Stability of biomass-derived black carbon in soils

Black carbon (BC) may play an important role in the global C budget, due to its potential to act as a significant sink of atmospheric CO₂. In order to fully evaluate the influence of BC on the global C cycle, an understanding of the stability of BC is required. The biochemical stability of BC was assessed in a chronosequence of high-BC-containing Anthrosols from the central Amazon, Brazil, using a range of spectroscopic and biological methods. Results revealed that the Anthrosols had 61-80% lower (P < 0.05) CO₂ evolution per unit C over 532 days compared to their respective adjacent soils with low BC contents. No significant (P > 0.05) difference in CO₂ respiration per unit C was observed between Anthrosols with contrasting ages of BC (600-8700 years BP) and soil textures (0.3-36% clay). Similarly, the molecular composition of the core regions of micrometer-sized BC particles quantified by synchrotron-based Near-Edge X-ray Fine Structure (NEXAFS) spectroscopy coupled to Scanning Transmission X-ray Microscopy (STXM) remained similar regardless of their ages and closely resembled the spectral characteristics of fresh BC. BC decomposed extremely slowly to an extent that it was not possible to detect chemical changes between youngest and oldest samples, as also confirmed by X-ray Photoelectron Spectroscopy (XPS). Deconvolution of NEXAFS spectra revealed greater oxidation on the surfaces of BC particles with little penetration into the core of the particles. The similar C mineralization between different BC-rich soils regardless of soil texture underpins the importance of chemical recalcitrance for the stability of BC, in contrast to adjacent soils which showed the highest mineralization in the sandiest soil. However, the BC-rich Anthrosols had higher proportions (72-90%) of C in the more stable organo-mineral fraction than BC-poor adjacent soils (2-70%), suggesting some degree of physical stabilization.     

Carbon and hydrogen isotope fractionation associated with the aerobic microbial oxidation of methane, ethane, propane and butane

Carbon isotope fractionation factors associated with the aerobic consumption of methane (C1), ethane (C2), propane (C3), and n-butane (C4) were determined from incubations of marine sediment collected from the Coal Oil Point hydrocarbon seep field, located offshore Santa Barbara, CA. Hydrogen isotope fractionation factors for C1, C2 and C3 were determined concurrently. Fresh sediment samples from two seep areas were each slurried with sea water and treated with C1, C2, C3 or C4, or with mixtures of all four gases. Triplicate samples were incubated aerobically at 15 °C, and the stable isotope composition and headspace levels of C1-C4 were monitored over the course of the experiment. Oxidation was observed for all C1-C4 gases, with an apparent preference for C3 and C4 over C1 and C2 in the mixed-gas treatments. Fractionation factors were calculated using a Rayleigh model by comparing the δ¹³C and δD of the residual C1-C4 gases to their headspace levels. Carbon isotope fractionation factors (reported in ε or (α-1) × 1000 notation) were consistent between seep areas and were −26.5‰ ± 3.9 for C1, −8.0‰ ± 1.7 for C2, −4.8‰ ± 0.9 for C3 and −2.9‰ ± 0.9 for C4. Fractionation factors determined from mixed gas incubations were similar to those determined from individual gas incubations, though greater variability was observed during C1 consumption. In the case of C1 and C3 consumption, carbon isotope fractionation appears to decrease as substrate becomes limiting. Hydrogen isotope fractionation factors determined from the two seep areas differed for C1 oxidation but were similar for C2 and C3. Hydrogen isotope fractionation factors ranged from −319.9‰ to −156.4‰ for C1 incubations, and averaged −61.9‰ ± 8.3 for C2 incubations and −15.1‰ ± 1.9 for C3 incubations. The fractionation factors presented here may be applied to estimate the extent of C1-C4 oxidation in natural gas samples, and should prove useful in further studying the microbial oxidation of these compounds in the natural environment.     

