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1.
Sediments from the Aquia aquifer in coastal Maryland were collected as part of a larger study of As in the Aquia groundwater flow system where As concentration are reported to reach levels as high as 1072 nmol kg−1, (i.e., ∼80 μg/L). To test whether As release is microbially mediated by reductive dissolution of Fe(III) oxides/oxyhydroxides within the aquifer sediments, the Aquia aquifer sediment samples were employed in a series of microcosm experiments. The microcosm experiments consisted of sterilized serum bottles prepared with aquifer sediments and sterilized (i.e., autoclaved), artificial groundwater using four experimental conditions and one control condition. The four experimental conditions included the following scenarios: (1) aerobic; (2) anaerobic; (3) anaerobic + acetate; and (4) anaerobic + acetate + AQDS (anthraquinone-2,6-disulfonic acid). AQDS acts as an electron shuttle. The control condition contained sterilized aquifer sediments kept under anaerobic conditions with an addition of AQDS. Over the course of the 27 day microcosm experiments, dissolved As in the unamended (aerobic and anaerobic) microcosms remained constant at around ∼28 nmol kg−1 (2 μg/L). With the addition of acetate, the amount of As released to the solution approximately doubled reaching ∼51 nmol kg−1 (3.8 μg/L). For microcosm experiments amended with acetate and AQDS, the dissolved As concentrations exceeded 75 nmol kg−1 (5.6 μg/L). The As concentrations in the acetate and acetate + AQDS amended microcosms are of similar orders of magnitude to As concentrations in groundwaters from the aquifer sediment sampling site (127-170 nmol kg−1). Arsenic concentrations in the sterilized control experiments were generally less than 15 nmol kg−1 (1.1 μg/L), which is interpreted to be the amount of As released from Aquia aquifer sediments owing to abiotic, surface exchange processes. Iron concentrations released to solution in each of the microcosm experiments were higher and more variable than the As concentrations, but generally exhibited similar trends to the As concentrations. Specifically, the acetate and acetate + AQDS amended microcosm typically exhibited the highest Fe concentrations (up to 1725 and 6566 nmol kg−1, respectively). The increase in both As and Fe in the artificial groundwater solutions in these amended microcosm experiments strongly suggests that microbes within the Aquia aquifer sediments mobilize As from the sediment substrate to the groundwaters via Fe(III) reduction.  相似文献   

2.
This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr−1. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m−2 d−1, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m−2 d−1 of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m−2 d−1 of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m−2 d−1 to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m−2 d−1 of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100-200 nmol cm−3 d−1). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m−2 d−1 or 96 mW m−2 of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide oxidation and anaerobic oxidation of methane (AOM) produce 95% and 2% of this energy flux, respectively. The low power output by AOM is due to strong bioenergetic constraints imposed on the reaction rate by the composition of the chemical environment. These constraints provide a high potential for dissolved methane efflux from the sediment (12.0 mmol m−2 d−1) and indicates a much lower efficiency of (dissolved) methane sequestration by AOM at seeps than considered previously. Nonetheless, AOM is able to consume a third of the ascending methane flux (5.9 mmol m−2 d−1 of CH4) with a high efficiency of energy expenditure (35 mmol CH4 kJ−1). It is further proposed that bioenergetic limitation of AOM provides an explanation for the non-zero sulfate concentrations below the AOM zone observed here and in other active and passive margin sediments.  相似文献   

3.
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4.
Sorption of Ni(II) onto chlorite surfaces was studied as a function of pH (5–10), ionic strength (0.01–0.5 M) and Ni concentration (10−8–10−6 M) in an Ar atmosphere using batch sorption with radioactive 63Ni as tracer. Such studies are important since Ni(II) is one of the major activation products in spent nuclear fuel and sorption data on minerals such as chlorite are lacking. The sorption of Ni(II) onto chlorite was dependent on pH but not ionic strength, which indicates that the process primarily comprises sorption by surface complexation. The maximum sorption was at pH ∼ 8 (Kd = ∼10−3 cm3/g). Desorption studies over a period of 1–2 weeks involving replacement of the aqueous solution indicated a low degree of desorption. The acid–base properties of the chlorite mineral were determined by titration and described using a non-electrostatic surface complexation model in FITEQL. A 2-pK NEM model and three surface complexes, Chl_OHNi2+, Chl_OHNi(OH)+ and Chl_OHNi(OH)2, gave the best fit to the sorption results using FITEQL. The high Kd values and low degree of desorption observed indicate that under expected groundwater conditions, a large fraction of Ni(II) that is potentially leachable from spent nuclear fuel may be prevented from migrating by sorption onto chlorite surfaces.  相似文献   

