Pyrite oxidation in moist air

The rate of pyrite oxidation in moist air was determined by measuring, over time, the pressure difference between a sealed chamber containing pyrite plus oxygen and a control. The experiments carried out at 25°C, 96.7% fixed relative humidity, and oxygen partial pressures of 0.21, 0.61, and 1.00 atm showed that the rate of oxygen consumption is a function of oxygen partial pressure and time. The rates of oxygen consumption (r, mol/m²sec) fit the expression

(A)     

Oxygen-exchange pathways in aluminum polyoxocations

Using molecular dynamics simulations and electronic structure methods, we postulate a mechanism to explain the complicated reactivity trends that are observed for oxygen isotope exchange reactions between sites in aluminum polyoxocations of the ε-Keggin type and bulk solution. Experimentally, the molecules have four nonequivalent oxygens that differ considerably in reactivity both within a molecule, and between molecules in the series: Al₁₃, GaAl₁₂, and GeAl₁₂ [MO₄Al₁₂(OH)₂₄(H₂O)₁₂ⁿ⁺(aq); with M = Al(III) for Al₁₃, n = 7; M = Ga(III) for GaAl₁₂, n = 7; M = Ge(IV) for GeAl₁₂, n = 8]. We find that a partly dissociated, metastable intermediate molecule of expanded volume is necessary for exchange of both sets of μ₂-OH and that the steady-state concentration of this intermediate reflects the bond strengths between the central metal and the μ₄-O. Thus the central metal exerts extraordinary control over reactions at hydroxyl bridges, although these are three bonds away.This mechanism not only explains the reactivity trends for oxygen isotope exchange in μ₂-OH and η-OH₂ sites in the ε-Keggin aluminum molecules, but also explains the observation that the reactivities of minerals tend to reflect the presence of highly coordinated oxygens, such as the μ₄-O in boehmite, α-, and γ-Al₂O₃ and their Fe(III) analogs. The partial dissociation of these highly coordinated oxygens, coupled with simultaneous activation and displacement of neighboring metal centers, may be a fundamental process by which metals atoms undergo ligand exchanges at mineral surfaces.     

Manganese-chromium isotope systematics of enstatite meteorites

We present results of a study of the ⁵³Mn-⁵³Cr isotope systematics in the enstatite chondrites and achondrites (aubrites). The goal of this study was to explore the capabilities of this isotope system to obtain chronological information on these important classes of meteorites and to investigate the original distribution in the inner solar system of the short-lived radionuclide ⁵³Mn. Our earlier work (Lugmair and Shukolyukov, 1998; Shukolyukov and Lugmair, 2000a) has shown that the asteroid belt bodies are characterized by essentially the same initial ⁵³Mn abundance. However, we have found the presence of a gradient in the abundance of the radiogenic ⁵³Cr between the earth-moon system, Mars, and the asteroid Vesta. If this gradient is considered as a function of the heliocentric distance a linear radial dependence is indicated. This can be explained either by an early, volatility controlled Mn/Cr fractionation in the nebula or by an original radially heterogeneous distribution of ⁵³Mn. The enstatite chondrites are suggested to form in the inner zones of the solar nebula, much closer to the Sun than the ordinary chondrites. Therefore, their investigation may be an important test on the hypothesis on a radial heterogeneity in the initial ⁵³Mn.We have studied the bulk samples of the EH4-chondrites Indarch and Abee and the EL6-chondrite Khairpur. Although these meteorites have essentially the same Mn/Cr ratio as the ordinary chondrites, the relative abundance of the radiogenic ⁵³Cr is three times smaller than in the ordinary chondrites. Because these meteorites are primitive (undifferentiated) and no Mn/Cr fractionation had occurred within their parent bodies, this difference is a strong argument in favor of an initially heterogeneous distribution of ⁵³Mn in the early inner solar system. This finding is also consistent with formation of the enstatite chondrites in the inner zones of the solar nebula. Using the characteristic ⁵³Cr excess of the enstatite chondrites and the observed gradient, their place of origin falls at about 1.4 AU or somewhat closer to the Sun (i.e. >1.0-1.4 AU).We also present chronological results for the enstatite chondrites and achondrites. The ‘absolute’ ⁵³Mn-⁵³Cr ages of the EH4-chondrites are old: ∼4565 Ma. The EL6-chondrite Khairpur is ∼4.5 Ma younger, which is in good agreement with the ¹²⁹I-¹²⁹Xe data from the literature. The age of the aubrite Peña Blanca Spring appears to be similar to those of the enstatite chondrites while that of the aubrite Bishopville is at least ∼10 Ma younger, which is also in agreement with the ¹²⁹I-¹²⁹Xe data. The results from bulk samples of aubrites indicate that the last Mn/Cr fractionation in their parent body occurred ∼ 4563 Ma ago and imply an evolution of the Mn-Cr isotope system in an environment with an higher than chondritic Mn/Cr ratio for several millions of years.     