O/O and D/H ratios of pedogenic kaolinite in a North American Cenomanian laterite: Paleoclimatic implications

Kaolinite, gibbsite and quartz are the dominant minerals in samples collected from two outcrops of a Cenomanian (∼95 Ma) laterite in southwestern Minnesota. A combination of measured yields and isotope ratios permitted mass balance calculations of the δD and δ¹⁸O values of the kaolinite in these samples. These calculations yielded kaolinite δD values of about −73‰ and δ¹⁸O values of about +18.7‰. The δD and δ¹⁸O values appear to preserve information on the ancient weathering system.If formed in hydrogen and oxygen isotope equilibrium with water characterized by the global meteoric water line (GMWL), the kaolinite δD and δ¹⁸O values indicate a crystallization temperature of 22 (±5) °C. A nominal paleotemperature of 22 °C implies a δ¹⁸O value for the corresponding water of −6.3‰. The combination of temperature and meteoric water δ¹⁸O values is consistent with relatively intense rainfall at that mid-paleolatitude location (∼40°N) on the eastern shore of the North American Western Interior Seaway. The inferred Cenomanian paleosol temperature of ∼22 °C is in general accord with published mid-Cretaceous continental mean annual temperatures (MAT) estimated from leaf margin analyses of fossil plants.When compared with results from a published GCM-based Cenomanian climate simulation which specifies a latitudinal sea surface temperature (SST) gradient that was either near modern or smaller-than-modern, the kaolinite paleotemperature of 22 °C is closer to the GCM-predicted MAT for a smaller equator-to-pole temperature difference in the mid-Cretaceous. Moreover, the warm, kaolinite-derived, mid-paleolatitude temperature of 22 °C is associated with proxy estimates of high concentrations of atmospheric CO₂ in the Cenomanian. The overall similarity of proxy and model results suggests that the general features of Cenomanian continental climate in that North American locale are probably being revealed.     

Nanoparticles in natural systems I: The effective reactive surface area of the natural oxide fraction in field samples

Information on the particle size and reactive surface area of natural samples is essential for the application of surface complexation models (SCM) to predict bioavailability, toxicity, and transport of elements in the natural environment. In addition, this information will be of great help to enlighten views on the formation, stability, and structure of nanoparticle associations of natural organic matter (NOM) and natural oxide particles.Phosphate is proposed as a natively present probe ion to derive the effective reactive surface area of natural samples. In the suggested method, natural samples are equilibrated (?10 days) with 0.5 M NaHCO₃ (pH = 8.5) at various solid-solution ratios. This matrix fixes the pH and ionic strength, suppresses the influence of Ca²⁺ and Mg²⁺ ions by precipitation these in solid carbonates, and removes NOM due to the addition of activated carbon in excess, collectively leading to the dominance of the PO₄-CO₃ interaction in the system. The data have been interpreted with the charge distribution (CD) model, calibrated for goethite, and the analysis results in an effective reactive surface area (SA) and a reversibly bound phosphate loading Γ for a series of top soils.The oxidic SA varies between about 3-30 m²/g sample for a large series of representative agricultural top soils. Scaling of our data to the total iron and aluminum oxide content (dithionite-citrate-bicarbonate extractable), results in the specific surface area between about 200-1200 m²/g oxide for most soils, i.e. the oxide particles are nano-sized with an equivalent diameter in the order of ∼1-10 nm if considered as non-porous spheres. For the top soils, the effective surface area and the soil organic carbon fraction are strongly correlated. The oxide particles are embedded in a matrix of organic carbon (OC), equivalent to ∼1.4 ± 0.2 mg OC/m² oxide for many soils of the collection, forming a NOM-mineral nanoparticle association with an average NOM volume fraction of ∼80%. The average mass density of such a NOM-mineral association is ∼1700 ± 100 kg/m³ (i.e. high-density NOM). The amount of reversibly bound phosphate is rather close to the amount of phosphate that is extractable with oxalate. The phosphate loading varies remarkably (Γ ≈ 1-3 μmol/m² oxide) in the samples. As discussed in part II of this paper series (Hiemstra et al., 2010), the phosphate loading (Γ) of field samples is suppressed by surface complexation of NOM, where hydrophilic, fulvic, and humic acids act as a competitor for (an)ions via site competition and electrostatic interaction.     