5.
Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of 90Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of 90Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L−1), pH variation is the main control on sorption. The sorption edge for 90Sr was observed between pH 4 and 6 with maximum sorption occurring (Kd ∼ 103 L kg−1) at pH 6–8. At ionic strengths above 10 mmol L−1, and at pH values between 6 and 8, cation exchange processes reduced 90Sr uptake to the sediment. This exchange process explains the lower 90Sr sorption (Kd ∼ 40 L kg−1) in the presence of artificial Magnox tank liquor (IS = 29 mmol L−1). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr2+ in either HCO3-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr2+ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated 90Sr was exchangeable with 1 M MgCl2 in all experiments. These results suggest that over long periods, 90Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of 90Sr is to be expected.  相似文献   

6.
Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH4) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH4 was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH4 with depth (5500 μmol L−1 DIC, 500 μmol L−1 CH4). Highest DIC and CH4 production rates occurred close to the water table (decomposition constant kd ∼ 10−3-10−4 a−1) or in some distinct zones at depth (kd ∼ 10−4 a−1). Deeper into the peat, decomposition proceeded very slowly at about kd = 10−7 a−1. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (−20 to −25 kJ mol−1 CH4). The methanogenic precursor acetate also accumulated (150 μmol L−1). In line with these findings, CH4 was formed by hydrogenotrophic methanogenesis at Gibbs free energies of −35 to −40 kJ mol−1 CH4. This was indicated by an isotopic fractionation αCO2-CH4 of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol−1 substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH4 may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.  相似文献   

7.
Methane microseepage is the result of natural gas migration from subsurface hydrocarbon accumulations to the Earth’s surface, and it is quite common in commercial petroleum fields. While the role of microseepage as a pathfinder in petroleum exploration has been known for about 80 a, its significance as an atmospheric CH4 source has only recently been studied, and flux data are currently available only in the USA and Europe. With the aim of increasing the global data-set and better understanding flux magnitudes and variabilities, microseepage is now being extensively studied in China. A static flux chamber method was recently applied to study microseepage emissions into the atmosphere in four different sectors of the Yakela condensed gas field in Tarim Basin, Xinjiang, China, and specifically in: (a) a faulted sector, across the Luntai fault systems; (b) an oil–water interface sector, at the northern margin of the field; (c) an oil–gas interface sector, in the middle of the field; (d) an external area, outside the northern gas field boundaries. The results show that positive CH4 fluxes are pervasive in all sectors and therefore, only part of the CH4 migrating from the deep oil–gas reservoirs is consumed in the soil by methanotrophic oxidation. The intensity of gas seepage seems to be controlled by subsurface geologic settings and lateral variabilities of natural gas pressure in the condensed gas field. The highest CH4 fluxes, up to ∼14 mg m−2 d−1 (mean of 7.55 mg m−2 d−1) with higher spatial variability (standard deviation, σ: 2.58 mg m−2 d−1), occur in the Luntai fault sector. Merhane flux was lower in the oil–water area (mean of 0.53 mg m−2 d−1) and the external area (mean of 1.55 mg m−2 d−1), and at the intermediate level in the gas–oil sector (mean of 2.89 mg m−2 d−1). These values are consistent with microseepage data reported for petroleum basins in the USA and Europe. The build-up of methane concentration in the flux chambers is always coupled with an enrichment of 13C, from δ13C1 of −46‰ to −42.5‰ (VPDB), which demonstrates that seeping methane is thermogenic, as that occurring in the deep Yakela reservoir. Daily variations of microseepage are very low, with minima in the afternoon, corresponding to higher soil temperature (and higher methanotrophic consumption), and maxima in the early morning (when soil temperatures are lowest). A preliminary and rough estimate of the total amount of CH4 exhaled from the Yakela field is in the order of 102 tonnes a−1.  相似文献   