Neodymium isotopic variations in Northwest Pacific waters

Four vertical profiles of the concentration and isotopic composition of Nd in seawater were obtained in the western North Pacific. Two profiles from the Kuroshio Current regime showed congruently that although the Nd concentration increases gradually with depth, its isotopic composition varies significantly with depth depending upon the water mass occupying the water column. The high-salinity Kuroshio waters originating from the North Pacific Tropical Water (NPTW) carry the least radiogenic Nd (?_Nd = −7.4 to −8.7) to this region at ∼250 m from the western margin continental shelves, most likely from the East China Sea. The Nd isotopic compositions in the North Pacific Intermediate Water (NPIW) that occurs at 600 to 1000 m in the subtropical region are fairly uniform at ?_Nd = −3.7. The profile data from the ∼38° to 40°N Kuroshio/Oyashio mixed water region off Sanriku of Honshu, Japan, also suggest that the newest NPIW with ?_Nd = −3.2 is formed there by the mixing of various source waters, and the radiogenic component of Nd is derived mainly from the Oyashio waters.In the Pacific Deep Water (PDW) below ∼1000 m, the Nd isotopic composition is neither vertically nor horizontally homogeneous, suggesting that it serves as a useful tracer for sluggish deep water circulation as well. Two profiles from the Izu-Ogasawara Trench showed a minimum ?_Nd value at ∼2000 m, suggesting that there exists a horizontal advective flow in the vicinity of Honshu, Japan. There is some evidence from other chemical properties to support this observation. The waters below 4000 m including those within the trench in the subtropical region have ?_Nd values of around −5, suggesting that the deep waters are fed from the south along the western boundary, ultimately from the Antarctic Bottom Water (AABW) in the South Pacific. This extends up to ∼40°N along the Japanese Islands. In the subarctic region (>∼42°N), the waters have more radiogenic Nd with ?_Nd > −4.0 throughout the water column, presumably due to the supply of Nd by weathering in such igneous provinces as the Kuril-Kamchatska-Aleutian Island chain. The lateral inhomogeneity of the Nd isotopic composition in PDW suggests that there may be different circulation and mixing regimes in the North Pacific Basin.     

Thermochemistry of jarosite-alunite and natrojarosite-natroalunite solid solutions

The thermochemistry of jarosite-alunite and natrojarosite-natroalunite solid solutions was investigated. Members of these series were either coprecipitated or synthesized hydrothermally and were characterized by XRD, FTIR, electron microprobe analysis, ICP-MS, and thermal analysis. Partial alkali substitution and vacancies on the Fe/Al sites were observed in all cases, and the solids studied can be described by the general formula K_1-x-yNa_y(H₃O)_xFe_zAl_w(SO₄)₂(OH)_6-3(3-z-w)(H₂O)_3(3-z-w). A strong preferential incorporation of Fe over Al in the jarosite/alunite structure was observed. Heats of formation from the elements, ΔH°_f, were determined by high-temperature oxide melt solution calorimetry. The solid solutions deviate slightly from thermodynamic ideality by exhibiting positive enthalpies of mixing in the range 0 to +11 kJ/mol. The heats of formation of the end members of both solid solutions were derived. The values ΔH°_f = −3773.6 ± 9.4 kJ/mol, ΔH°_f = −4912.2 ± 24.2 kJ/mol, ΔH°_f = −3734.6 ± 9.7 kJ/mol and ΔH°_f = −4979.7 ± 7.5kJ/mol were found for K_0.85(H₃O)_0.15Fe_2.5(SO₄)₂(OH)_4.5(H₂O)_1.5, K_0.85(H₃O)_0.15Al_2.5(SO₄)₂(OH)_4.5(H₂O)_1.5, Na_0.7(H₃O)_0.3Fe_2.7(SO₄)₂(OH)_5.1(H₂O)_0.9, and Na_0.7(H₃O)_0.3Al_2.7(SO₄)₂(OH)_5.1(H₂O)_0.9 respectively. To our knowledge, this is the first experimentally-based report of ΔH°_f for such nonstoichiometric alunite and natroalunite samples. These thermodynamic data should prove helpful to study, under given conditions, the partitioning of Fe and Al between the solids and aqueous solution.     