Environmental controls on bacterial tetraether membrane lipid distribution in soils

Over the last years a novel group of branched glycerol dialkyl glycerol tetraether (GDGT) membrane lipids has been discovered in peat bogs and soils. They consist of components with 4-6 methyl groups attached to the n-alkyl chains and 0 to 2 cyclopentyl moieties in the alkyl chain. These branched membrane lipids are produced by an as yet unknown group of anaerobic soil bacteria. In this study we analysed the branched membrane lipid content of 134 soil samples from 90 globally distributed locations to study the environmental factors controlling the relative distribution of the different branched GDGT isomers. Our results show that the relative amount of cyclopentyl moieties, expressed in the cyclisation ratio of branched tetraethers (CBT), is primarily related to the pH of the soil (R² = 0.70) and not to temperature (R² = 0.03). The relative amount of methyl branches, expressed in the methylation index of branched tetraethers (MBT), is positively correlated with the annual mean air temperature (MAT) (R² = 0.62) and, to a lesser extent, negatively correlated with the pH of the soil (R² = 0.37). If both parameters are combined, however, it appears that the variation in the MBT is largely explained by both MAT and pH (R² = 0.82). These results suggest that the relative distribution of soil-derived GDGT membrane lipids can be used in palaeoenvironmental studies to estimate past annual MAT and soil pH.     

50-year record and solid state speciation of mercury in natural and contaminated reservoir sediment

Contaminated fluvial sediments represent both temporary sinks for river-borne pollutants and potential sources in case of natural and/or anthropogenic resuspension. Reservoir lakes play a very important role in sediment dynamics of watersheds and may offer great opportunities to study historical records of river-borne particles and associated elements transported in the past. The fate and potential environmental impact of Hg depends on its abundance, its carrier phases and its chemical speciation. Historical Hg records and solid state Hg speciation were compared in sediments from two contrasting reservoirs of the Lot River (France) upstream and downstream from a major polymetallic pollution (e.g. Cd, Zn) source. Natural (geochemical background) and anthropogenic Hg concentrations and their relationships with predominant carrier phases were determined. The results reveal important historical Hg contamination (up to 35 mg kg⁻¹) of the downstream sediment, reflecting the historical evolution of industrial activity at the point source, i.e. former coal mining, Zn ore treatment and post-industrial remediation work. Single chemical extractions (ascorbate, H₂O₂, KOH) suggest that at both sites most (∼75%) of the Hg is bound to organic and/or reactive sulphide phases. Organo-chelated (KOH-extracted) Hg, representing an important fraction in the uncontaminated sediment, shows similar concentrations (∼0.02 mg kg⁻¹) at both sites and may be mainly attributed to natural inputs and/or processes. Although, total Hg concentrations in recent surface sediments at both sites are still very different, similar mono-methylmercury concentrations (up to 4 μg kg⁻¹) and vertical distributions were observed, suggesting comparable methylation-demethylation processes. High mono-methylmercury concentrations (4–15 μg kg⁻¹) in 10–40 a-old, sulphide-rich, contaminated sediment suggest long-term persistence of mono-methylmercury. Beyond historical records of total concentrations, the studied reservoir sediments provided new insights in solid state speciation and carrier phases of natural and anthropogenic Hg. In case of sediment resuspension, the major part of the Hg historically stored in the Lot River sediments will be accessible to biogeochemical recycling in the downstream fluvial-estuarine environment.     

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ∼7-8 (I = 0.1 M NaNO₃ solution, suspension density = 0.4 g/L [U(VI)]_i = 0.01-30 μM, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and β charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (∼5-9), even at the partial pressure of carbon dioxide of ambient air (p_CO2 = 10^−3.45 atm).     