8.
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9.
The dissolution rates of natural, well crystallized variscite (AlPO4·2H2O) were determined from the evolution of aqueous Al and P concentrations in closed and open-system mixed-flow reactors at 25 °C and pH from 1.5 to 9.0. Measured dissolution rates decrease with increasing pH, from 6 × 10−16 mol/cm2/s at pH 1.5 to 5 × 10−17 mol/cm2/s at pH 5.89, and then increase with increasing pH to 4 × 10−16 mol/cm2/s at pH 9.0. Geochemical modeling calculations, performed using measured dissolution rates, indicate that it would take no more than a few weeks or months to equilibrate a mildly acidic, Al and P-free solution with variscite. Hence, variscite can buffer aqueous phosphate concentrations in mildly acidic near surface environments. This conclusion is confirmed by consideration of the compositions of natural waters.  相似文献   

10.
We performed density measurements on a synthetic equivalent of lunar Apollo 17 74,220 “orange glass”, containing 9.1 wt% TiO2, at superliquidus conditions in the pressure range 0.5-8.5 GPa and temperature range 1723-2223 K using the sink/float technique. In the lunar pressure range, two experiments containing pure forsterite (Fo100) spheres at 1.0 GPa and 1727 K, and at 1.3 GPa-1739 K, showed neutral buoyancies, indicating that the density of molten orange glass was equal to the density of Fo100 at these conditions (3.09 ± 0.02 g cm−3). A third tight sink/float bracket using Fo90 spheres corresponds to a melt density of 3.25 ± 0.02 g cm−3 at ∼2.8 GPa and ∼1838 K.Our data predict a density crossover for the molten orange glass composition with equilibrium orthopyroxene at ∼2.8 GPa, equivalent to a depth of ∼600 km in the lunar mantle, and a density of ∼3.25 g cm−3. This crossover depth is close to the orange glass multiple saturation point, representing its minimum formation depth, at the appropriate oxygen fugacity (2.8-2.9 GPa). A density crossover with equilibrium olivine is predicted to fall outside the lunar pressure range (>4.7 GPa), indicating that molten orange glass is always less dense than its equilibrium olivines in the Moon. Our data therefore suggest that that lunar liquids with orange glass composition are buoyant with respect to their source region at P < ∼2.8 GPa, enabling their initial rise to the surface without the need for additional external driving forces.Fitting the density data to a Birch-Murnaghan equation of state at 2173 K leads to an array of acceptable solutions ranging between 16.1 and 20.3 GPa for the isothermal bulk modulus K2173 and 3.6-8 for its pressure derivative K′, with best-fit values K2173 = 18.8 GPa and K′ = 4.4 when assuming a model 1 bar density value of 2.86 g cm−3. When assuming a slightly lower 1 bar density value of 2.84 g cm−3 we find a range for K2173 of 14.4-18.0 and K′ 3.7-8.7, with best-fit values of 17.2 GPa and 4.5, respectively.  相似文献   

11.
Diffuse CO2 efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO2 efflux, in many places exceeding 1000 g m−2 d−1, was found in conspicuous zones of plant damage or kill that cover 30,000–50,000 m2 in area. Total diffuse CO2 emission was estimated at 21–44 t d−1. Gas vents 3-km away at The Gas Rocks produce 0.5 t d−1 of CO2 that probably derives from the Ukinrek Maars basalt based on similar δ13C values (∼−6‰), 3He/4He ratios (5.9–7.2 RA), and CO2/3He ratios (1–2 × 109) in the two areas. A lower 3He/4He ratio (2.7 RA) and much higher CO2/3He ratio (9 × 1010) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO2 emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas–water–rock interactions play a major role in the location, magnitude and chemistry of the emissions.  相似文献   

12.
The impact of salinity on the metabolic activity of sulfate-reducing bacteria in five highly saline to hypersaline coastal pans was studied using a radioactive tracer technique. We recorded sulfate reduction at in situ porewater salinities of up to 422. Furthermore, enumeration of sulfate reduction rates in whole core incubations conducted under in situ conditions suggested a high variability in the activity of sulfate-reducers. Average reduction rates (27-3685 nmol cm−3 d−1) varied according to depth, season and site sampled. The highest reduction rates measured in the hypersaline pan were comparable to the highest reported rates from highly productive salt marsh and microbial mat ecosystems. Correspondingly, the depth-integrated rates (integrated to 12 cm) varied from 6 to 241 mmol m−2 d−1 and were also among the highest ever reported rates. The reduction rates decreased down-core and, surprisingly, were highest in the winter season when the lowest sediment temperatures were encountered.High salt concentrations did not inhibit sulfate reduction rates. Rather, higher rates were measured at pans with higher in situ salinities. In laboratory slurry incubation experiments, sediments from the saltpans were treated with increasing salt concentrations. Regression analysis suggested that the short term response of microbial consortia to up-shock was an increase in sulfate reduction activity up to salinities of 272-311 and 134-244, in hypersaline and highly saline pans, respectively. Beyond these salinities, the cells showed evidence of reduced activities.  相似文献   