Carbonate complexation of yttrium and the rare earth elements in natural waters

Potentiometric measurements of Yttrium and Rare Earth Element (YREE) complexation by carbonate and bicarbonate indicate that the quality of carbonate complexation constants previously obtained via solvent exchange analyses are superior to characterizations obtained using solubility and adsorptive exchange analyses. The results of our analyses at 25°C are combined with the results of previous solvent exchange analyses to obtain YREE carbonate complexation constants over a wide range of ionic strength (0 ≤ I ≤3 molal). YREE carbonate complexation constants are reported for the following equilibria, M³⁺+nHCO₃⁻?M(CO₃)_n³⁻²ⁿ+nH⁺, where n = 1 or 2. Formation constants written in terms of HCO₃⁻ concentrations require only minor corrections for ion pairing relative to the corrections required for constants expressed in terms of CO₃²⁻ concentrations. Formation constants for the above complexation equilibria, _CO3^Hβ₁=[MCO₃⁺][H⁺][M³⁺]⁻¹[HCO₃⁻]⁻¹ and _CO3^Hβ₂=[M(CO₃)₂⁻][H⁺]²[M³⁺]⁻¹[HCO₃⁻]⁻², have very similar dependencies on ionic strength because the reaction MCO₃⁺+HCO₃⁻?M(CO₃)₂⁻+H⁺ is isocoulombic. Potentiometric analyses indicate that the dependence of log_CO3^Hβ₁ and log_CO3^Hβ₂ on ionic strength at 25°C is given as

(A)     

The effect of sodium and titanium on crystal-melt partitioning of trace elements

Eclogite of recycled slab origin has often been invoked in the source region of mid-ocean ridge and ocean-island basalts. Melts of this eclogitic material are expected to be enriched in incompatible elements including major elements such as Na and Ti. In order to investigate the controls on trace element chemistry of a melt from such a recycled component we have performed trace element partitioning experiments in the simple systems CMAS (CaO-MgO-Al₂O₃-SiO₂), NCMAS (Na₂O-CMAS) and Ti-CMAS (TiO₂-CMAS) at 3 GPa and 1298-1500°C using analogue eclogitic compositions.We show that sodium has a profound effect on clinopyroxene-melt partition coefficients. NCMAS is characterized by elevated partition coefficients, relative to CMAS for all elements except Li. The increase is more pronounced for more highly charged cations, resulting in negative partitioning anomalies for Li, Sr, Ba and Pb. In contrast to sodium, titanium has very little effect on trace element partitioning for all elements except Nb and Ta, which are retained by the rutile that is saturated in this run.     

A stable isotope-based approach to tropical dendroclimatology

We describe a strategy for development of chronological control in tropical trees lacking demonstrably annual ring formation, using high resolution δ¹⁸O measurements in tropical wood. The approach applies existing models of the oxygen isotopic composition of alpha-cellulose (Roden et al., 2000), a rapid method for cellulose extraction from raw wood (Brendel et al., 2000), and continuous flow isotope ratio mass spectrometry (Brenna et al., 1998) to develop proxy chronological, rainfall and growth rate estimates from tropical trees lacking visible annual ring structure. Consistent with model predictions, pilot datasets from the temperate US and Costa Rica having independent chronological control suggest that observed cyclic isotopic signatures of several permil (SMOW) represent the annual cycle of local rainfall and relative humidity. Additional data from a plantation tree of known age from ENSO-sensitive northwestern coastal Peru suggests that the 1997-8 ENSO warm phase event was recorded as an 8‰ anomaly in the δ¹⁸O of α-cellulose. The results demonstrate reproducibility of the stable isotopic chronometer over decades, two different climatic zones, and three tropical tree genera, and point to future applications in paleoclimatology.     