8000 yr of black carbon accumulation in a colluvial soil from NW Spain

Analytical pyrolysis-GC/MS and solid-state ¹³C NMR (nuclear magnetic resonance) were applied to the NaOH-extractable organic matter fraction of a colluvial soil from Galicia (NW Spain) that represents more than 8500 yr of accumulation. While molecular indicators of vegetation change were looked for, it seemed likely that any such signal was disturbed by the intense fire regime of the area. This conclusion was drawn from (1) the presence of three charcoal layers, (2) the high proportion of aryl C in NMR spectra (non-quantitative) and (3) the prevalence of benzenes and polycyclic aromatic hydrocarbons (PAHs) in the chromatograms (38 ± 6% of total identified peak area), also in charcoal-poor samples. If this conclusion is accurate, the area has been subjected to burning episodes for at least 8000 yr. Additionally, the results indicate that biomass burning residues (black carbon; BC) may become NaOH extractable after long periods of degradation in mineral soil. These results add to our knowledge of the long-term fate of BC in soil, which is a potential agent in the global C cycle.     

An absolute paleotemperature record from 10 to 6 Ka inferred from fluid inclusion D/H ratios of a stalagmite from Vancouver Island, British Columbia, Canada

By using continuous helium flow during the crushing of calcite speleothem samples, we are able to recover liberated inclusion waters without isotopic fractionation. A paleotemperature record for the Jacklah Jill Cave locality, Vancouver Island, BC, was obtained from a 30-cm tall stalagmite that grew 10.3-6.3 Ka ago, using δ¹⁸O values of the crushed calcite and of the inclusion water as inferred from its δD. It is found that the locality experienced mean annual temperature variations up to 11 °C over a 4-Ka period in the early Holocene. At the beginning of the period, local temperature quickly increased from a minimum of ∼1 °C to around 10 °C, but this early climate optimum, about 3 °C warmer than today, only lasted for ∼1200 years. About 8.6 Ka ago, temperature had declined to ∼7 °C, approximately the same as the modern cave temperature. Since then, the study area has experienced only minor temperature fluctuations, but there was a brief fall to ∼4 °C at around 7 Ka ago, which might be caused by a short lived expansion of local alpine glaciers. The long-term T-dependence of δD was 1.47‰/°C, identical to the value in modern precipitation.     

Sorption and catalytic oxidation of Fe(II) at the surface of calcite

The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO₃Fe⁺ and >CO₃FeCO₃H⁰. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t_1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t_1/2 = 41 ± 1 min and t_1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO₃FeCO₃H⁰, for which the species specific rate constant was estimated.     

Continental-scale patterns in modern wood cellulose δO: Implications for interpreting paleo-wood cellulose δO

The isotopic composition of ancient wood may be a useful archive of some climatic or geochemical conditions of the past, but presently there are many uncertainties that constrain such interpretations. We sampled naturally growing, predominantly native trees in forested regions of North America and the Caribbean to evaluate the strength of the relationships among cellulose δ¹⁸O (δ¹⁸O_cel), relative humidity (RH), precipitation δ¹⁸O (δ¹⁸O_ppt), and mean annual temperature (MAT) at the continental scale, and the general range of variability in δ¹⁸O_cel associated with site hydrologic conditions and species differences. We found up to 4‰ differences among different species growing at the same site, that conifer cellulose at a site is more enriched than angiosperm cellulose by 1.5‰ (p < 0.001), and that differences in landscape position, reflecting differing access to the water table, produced differences of <1‰ in δ¹⁸O_cel. At the continental scale, δ¹⁸O_cel was strongly influenced by modeled δ¹⁸O_ppt (R² = 0.80, p < 0.001). Average summer minimum RH (RH_min) combined with δ¹⁸O_ppt explained more of the variability (R² = 0.93, p < 0.001) in δ¹⁸O_cel across North American and Caribbean forests. MAT and δ¹⁸O_cel were also strongly correlated across North America (R = 0.91 and 0.95, p < 0.001, for angiosperms and conifers, respectively). The difference between δ¹⁸O_ppt and δ¹⁸O_cel is not constant (varying from 35-44‰) and is inversely correlated with δ¹⁸O_ppt. The relationships among δ¹⁸O_ppt, RH_min, δ¹⁸O_cel, and MAT established for North America and the Caribbean applied reasonably well when δ¹⁸O_cel was used to estimate MAT and δ¹⁸O_ppt in Asia, Europe, and South America, but there were important exceptions. The most accurate predictions of MAT and δ¹⁸O_ppt from δ¹⁸O_cel require RH_min. Predictions of δ¹⁸O_ppt and MAT made from δ¹⁸O_cel alone produced errors of up to 8‰ and 16 °C, respectively.     