13.
Determination of the area density of spontaneous fission tracks (ρs) in glass shards of Toba tephra is a reliable way to distinguish between the Youngest Toba Tuff (YTT) and the Oldest Toba Tuff (OTT). The ρs values for YTT, uncorrected for partial track fading, range from 70 to 181 tracks/cm2 with a weighted mean of 108 ± 5 tracks/cm2, based on 15 samples. Corrected ρs values for YTT are in the range of 77–140 tracks/cm2 with a weighted mean of 113 ± 8 tracks/cm2, within the range of uncorrected ρs values. No significant difference in ρs exists between YTT samples collected from marine and continental depositional settings. The uncorrected ρs for OTT is 1567 ± 114 tracks/cm2 so that confusion with YTT is unlikely.  相似文献   

14.
A multisite surface complexation (MUSIC) model for ferrihydrite (Fh) has been developed. The surface structure and composition of Fh nanoparticles are described in relation to ion binding and surface charge development. The site densities of the various reactive surface groups, the molar mass, the mass density, the specific surface area, and the particle size are quantified. As derived theoretically, molecular mass and mass density of nanoparticles will depend on the types of surface groups and the corresponding site densities and will vary with particle size and surface area because of a relatively large contribution of the surface groups in comparison to the mineral core of nanoparticles. The nano-sized (∼2.6 nm) particles of freshly prepared 2-line Fh as a whole have an increased molar mass of M ∼ 101 ± 2 g/mol Fe, a reduced mass density of ∼3.5 ± 0.1 g/cm3, both relatively to the mineral core. The specific surface area is ∼650 m2/g. Six-line Fh (5-6 nm) has a molar mass of M ∼ 94 ± 2 g/mol, a mass density of ∼3.9 ± 0.1 g/cm3, and a surface area of ∼280 ± 30 m2/g. Data analysis shows that the mineral core of Fh has an average chemical composition very close to FeOOH with M ∼ 89 g/mol. The mineral core has a mass density around ∼4.15 ± 0.1 g/cm3, which is between that of feroxyhyte, goethite, and lepidocrocite. These results can be used to constrain structural models for Fh. Singly-coordinated surface groups dominate the surface of ferrihydrite (∼6.0 ± 0.5 nm−2). These groups can be present in two structural configurations. In pairs, the groups either form the edge of a single Fe-octahedron (∼2.5 nm−2) or are present at a single corner (∼3.5 nm−2) of two adjacent Fe octahedra. These configurations can form bidentate surface complexes by edge- and double-corner sharing, respectively, and may therefore respond differently to the binding of ions such as uranyl, carbonate, arsenite, phosphate, and others. The relatively low PZC of ferrihydrite can be rationalized based on the estimated proton affinity constant for singly-coordinated surface groups. Nanoparticles have an enhanced surface charge. The charging behavior of Fh nanoparticles can be described satisfactory using the capacitance of a spherical Stern layer condenser in combination with a diffuse double layer for flat plates.  相似文献   

15.
Partitioning of Ni in calcite, CaCO3, was evaluated with the aim of collecting data on partition and distribution coefficients and to enhance understanding about the interaction of Ni with the calcite surface and further incorporation into the bulk. This information will aid in the interpretation of geological processes for safety assessment of waste repositories and contamination of groundwater. Coprecipitation experiments were carried out by the constant addition method at 25 °C and pCO2 = 1 and 10−3.5 atm. Ni was moderately partitioned from solution into calcite. For dilute solid solutions (XNi < 0.001), Ni partition coefficients were estimated to be ∼1 and found to be weakly dependent on calcite precipitation rate in the range of 3-230 nmol m−2 s−1. Ni molar fraction in the solid is directly proportional to Ni concentration in the solution. The fit of the data to such a model is good evidence that Ni is taken up as a true solid solution, not simply by physical trapping.  相似文献   