Transient dissolution patterns on stressed crystal surfaces

We present an experimental investigation on the dissolution of uniaxially stressed crystals of NaClO₃ in contact with brine. The crystals are immersed in a saturated fluid, stressed vertically by a piston and monitored constantly in situ with a CCD camera. The experiments are temperature-controlled and uniaxial shortening of the sample is measured with a high-resolution capacitance analyzer. Once the crystal is stressed it develops dissolution grooves on its free surface. The grooves are oriented with their long axis perpendicular to the direction of compressive stress and the initial distance between the parallel grooves is in accordance with the Asaro-Tiller-Grinfeld instability. We observe a novel, transient evolution of this roughness: The grooves on the crystal surface migrate upwards (against gravity), grow in size and the inter-groove distance increases linearly with time. During the coarsening of the pattern this switches from a one-dimensional geometry of parallel grooves to a two-dimensional geometry with horizontal and vertical grooves. At the end of the experiment one large groove travels across the crystal and the surface becomes smooth again. Uniaxial shortening of the crystal by pressure solution creep decays exponentially with time and shows no long term creep within the range of the resolution of the capacitance analyzer (accuracy of 100nm over a period of 14 days). This indicates that, while active, the fast transient processes on the free surface increase the solution concentration and thereby significantly slow down or stop pressure solution at the top of the crystal. This novel feedback mechanism can explain earlier results of cyclic pressure solution creep and demands development of a more complex theory of pressure-solution creep including processes that act on free surfaces.     

Oxygen isotope fractionation in synthetic magnesian calcite

Mg-bearing calcite was precipitated at 25°C in closed system free-drift experiments from solutions containing NaHCO₃, CaCl₂ and MgCl₂. The chemical and isotope composition of the solution and precipitate were investigated during time course experiments of 24-h duration. Monohydrocalcite and calcite precipitated early in the experiments (<8 h), while Mg-calcite was the predominant precipitate (>95%) thereafter. Solid collected at the end of the experiments displayed compositional zoning from pure calcite in crystal cores to up to 23 mol% MgCO₃ in the rims. Smaller excursions in Mg were superimposed on this chemical record, which is characteristic of oscillatory zoning observed in synthetic and natural solid-solution carbonates of differing solubility. Magnesium also altered the predominant morphology of crystals over time from the {104} to {100} and {110} growth forms.The oxygen isotope fractionation factor for the magnesian-calcite-water system (as 10³lnα_Mg-cl-H2O) displayed a strong dependence on the mol% MgCO₃ in the solid phase, but quantification of the relationship was difficult due to the heterogeneous nature of the precipitate. Considering only the Mg-content and δ¹⁸O values for the bulk solid, 10³lnα_Mg-cl-H2O increased at a rate of 0.17 ± 0.02 per mol% MgCO₃; this value is a factor of three higher than the single previous estimate (Tarutani T., Clayton R.N., and Mayeda T. K. (1969) The effect of polymorphims and magnesium substitution on oxygen isotope fractionation between calcium carbonate and water. Geochim. Cosmochim. Acta 33, 987-996). Nevertheless, extrapolation of our relationship to the pure calcite end member yielded a value of 27.9 ± 0.02, which is similar in magnitude to published values for the calcite-water system. Although no kinetic effect was observed on 10³lnα_Mg-cl-H2O for precipitation rates that ranged from 10^3.21 to 10^4.60 μmol · m⁻² · h⁻¹, it was impossible to disentangle the potential effect(s) of precipitation rate and Mg-content on 10³lnα_Mg-cl-H2O due to the heterogeneous nature of the solid.The results of this study suggest that paleotemperatures inferred from the δ¹⁸O values of high magnesian calcite (>10 mol% MgCO₃) may be significantly underestimated. Also, the results underscore the need for additional experiments to accurately characterize the effect of Mg coprecipitation on the isotope systematics of calcite from a chemically homogeneous precipitate or a heterogeneous material that is analyzed at the scale of chemical and isotopic zonation.     