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid–sulfate waters

Many waters sampled in Yellowstone National Park, both high-temperature (30–94 °C) and low-temperature (0–30 °C), are acid–sulfate type with pH values of 1–5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H₂S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <±10%. When the charge imbalance was generally >±10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H₂S or S₂O₃ oxidation, CO₂ degassing, and the temperature-dependence of pK₂ for H₂SO₄. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO₄ concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high δ¹⁸O values (−10‰ to −3‰) and a δD vs. δ¹⁸O slope of 3, reflecting kinetic fractionation. Low SO₄ concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl⁻ concentration increases from boiling which appears inconsistent with the hypothesis of H₂S oxidation as a source of hydrothermal SO₄. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid–sulfate water analyses are occasionally high in As, Hg, and NH₃ concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO₄, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone’s acid waters but have not been observed in acid rock drainage of the same pH.     

Black carbon decomposition under varying water regimes

The stability of biomass-derived black carbon (BC) or biochar as a slow cycling pool in the global C cycle is an important property and is likely governed by environmental conditions. This study investigated the effects of water regimes (saturated, unsaturated and alternating saturated–unsaturated conditions) and differences in BC materials, produced by carbonizing corn residues and oak wood at two temperatures (350 °C and 600 °C) on BC degradation at 30 °C over 1 year in a full factorial experiment. Effects of water regime on C loss and potential cation exchange capacity (CECp at pH 7) significantly depended on biomass type. Corn BC was both mineralized (16% C loss for the first year) and was oxidized [1000 mmole(+) kg^?1 C] significantly faster under unsaturated conditions than under other water regimes, whereas oak BC mineralized most rapidly (12%) under alternating saturated–unsaturated conditions with similar oxidation, irrespective of water regime. Over 1 year of saturated incubation, the O/C ratio values did not significantly (P > 0.05) increase even though BC was mineralized by 9% and CECp increased by 170 mmole(+) kg^?1 C, in contrast to unsaturated and alternating saturated–unsaturated conditions. While mineralization and oxidation significantly decreased at higher charring temperature for corn, no difference was observed for oak (P > 0.05). Unsaturated and alternating conditions increased carboxylic and OH functional groups, while they decreased aliphatic groups. The pH increased by about one unit for corn BC, but decreased by 0.2 units for oak BC, indicating strong mineral dissolution of corn BC. Carbon loss strongly correlated with changes in O/C values of both corn BC and oak BC, indicating that oxidation of BC was most likely the major mechanism controlling its stability. However, under saturated conditions, additional mechanisms may govern BC degradation and require further investigation.     

Environmental memory and a possible seasonal bias in the stable isotope composition of (U-Th)/He-dated goethite from the Canadian Arctic

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.     

Cementation of kerogen-rich marls by alkaline fluids released during weathering of thermally metamorphosed marly sediments. Part II: Organic matter evolution,magnetic susceptibility and metals (Ti,Cr, Fe) at the Khushaym Matruk natural analogue (Central Jordan)

