matter. The different methods used here yield the peak of pressure for the lower structural unit of the Schistes Lustrés at 480 °C and 23 kbar and document the retrograde path for both the Median and Lower Units. The results show that P–T conditions are recorded almost continuously and can be determined with a precision of ±1 kbar and ±30 °C at best. This study underlines the complementarity of the various thermobarometric methods and demonstrates that precision could be increased by improving solid solution models for chlorite. Observed tectonic patterns, major lithological boundaries, pressure–temperature and T_max data suggest that underplating processes and early structural development played a key role in the Schistes Lustrés accretionary complex.     

Hydrological budget,carbon sources and biogeochemical processes in Lac Pavin (France): Constraints from δO of water and δC of dissolved inorganic carbon

Lac Pavin (French Massif Central) is a permanently stratified lake: the upper water layers (mixolimnion, from 0 to 60 m depth) are affected by seasonal overturns, whereas the bottom water layers (monimolimnion, from 60 to 90 m depth) remain isolated and are never mixed. Hence, they are capable of storing important quantities of dissolved gases, mainly CO₂. With the aim of better constraining the water balance and of gaining new insights into the carbon cycle of Lac Pavin, an isotopic approach is used. The δ¹⁸OH₂O$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}$ profiles lead the authors to give a new evaluation of the evaporation flow rate (8 L s⁻¹), and to propose and characterize two sub-surface springs. The sub-surface spring located at the bottom of the lake can be deduced from the 1% isotopic difference between the upper water layers (mean δ¹⁸OH₂O$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}$ value: −7.3‰) and the bottom water layers (δ¹⁸OH₂O=-8.4‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}=-8.4‰$). It is argued that this sub-surface spring has isotopic and chemical characteristics similar to those of the magmatic CO₂-rich spring (i.e. Fontaine Goyon, δ¹⁸OH₂O=-9.4‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}=-9.4‰$), and we calculate its flow rate of 1.6 L s⁻¹. The second sub-surface spring is located around 45 m depth, with a composition close to those of the water surface streams (δ¹⁸OH₂O<-7.6‰$\delta {}^{18}{\text{O}}_{{\text{H}}_2\text{O}}<-7.6‰$).     

How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II), mn(II), and S(?II) in undisturbed soils and sediments using voltammetry

Background

Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach??the pilot ion method??has not been documented in detail.

Results

A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II) and Mn(II), subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II) to Fe(II) varied by no more than 11% from one Hg/Au electrode to another and Fe(II) concentrations predicted by the Mn(II) pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15???M Fe(II) (46% different on average). The ratio of calibration slopes of Mn(II) to S(?II) varied by almost 20% from one Hg/Au electrode to another, and S(?II) predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II) and S(?II) concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At medium-to-high concentration for the ocean, naturally derived dissolved organic carbon did not significantly affect the baseline-corrected electrode response of Mn(II) and Fe(II), but did significantly affect the response of S(?II).

Conclusions

Despite their intrinsic variability, Hg/Au electrodes fabricated by hand can be used to quantify O₂, S(?II), Fe(II), and Mn(II) without calibrating every electrode for every constituent of interest. The pilot ion method can achieve accuracies to within 20% or less, provided that the underlying principle??the independence of slope ratios??is demonstrated for all voltammetric techniques used, and effects of the physicochemical properties of the system on voltammetric signals are addressed through baseline subtraction.     

Fatty acid and stable isotope (δC, δN) signatures of particulate organic matter in the lower Amazon River: Seasonal contrasts and connectivity between floodplain lakes and the mainstem

Fatty acid (FA) composition and stable isotope (δ¹³C, δ¹⁵N) signatures of four aquatic plants, plankton, sediment, soil and suspended particulate organic matter (SPOM) collected from open floodplain lakes (Várzea) and rivers of the central Brazilian Amazon basin were gathered during high and low water stages in 2009. SPOM from Várzea had a major contribution of autochthonous material from phytoplankton and C₃ aquatic plants. As shown from stable isotope composition of SPOM (δ¹³C −31.3 ± 3.2‰; δ¹⁵N 3.6 ± 1.5‰), the C₄ aquatic phanerogam (δ¹³C −13.1 ± 0.5‰; δ¹⁵N 4.1 ± 1.7‰) contribution appeared to be weak, although these plants were the most abundant macrophyte in the Várzea. During low water season, increasing concentration of 18:3ω3 was recorded in the SPOM of lakes. This FA, abundant mainly in the Várzea plants (up to 49% of total FAs), was due to the accumulation of their detritus in the ecosystem. This dry season, when connectivity with the river mainstem was restricted, was also characterized by a high concentration in the SPOM of the cyanobacteria marker 16:1ω7 (up to 21% of total FAs). The FA compositions of SPOM from the Amazon River also exhibited significant seasonal differences, in particular a higher concentration of 16:1ω7 and 18:3ω3 during the dry season. This suggests a seasonal contribution of autochthonous material produced in Várzea to the Amazon River SPOM.     