16.
Kinetics of microbial sulfate reduction in estuarine sediments   总被引：2，自引：0，他引：2  
Kinetic parameters of microbial sulfate reduction in intertidal sediments from a freshwater, brackish and marine site of the Scheldt estuary (Belgium, the Netherlands) were determined. Sulfate reduction rates (SRR) were measured at 10, 21, and 30 °C, using both flow-through reactors containing intact sediment slices and conventional sediment slurries. At the three sites, and for all depth intervals studied (0-2, 2-4, 4-6 and 6-8 cm), the dependence of potential SRR on the sulfate concentration followed the Michaelis-Menten rate equation. Apparent sulfate half-saturation concentrations, Km, measured in the flow-through reactor experiments were comparable at the freshwater and marine sites (0.1-0.3 mM), but somewhat higher at the brackish site (0.4-0.9 mM). Maximum potential SRR, Rmax, in the 0-4 cm depth interval of the freshwater sediments were similar to those in the 0-6 cm interval of the marine sediments (10-46 nmol cm−3 h−1 at 21 °C), despite much lower in situ sulfate availability and order-of-magnitude lower densities of sulfate-reducing bacteria (SRB), at the freshwater site. Values of Rmax in the brackish sediments were lower (3.7-7.6 nmol cm−3 h−1 at 21 °C), probably due to less labile organic matter, as inferred from higher Corg/N ratios. Inflow solutions supplemented with lactate enhanced potential SRR at all three sites. Slurry incubations systematically yielded higher Rmax values than flow-through reactor experiments for the freshwater and brackish sediments, but similar values for the marine sediments. Transport limitation of potential SRR at the freshwater and brackish sites may be related to the lower sediment porosities and SRB densities compared to the marine site. Multiple rate controls, including sulfate availability, organic matter quality, temperature, and SRB abundance, modulate in situ sulfate-reducing activity along the estuarine salinity gradient.  相似文献   

17.
Lead (Pb) isotopic compositions and concentrations, and barium (Ba) and indium (In) concentrations have been determined at monthly resolution in five Law Dome (coastal Eastern Antarctica) ice core sections dated from ∼1757 AD to ∼1898 AD. ‘Natural’ background Pb concentrations in ∼1757 AD average ∼0.2 pg g−1 and can be attributed to mineral dust and volcanic emissions, with 206Pb/207Pb ratios reaching up to 1.266 ± 0.002. From ∼1887 AD to ∼1898 AD, Pb concentrations reached ∼5 pg g−1 and 206Pb/207Pb ratios decreased to 1.058 ± 0.001 as a result of additional inputs of Pb from anthropogenic sources. Seasonal variability in the late 1880s has been investigated by decoupling volcanic Pb from the total measured Pb concentrations, revealing spring and autumn maxima, and consistent winter minima, in anthropogenic Pb and mineral dust (Ba) concentrations. We link this variability to the annual cycle in the position and strength of the Antarctic Circumpolar Trough and, the Southern Ocean westerly winds to the north of the trough region. During the autumn and spring seasons, these systems increase in strength, transporting more impurity laden air from the Southern Hemisphere continental regions to Eastern Antarctica and Law Dome. As this Pb is isotopically identical to that emitted from south-eastern Australia (Broken Hill, Port Pirie) this implies a relatively direct air trajectory pathway from southern Australia to Law Dome (Eastern Antarctica).  相似文献   