Spontaneous combustion, less than 1 Ma ago, affected a 60-m thick sediment pile of biomicrite at the Khushaym Matruck site (Jordan). The present study shows that three retrograde alteration stages occurred: weathering, thermal stress and oxidative alkaline perturbation. μ-FT-i.r. spectra of isolated kerogens and oxygen index of whole rocks indicate that oxidation of organic matter occurred down to ∼10 m beneath the metamorphosed zone at Khushaym Matruck. The occurrence of the oxidative weathering bacterially mediated, as suggested by the mass chromatograms of saturated hydrocarbons, can explain high Rock-Eval T_max values and low petroliferous potential measured along the sedimentary pile. On the other hand, the thermal extent of combustion events was limited to the first 2 m from the contact. The mean reflectance of 0.20–0.24% and porosity of ca. 50% of the grey clayey biomicrites indicate that organic matter was very immature and sediments were unconsolidated at the time of the combustion event. Using mineralogy, microscopic analyses of vegetable debris and magnetic susceptibility, a suite of characteristic points corresponding to the thermal imprint can be assessed: (i) x = 0m, T ∼ 1000 °C, (ii) x = 1 m, T ∼ 350 °C, (iii) x = 2 m, T ∼ 150 °C and (iv) x > ∼ 8 m, T ∼ 30 °C. Paleocirculation of meteoric groundwater in the ‘cement-marbles’ generated high-pH fluids that have circulated via fractures and through the matrix porosity of the underlying biomicrites but have also induced alkaline hydrolysis and oxidative attack of the organic matter. The polysaccharide/lignin ratio derived from μ-FT-i.r. analyses shows that the delignification of vegetable debris and degradation of polysaccharides progressively decline in the indurated zone, which indicates a decrease in the pH of migrating solutions. The latter also severely oxidized organic matter at 2.10 and 3.05 m as revealed by the oxygen index and induced the generation of bitumen. The spatial correlation between the oxidation levels of organic matter and the metal contents (Fe, Ti and Cr) suggests that redox reactions were responsible for the immobilization of metals in the indurated biomicrites. The intensity of these reactions is attributed to changes in the fluid flow regime within the sedimentary column.     

Cation sorption on the muscovite (0 0 1) surface in chloride solutions using high-resolution X-ray reflectivity

The structure and mechanism of cation sorption at the (0 0 1) muscovite-water interface were investigated in 0.01 and 0.5 m KCl, CsCl, and CaCl₂ and 0.01 m BaCl₂ solutions at slightly acidic pH by high-resolution X-ray reflectivity. Structural relaxations of atom positions in the 2M₁ muscovite were small (?0.07 Å) and occurred over a distance of 30 to 40 Å perpendicular to the interface. Cations in all solutions were sorbed dominantly in the first and second solution layers adjacent to the mineral surface. The derived heights of the first solution layer in KCl and CsCl solutions, 1.67(6)-1.77(7) and 2.15(9)-2.16(2) Å, respectively, differ in magnitude by the approximate difference in crystallographic radii between K and Cs, and correspond closely to the interlayer cation positions in bulk K- and Cs-mica structures. The first solution layer heights in CaCl₂ and BaCl₂ solutions, 2.46(5)-2.56(11) and 2.02(5) Å, respectively, differ in a sense opposite to that expected based on crystallographic or hydrated radii of the divalent cations. The derived ion heights in all solutions imply that there is no intercalated water layer between the first solution layer and the muscovite surface. Molecular compositions were assigned to the first two solution layers in the electron density profiles using models that constrain the number density of sorbed cations, water molecules, and anions by considering the permanent negative charge of the muscovite and average solution density. The models result in partial charge balance (at least 50%) by cations sorbed in the first two layers in the 0.01 m solutions and approximately full charge balance in the 0.5 m solutions. Damped oscillations of model water density away from the first two solution layers agree with previous X-ray reflectivity results on the muscovite (0 0 1) surface in pure water.     

Solubility of plutonium(VI) carbonate in saline solutions

Among the plutonium oxidation states found to form in the environment, mobile plutonium(VI) can exist under oxidizing conditions and in waters with high chloride content due to radiolysis effects. We are investigating the solubility and speciation of plutonium(VI) carbonate under conditions relevant to natural waters and brines such as those found near some geologic radioactive waste repositories. The solid Pu(VI) phase PuO₂CO₃(s) was prepared and its solubility was measured in NaCl and NaClO₄ solutions in a CO₂ atmosphere as a function of pH and ionic strength (0.1-5.6 m). The concentration of soluble plutonium in solution was calculated from spectroscopic data and liquid scintillation counting. Spectroscopic measurements also revealed the plutonium oxidation state. The apparent solubility product of PuO₂CO₃(s) was determined at selected electrolyte concentrations to be, log K_s,0 = −13.95 ± 0.07 (0.1 m NaCl), log K_s,0 = −14.07 ± 0.13 (5.6 m NaCl), and log K_s,0 = −15.26 ± 0.11 (5.6 m NaClO₄). Specific ion interaction theory was used to calculate the solubility product at zero ionic strength, .     