Reactivity of organic matter in aquifer sediments: geological and geochemical controls

Reduction rates in aquifers are commonly carbon limited, but little is known about the molecular composition and degradability of sedimentary organic matter (SOM) in aquifer sediments. The composition, source and degradation status of SOM in aquifer sediments of fluvio-glacial (Pleistocene) and shallow marine (Pliocene) origin, were determined using flash pyrolysis-gas chromatography/mass spectrometry. Incubation experiments (106 d) were used to assess the reactivity of SOM towards molecular oxygen. A dominance of lignin-derived components and long chain odd-over-even predominant alkanes indicate that terrestrial higher land plants were the main source of SOM even in the shallow marine sediments, while bacterial lipid-derived hopanoids and iso- and anteiso-C₁₅ and C₁₇ fatty acids indicate a minor contribution of microbial biomass. No compositional difference was observed between SOM present in the fine (<63 μm) and coarse fraction (63-2000 μm). A significant part of SOM was not present as low-molecular-weight compounds but was macromolecularly bound. For the fluvio-glacial sediments, a relatively higher abundance of resistant macromolecular compounds was in agreement with stronger signs of aerobic lignin, alkane and hopanoid oxidation. The more degraded status of SOM in the fluvio-glacial sediments was consistent with their significantly lower SOM mineralization (2-6%) during incubation, as compared with the shallow marine sediments (9-14%). The reactivity towards oxygen of SOM was controlled by the extent of past aerobic oxidation. Not the age of SOM, but the extent of oxygen exposure during syn- and postdepositional conditions seems most important in affecting the degradation status of SOM in aquifer sediments and thus their ability to reduce oxidants.     

Particle geochemistry in the Rainbow hydrothermal plume, Mid-Atlantic Ridge

We report the analysis of 18 large volume (500-1500 L) in situ filtered samples of particulate material from the largest hydrothermal plume on the Mid-Atlantic Ridge, overlying the ultramafic-hosted Rainbow hydrothermal field at 36° 14′N. Measured particulate iron concentrations reach 614 nM. High concentrations of particulate Fe oxyhydroxides result from the extremely high Fe concentration (∼24 mM) and Fe/H₂S ratio (∼24) of the vent fluids, and persist to at least 10 km away from the vent site due to the advection of plume material with the ambient along-axis flow. Two of the nine pairs of pump deployments appear to have intercepted the buoyant or otherwise very young portion of the hydrothermal plume. These samples are characterized by anomalously (compared to neutrally buoyant plume samples) high concentrations of Mg, U, and chalcophile elements, and low concentrations of Mn, Ca, V, Y, and the rare earth elements (REE). Within the neutrally buoyant plume, elemental distributions are largely consistent with previously observed behaviors: preferential removal of chalcophile elements, conservative behavior of oxyanions (P, V, and U), and continuous scavenging of Y and the REE. This consistency is particularly significant in light of the underlying differences in fluid chemistry between Rainbow and other studied sites. Chalcophile elements are preferentially removed from the plume in the order Cd>Zn>Co>Cu. Phosphorus/iron and vanadium/iron ratios for the neutrally buoyant plume are consistent with global trends with respect to the concentration of dissolved phosphate in ambient seawater. Comparison of buoyant and neutrally buoyant plume ratios with data from hydrothermal sediments underlying the Rainbow plume (Cave et al., 2002) indicates, however, that while P/Fe ratios are indeed constant V/Fe ratios increase progressively from early stage plume particles to sediments. REE distributions in the buoyant and neutrally buoyant plume appear most consistent with a continuous scavenging process during dispersion through the water column.     

Increased concentrations of dissolved trace metals and organic carbon during snowmelt in rivers of the alaskan arctic