18.
Bacteriohopanepolyols (BHPs) are lipid constituents of many bacterial groups. Geohopanoids, the diagenetic products, are therefore ubiquitous in organic matter of the geosphere. To examine the potential of BHPs as environmental markers in marine sediments, we investigated a Holocene sediment core from the Black Sea. The concentrations of BHPs mirror the environmental shift from a well-mixed lake to a stratified marine environment by a strong and gradual increase from low values (∼30 μg g−1 TOC) in the oldest sediments to ∼170 μg g−1 TOC in sediments representing the onset of a permanently anoxic water body at about 7500 years before present (BP). This increase in BHP concentrations was most likely caused by a strong increase in bacterioplanktonic paleoproductivity brought about by several ingressions of Mediterranean Sea waters at the end of the lacustrine stage (∼9500 years BP). δ15N values coevally decreasing with increasing BHP concentrations may indicate a shift from a phosphorus- to a nitrogen-limited setting supporting growth of N2-fixing, BHP-producing bacteria. In sediments of the last ∼3000 years BHP concentrations have remained relatively stable at about 50 μg g−1 TOC.The distributions of major BHPs did not change significantly during the shift from lacustrine (or oligohaline) to marine conditions. Tetrafunctionalized BHPs prevailed throughout the entire sediment core, with the common bacteriohopanetetrol and 35-aminobacteriohopanetriol and the rare 35-aminobacteriohopenetriol, so far only known from a purple non-sulfur α-proteobacterium, being the main components. Other BHPs specific to cyanobacteria and pelagic methanotrophic bacteria were also found but only in much smaller amounts.Our results demonstrate that BHPs from microorganisms living in deeper biogeochemical zones of marine water columns are underrepresented or even absent in the sediment compared to the BHPs of bacteria present in the euphotic zone. Obviously, the assemblage of molecular fossils in the sediments does not represent an integrated image of the entire community living in the water column. Remnants of organisms living in zones where effective transport mechanisms - such as the fecal pellet express - exist are accumulated while those of others are underrepresented. Our work shows a high stability of BHPs over geological time scales. Largely uniform distributions and only minor changes in structures like an increasing prevalence of saturated over unsaturated BHPs with time were observed. Consequently, sedimentary BHP distributions are less suitable as markers for in situ living bacteria but are useful for paleoreconstructions of bacterioplanktonic communities and productivity changes.  相似文献   

19.
Goethite (Ax-2) from Axel Heiberg Island (∼80°N) on the margin of the Arctic Ocean is the dominant mineral in a sample of “petrified” Eocene wood, but U, Th, and He measurements suggest that the goethite (α-FeOOH) crystallized in the latest Miocene/Pliocene (ca. 5.5 to 2.8 Ma). Measured δD and δ18O values of Ax-2 are −221 (±6)‰ and −9.6 (±0.5)‰, respectively. The inferred δD and δ18O values of the ancient water were about −139‰ and −18.6‰, respectively, with a calculated temperature of crystallization of 3 (±5)°C, which compares with the modern summer (J-J-A) temperature of 3 °C and contrasts with a modern MAT of −19 °C. Published results from various biological proxies on nearby Ellesmere Island indicate a Pliocene (∼4 Ma) MAT of either −6 or −0.4 °C and corresponding seasonal amplitudes of about 18 or 13 °C. A conductive heat flow model suggests that a temperature of 3 °C could represent goethite crystallization at depths of ∼100-200 cm (for MAT = −6 °C) or ∼250-450 cm (for MAT = −0.4 °C) over seasonally restricted intervals of time.The δ18O value of the Ax-2 water (−18.6‰) is more positive than the modern J-J-A precipitation (−22‰). In combination, the paleotemperatures and δ18O values of ancient waters (from Ax-2 and published results from three Eocene or Pliocene proxy sites on Axel Heiberg and Ellesmere Islands) are consistent with a warm season bias in those isotopic proxies. The results are also consistent with higher proportions of J-J-A precipitation in the annual total. If so, this emphasizes the importance of seasonality at high latitudes even in times of warmer global climates, and suggests that the Arctic hydrologic cycle, as expressed in the seasonal distribution and isotopic composition of precipitation (perhaps modified by a warmer Arctic Ocean), differed from modern.The δ13C value of the Fe(CO3)OH component in the Ax-2 goethite is +6.6‰, which is much more positive than expected if crystallizing goethite incorporated CO2 derived primarily from oxidation of relict Eocene wood with δ13C values of about −24‰. This apparent paradox may be resolved if the goethite is a product of oxidation of 13C-rich siderite, which had previously replaced wood in an Eocene methanogenic burial environment. Thus, the goethite retains a carbon isotope “memory” of a diagenetic Eocene event, but a δD and δ18O record of the latest Miocene/Pliocene Arctic climate.  相似文献   

20.
In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (∼2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ΔV of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction.Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 Å, forming “altered biotite”. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 × 10−14 mol biotite m−2 s−1. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 μm resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone.Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 × 10−13 mol hornblende m−2 s−1: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O2 at the bedrock-saprolite interface.  相似文献   

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