Experimental superheating of water and aqueous solutions

The metastable superheated solutions are liquids in transitory thermodynamic equilibrium inside the stability domain of their vapor (whatever the temperature is). Some natural contexts should allow the superheating of natural aqueous solutions, like the soil capillarity (low T superheating), certain continental and submarine geysers (high T superheating), or even the water state in very arid environments like the Mars subsurface (low T) or the deep crustal rocks (high T). The present paper reports experimental measurements on the superheating range of aqueous solutions contained in quartz as fluid inclusions (Synthetic Fluid Inclusion Technique, SFIT) and brought to superheating state by isochoric cooling. About 40 samples were synthetized at 0.75 GPa and 530-700 °C with internally-heated autoclaves. Nine hundred and sixty-seven inclusions were studied by micro-thermometry, including measuring the temperatures of homogenization (Th: L + V → L) and vapor bubbles nucleation (Tn: L → L + V). The Th-Tn difference corresponds to the intensity of superheating that the trapped liquid can undergo and can be translated into liquid pressure (existing just before nucleation occurs at Tn) by an equation of state. Pure water (840-935 kg m⁻³), dilute NaOH solutions (0.1 and 0.5 mol kg⁻¹), NaCl, CaCl₂ and CsCl solutions (1 and 5 mol kg⁻¹) demonstrated a surprising ability to undergo tensile stress. The highest tension ever recorded to the best of our knowledge (−146 MPa, 100 °C) is attained in a 5 m CaCl₂ inclusion trapped in quartz matrix, while CsCl solutions qualitatively show still better superheating efficiency. These observations are discussed with regards to the quality of the inner surface of inclusion surfaces (high P-T synthesis conditions) and to the intrinsic cohesion of liquids (thermodynamic and kinetic spinodal). This study demonstrates that natural solutions can reach high levels of superheating, that are accompanied by strong changes of their physico-chemical properties.     

The oxidative dissolution of arsenopyrite (FeAsS) and enargite (Cu3AsS4) by Leptospirillum ferrooxidans

Arsenopyrite (FeAsS) and enargite (Cu₃AsS₄) fractured in a nitrogen atmosphere were characterised after acidic (pH 1.8), oxidative dissolution in both the presence and absence of the acidophilic microorganism Leptospirillum ferrooxidans. Dissolution was monitored through analysis of the coexisting aqueous solution using inductively coupled plasma atomic emission spectroscopy and coupled ion chromatography-inductively coupled plasma mass spectrometry, and chemical changes at the mineral surface observed using X-ray photoelectron spectroscopy and environmental scanning electron microscopy (ESEM). Biologically mediated oxidation of arsenopyrite and enargite (2.5 g in 25 ml) was seen to proceed to a greater extent than abiotic oxidation, although arsenopyrite oxidation was significantly greater than enargite oxidation. These dissolution reactions were associated with the release of ∼917 and ∼180 ppm of arsenic into solution. The formation of Fe(III)-oxyhydroxides, ferric sulphate and arsenate was observed for arsenopyrite, thiosulphate and an unknown arsenic oxide for enargite. ESEM revealed an extensive coating of an extracellular polymeric substance associated with the L. ferrooxidans cells on the arsenopyrite surface and bacterial leach pits suggest a direct biological oxidation mechanism, although a combination of indirect and direct bioleaching cannot be ruled out. Although the relative oxidation rates of enargite were greater in the presence of L. ferrooxidans, cells were not in contact with the surface suggesting an indirect biological oxidation mechanism. Cells of L. ferrooxidans appear able to withstand several hundreds of ppm of As(III) and As(V).