Arctic rivers typically transport more than half of their annual amounts of water and suspended sediments during spring floods. In this study, the Sagavanirktok, Kuparuk and Colville rivers in the Alaskan Arctic were sampled during the spring floods of 2001 to determine levels of total suspended solids (TSS) and dissolved and particulate metals and organic carbon. Concentrations of dissolved organic carbon (DOC) increased from 167 to 742 μmol/L during peak discharge in the Sagavanirktok River, at about the same time that river flow increased to maximum levels. Concentrations of dissolved Cu, Pb, Zn and Fe in the Sagavanirktok River followed trends observed for DOC with 3- to 25-fold higher levels at peak flow than during off-peak discharge. Similar patterns were found for the Kuparuk and Colville rivers, where average concentrations of dissolved trace metals and DOC were even higher. These observations are linked to a large pulse of DOC and dissolved metals incorporated into snowmelt from thawing ponds and upper soil layers. In contrast with Cu, Fe, Pb and Zn, concentrations of dissolved Ba did not increase in response to increased discharge of water, TSS and DOC. Concentrations of particulate Cu, Fe, Pb and Zn were more uniform than observed for their respective dissolved species and correlated well with the Al content of the suspended particles. However, concentrations of particulate Al were poorly correlated with particulate organic carbon. Results from this study show that >80% of the suspended sediment and more than one-third of the annual inputs of dissolved Cu, Fe, Pb, Zn and DOC were carried to the coastal Beaufort Sea in 3 and 12 d, respectively, by the Kuparuk and Sagavanirktok rivers.     

Strontium incorporation into calcite generated by bacterial ureolysis

Strontium incorporation into calcite generated by bacterial ureolysis was investigated as part of an assessment of a proposed remediation approach for ⁹⁰Sr contamination in groundwater. Urea hydrolysis produces ammonium and carbonate and elevates pH, resulting in the promotion of calcium carbonate precipitation. Urea hydrolysis by the bacterium Bacillus pasteurii in a medium designed to mimic the chemistry of the Snake River Plain Aquifer in Idaho resulted in a pH rise from 7.5 to 9.1. Measured average distribution coefficients (D_EX) for Sr in the calcite produced by ureolysis (0.5) were up to an order of magnitude higher than values reported in the literature for natural and synthetic calcites (0.02-0.4). They were also higher than values for calcite produced abiotically by ammonium carbonate addition (0.3). The precipitation of calcite in these experiments was verified by X-ray diffraction. Time-of-flight secondary ion mass spectrometry (ToF SIMS) depth profiling (up to 350 nm) suggested that the Sr was not merely sorbed on the surface, but was present at depth within the particles. X-ray absorption near edge spectra showed that Sr was present in the calcite samples as a solid solution. The extent of Sr incorporation appeared to be driven primarily by the overall rate of calcite precipitation, where faster precipitation was associated with greater Sr uptake into the solid. The presence of bacterial surfaces as potential nucleation sites in the ammonium carbonate precipitation treatment did not enhance overall precipitation or the Sr distribution coefficient. Because bacterial ureolysis can generate high rates of calcite precipitation, the application of this approach is promising for remediation of ⁹⁰Sr contamination in environments where calcite is stable over the long term.     

Barite deposition resulting from phototrophic sulfide-oxidizing bacterial activity

Barite (BaSO₄) deposits generally arise from mixing of soluble barium-containing fluids with sulfate-rich fluids. While the role of biological processes in modulating barium solubility has been shown, no studies have shown that the biological oxidation of sulfide to sulfate leads to barite deposition. Here we present an example of microbially mediated barite deposition in a continental setting. A spring in the Anadarko Basin of southwestern Oklahoma produces water containing abundant barium and sulfide. As emergent water travels down a stream to a nearby creek, sulfate concentration increases from 0.06 mM to 2.2 mM while Ba²⁺ concentration drops from 0.4 mM to less than 7 μM. Stable isotope analysis, microbial activity studies, and in situ experiments provide evidence that as sulfide-rich water flows down the stream, anaerobic, anoxygenic, phototrophic bacteria play a dominant role in oxidizing sulfide to sulfate. Sulfate then precipitates with Ba²⁺ producing barite as travertine, cements, crusts, and accumulations on microbial mats. Our studies suggest that phototrophic sulfide oxidation and concomitant sulfur cycling could prove to be important processes regulating the cycling of barium in continental sulfur-containing systems.     