Punctual and continuous estimation of transit time from dissolved organic matter fluorescence properties in karst aquifers,application to groundwaters of ‘Fontaine de Vaucluse’ experimental basin (SE France)

For about 10 years, environmental tracing development using dissolved organic matter (DOM) has been the subject of several studies. Particularly, the use of characterization techniques, like fluorescence emission–excitation matrices has enabled the identification of DOM sources and monitoring them within mainland or marine hydrosystems. Moreover, hydrogeologists have shown the significance of total organic carbon content used as a fast seepage tracer in karstic aquifers. The aim of this study consists in using DOM fluorescence signals to develop a transit time semi-quantitative tracer in heterogeneous hydrosystems. The Low-Noise Underground Laboratory (Vaucluse, France) cuts the network of Fontaine de Vaucluse (FV) karstic vadose zone randomly, and offers a special access to different unstructured dripwaters, with different hydrodynamic behaviour, inside its galleries, i.e. not hierarchical as in natural caves. Previous long-term hydrodynamic and hydrochemical studies allowed the understanding of their hydrogeological behaviour and the estimation of mean transit times. That is why this site is adequate to develop new transit time tracers. After identification of the different DOM sources (i.e. lithic and rendzic leptosols), fluorescence intensities monitoring from soil leachates and dripwaters, for certain excitation–emission wavelength pairs, allowed the development of punctual transit time tracing, by spotting infiltration periods of fluorescent compounds, and monitoring their transfer within a hydrosystem. A fluorescence index (humification index) and the mean transit time of each gallery groundwater, stemmed from previous hydrodynamic and hydrochemical studies, allowed the calibration of a logarithmic relationship. This one allows the development of a continuous transit time tracing method that estimates transit times without long-term studies. It has been tested on two springs of FV catchment basin, providing transit time estimations for karstic hydrosystems that do not present a mixture between recent and pluriannual waters.     

U–Pb and Re–Os isotopic systematics and zircon Ce4 +/Ce3 + ratios in the Shiyaogou Mo deposit in eastern Qinling,central China: Insights into the oxidation state of granitoids and Mo (Au) mineralization

The newly-discovered Shiyaogou molybdenum deposit is located in the eastern Qinling metallogenic belt in central China. The deposit contains at least 152,000 t of Mo metal and bears typical porphyry-type features in terms of its concentric alteration zonation, quartz vein-hosted Mo mineralization, veining sequence and the spatial association with concealed granite porphyries. Re–Os isotope analyses of molybdenite from the deposit yield an ore-forming age of 132.3 ± 2.8 Ma. LA-ICP-MS U–Pb zircon dating of ore-related porphyries yields crystallization ages from 135 Ma to 132 Ma, indicating a temporal link between granitic magmatism and Mo mineralization. A population of captured magmatic zircons indicates another pulse of magmatism at ~ 143 Ma. A barren granite intrusion near the deposit gives a zircon U–Pb age of 148.1 ± 1.1 Ma. These magmatic activities were concurrent with the emplacement of the nearby Heyu granitic batholith, a largely ore-barren intrusive complex formed from ~ 148 Ma to ~ 127 Ma. Zircon Ce^4 +/Ce^3 + ratios of ore-related porphyries are obviously higher than those of contemporaneous barren granitoids, implying an affinity between Mo mineralization and highly oxidized magmas. Moreover, zircons from these granitoids overall have decreasing Ce^4 +/Ce^3 + ratios from 148 Ma to 132 Ma, reflecting decreasing oxygen fugacities during magma evolution. Available geological, radiometric and stable isotopic evidence suggests that the decrease of magma oxygen fugacity was probably associated with an increase of mantle contribution to granitic magmatism and metallogenesis, which probably gave rise to successive mineralization of Mo and Au in the eastern Qinling. The intense magmatic–metallogenic events in the eastern Qinling during Late Jurassic to Early Cretaceous times are interpreted as a response to the large-scale lithosphere thinning and subsequent asthenosphere upwelling beneath the eastern part of the North China Craton.