Carbon isotope effects in carbonate systems

Global carbon cycle models require a complete understanding of the δ¹³C variability of the Earth’s C reservoirs as well as the C isotope effects in the transfer of the element among them. An assessment of δ¹³C changes during CO₂ loss from degassing magmas requires knowledge of the melt-CO₂ carbon isotope fractionation. In order to examine the potential size of this effect for silicate melts of varying composition, ¹³C reduced partition functions were computed in the temperature range 275 to 4000 K for carbonates of varying bond strengths (Mg, Fe, Mn, Sr, Ba, Pb, Zn, Cd, Li, and Na) and the polymorphs of calcite. For a given cation and a given pressure the ¹³C content increases with the density of the carbonate structure. For a given structure the tendency to concentrate ¹³C increases with pressure. The effect of pressure (‰/10 kbar) on the size of the reduced partition function of aragonite varies with temperature; in the pressure range 1 to 10⁵ bars the change is given by:

(1)     

Long-range vs. short-range ordering in synthetic Cr-substituted goethites

A series of Cr-substituted goethites with (Cr:Fe molar ratio up to 0.12) were prepared. Thermal analysis of the solids indicates the formation of cation-deficient compounds that are more stable towards the transformation to hematite as the Cr content increases. Powder X-ray diffraction (PXRD) and extended X-ray absorption fine structure (EXAFS) techniques were used to assess the structural characteristics of the whole series of the substituted solids. XRD patterns demonstrate that the order around Fe remains typical of a goethite-like structure. Rietveld refinement of X-ray diffraction data indicates that the incorporation of Cr causes a slight decrease in the cell volume with the c-cell parameter following the Vegard’s law. This decrease is accompanied by changes in opposite directions of the various Me-Me distances. EXAFS spectra at the Fe K-edge indicate that the local order around the Fe atom changes slightly upon Cr substitution: Measurements in the Cr K-edge show that the Cr environment remains unchanged in the whole series. All the observed trends in both average Rietveld and local EXAFS distances can be traced back to the differences in the coordination polyhedra around Cr and Fe. The polyhedron around Cr is more symmetric and can be described as Cr(OH_0.5)₆ as opposed to the polyhedron around Fe that contains two distinct sets of ligands, FeO₃(OH)₃. The effects caused by substitution are governed by this difference, rather than by the smaller size of Cr(III) as compared to Fe(III). Simultaneous use of XAS and Rietveld refinement of XRD data permits tracing the trends in the average long range ordering (Me-Me distances) to local changes in distances and angles when Cr³⁺ substitutes Fe³⁺ in goethite. Complex changes in the various interatomic distances and angles may result in deceivingly simple long-range trends. These trends are therefore of limited value as probes for the atomic scale changes. On the other hand, XAS provide direct information on the fundamental, atomic-scale changes.     

Carbon and hydrogen isotope fractionation by moderately thermophilic methanogens

A series of laboratory studies were conducted to increase understanding of stable carbon (¹³C/¹²C) and hydrogen (D/H) isotope fractionation arising from methanogenesis by moderately thermophilic acetate- and hydrogen-consuming methanogens. Studies of the aceticlastic reaction were conducted with two closely related strains of Methanosaeta thermophila. Results demonstrate a carbon isotope fractionation of only 7‰ (α = 1.007) between the methyl position of acetate and the resulting methane. Methane formed by this process is enriched in ¹³C when compared with other natural sources of methane; the magnitude of this isotope effect raises the possibility that methane produced at elevated temperature by the aceticlastic reaction could be mistaken for thermogenic methane based on carbon isotopic content. Studies of H₂/CO₂ methanogenesis were conducted with Methanothermobacter marburgensis. The fractionation of carbon isotopes between CO₂ and CH₄ was found to range from 22 to 58‰ (1.023 ≤ α ≤ 1.064). Greater fractionation was associated with low levels of molecular hydrogen and steady-state metabolism. The fractionation of hydrogen isotopes between source H₂O and CH₄ was found to range from 127 to 275‰ (1.16 ≤ α ≤ 1.43). Fractionation was dependent on growth phase with greater fractionation associated with later growth stages. The maximum observed fractionation factor was 1.43, independent of the δD-H₂ supplied to the culture. Fractionation was positively correlated with temperature and/or metabolic rate. Results demonstrate significant variability in both hydrogen and carbon isotope fractionation during methanogenesis from H₂/CO₂. The relatively small fractionation associated with deuterium during H₂/CO₂ methanogenesis provides an explanation for the relatively enriched deuterium content of biogenic natural gas originating from a variety of thermal environments. Results from these experiments are used to develop a hypothesis that differential reversibility in the enzymatic steps of the H₂/CO₂ pathway gives rise to variability in the observed carbon isotope fractionation. Results are further used to constrain the overall efficiency of electron consumption by way of the hydrogenase system in M. marburgensis, which is calculated to be less than 55%.     

Reversibility of radiocaesium sorption on illite

Adsorption of trace amounts of radiocaesium on NH₄-, K-, and Na-saturated Fithian illite and subsequent desorption by 1 M NH₄ showed that a substantial amount of radiocaesium (44%, 46%, and 91% for NH₄-, K-, and Na-illite, respectively) cannot be desorbed after only 5 min of adsorption. Our results suggest that this instantaneous fixation is caused by the collapse of the frayed edges of the clay mineral and the relatively high concentration of radiocaesium building up in solution in the batch desorption experiments. Consequently, commonly applied high-NH₄ extractions underestimate truly exchangeable amounts of radiocaesium in soils and sediments containing illitic clay minerals. The rate of desorption of trace amounts of radiocaesium from the solids using high NH₄ or Cs concentrations has a half-life of about 2 yr, reflecting radiocaesium desorption from (partially) collapsed interlayers. Extraction of radiocaesium from illite after 5 min of contact time with a Cs-selective adsorbent or a 1 × 10^-6 M CsCl solution shows that 100% of the bound radiocaesium is readily available. The desorption rate in the presence of a Cs-selective adsorbent has a half-life of about 0.2 yr. Desorption of radiocaesium from illite using different ammonium concentrations shows that radiocaesium partitioning follows reversible ion-exchange theory if the NH₄ concentration is below 1 × 10^-4 M, and sufficient time (weeks) is allowed for the reaction to proceed. Thus, radiocaesium sorption reversibility in the natural environment is much higher than generally assumed, and equilibrium solid/liquid partitioning may be assumed for the long-term modelling of radiocaesium mobility in the natural environment. In the particular case of anoxic freshwater sediments with very high NH₄ concentrations in the pore waters (up to several mmol.L^-1), collapse of the frayed edges of illite may occur, influencing radiocaesium partitioning. If collapse occurs before radiocaesium adsorbs to illite, high caesium sorption reversibility as measured by high-NH₄ extraction can be expected because further collapse of the frayed edges during the extraction procedure will be limited. This effect has indeed been observed earlier in the extraction of radiocaesium from anoxic freshwater sediments with high-NH₄ solutions and was as yet unexplained.     

Behavior of Sm and Nd in a lateritic soil profile

A study of lateritic soils and samples of ground and river waters was carried out in the Nsimi-Zoetele, a tropical watershed in the southern Cameroon. The Nd isotopic compositions and concentrations of Nd and Sm were determined. It was found that the Nd isotopic composition of the river waters was much more radiogenic than the parent rocks, and that the Nd in the waters is not homogeneous but is carried by different dissolved and complexed components that are not isotopically homogenized. The soil profile shows a regular increase in ε_Nd going from the parent rock (ε_Nd = −36) to ε_Nd = −18 near the top of the profile. The Nd transported in the river is thus not representative of the parent rock but reflects the results of differential weathering of constituent minerals and the redeposition of REE in phosphates and a significant contribution of radiogenic Nd from dust. The concentration of Nd in the river water is far above that found in temperate climate rivers and thus this type of tropical river may play a dominant role in the marine Nd and REE budget. It is suggested that the correlation of REE with DOC is related to DOC fixing some dissolved REE but that the REE in solution is governed by other mechanisms. No major shifts were found in Sm/Nd; however, a regular progression from the parent rock through the lateritic profile was found. The upper laterite profile shows large, almost uniform depletions in all REE below Tb and enrichment above. Complementary behavior was found in the lower part of the section. The concentration of Nd relative to the immobile elements Zr and Ti in the laterite is depleted by a factor of ∼10. Th, Nd and Sm are enriched in the lowest zone sampled and must reflect redeposition of REE from the upper part of the weathering section and is associated with phosphate formation. It is concluded that the soil evolution involves both differential dissolution of primary phases from the parent rock, significant to major input of REE from atmospheric dust from other regions, and the formation of diagenetic phases, particularly phosphates.