Water release patterns of heated speleothem calcite and hydrogen isotope composition of fluid inclusions

Speleothem fluid inclusions are a potential paleo-precipitation proxy to reconstruct past rainwater isotopic composition (δ¹⁸O, δD). To get a better insight in the extraction of inclusion water from heated speleothem calcite, we monitored the water released from crushed and uncrushed speleothem calcite, heated to 900 °C at a rate of 300 °C/h, with a quadrupole mass spectrometer. Crushed calcite released water in three not well individualised peaks between 25 and 360 °C, 360 and 650 °C and between 650 and 800 °C while uncrushed calcite released water in two distinct temperature intervals: between 25 and 550 °C and between 550 and 900 °C.Water from two speleothems from the Han-sur-Lesse cave was recovered using three different techniques: i) the crushing and heating to 360 °C technique, ii) the decrepitation by heating to 550 °C and iii) the decomposition by heating to 900 °C technique. Measurements of the δD of water recovered by the decomposition of Han-sur-Lesse calcite heated to 900 °C did not show a 20 to 30‰ offset as found by previous authors. However a difference of 7‰ was observed between water released before and after decomposition of the calcite. Water recovery from the Han-sur-Lesse samples suggests that a simple heating technique (up to 550 °C) without crushing could both (a) recover water with δD representative of that of the drip water and (b) double the water yield as compared to the crushing and heating method.Our study warns for possible contamination of the recovered inclusion water with hydration water of lime, responsible for the recovery of water with very negative δD values.     

Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rocks: the Erongo granite and tourmalinites in the Damara Belt,Namibia

Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ¹¹B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ¹¹B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ¹¹B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Enhancing understanding of breakdown and collapse in the Yorkshire Dales using ground penetrating radar on cave sediments

Historical evidence shows block breakdown and collapse are actively occurring in large fault aligned caverns in the Yorkshire Dales karst. Deployment of ground penetrating radar at two such sites has provided detailed images of the sedimentary sequences below the present day cavern floor but no large blocks are imaged within the sediments. Solutional processes must be removing limestone from the sediment to allow continued cavern growth. Possible mechanisms to account for the lack of large blocks within the sediment fill are discussed.     

Assessing soil erosion in Mediterranean karst landscapes of Lebanon using remote sensing and GIS

Maps showing the potential for soil erosion at 1:100,000 scale are produced in a study area within Lebanon that can be used for evaluating erosion of Mediterranean karstic terrain with two different sets of impact factors built into an erosion model. The first set of factors is: soil erodibility, morphology, land cover/use and rainfall erosivity. The second is obtained by the first adding a fifth factor, rock infiltration. High infiltration can reflect high recharge, therefore decreasing the potential of surface runoff and hence the quantity of transported materials. Infiltration is derived as a function of lithology, lineament density, karstification and drainage density, all of which can be easily extracted from satellite imagery. The influence of these factors is assessed by a weight/rate approach sharing similarities between quantitative and qualitative methods and depending on pair-wise comparison matrix.The main outcome was the production of factorial maps and erosion susceptibility maps (scale 1:100,000). Spatial and attribute comparison of erosion maps indicates that the model that includes a measure of rock infiltration better represents erosion potential. Field investigation of rills and gullies shows 87.5% precision of the model with rock infiltration. This is 17.5% greater than the precision of the model without rock infiltration. These results indicate the necessity and importance of integrating information on infiltration of rock outcrops to assess soil erosion in Mediterranean karst landscapes.     

Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.     

Association of dissolved aluminum with silica: Connecting molecular structure to surface reactivity using NMR

We studied uptake mechanisms for dissolved Al on amorphous silica by combining bulk-solution chemistry experiments with solid-state Nuclear Magnetic Resonance techniques (²⁷Al magic-angle spinning (MAS) NMR, ²⁷Al{¹H} cross-polarization (CP) MAS NMR and ²⁹Si{¹H} CP-MAS NMR). We find that reaction of Al (1 mM) with amorphous silica consists of at least three reaction pathways; (1) adsorption of Al to surface silanol sites, (2) surface-enhanced precipitation of an aluminum hydroxide, and (3) bulk precipitation of an aluminosilicate phase. From the NMR speciation and water chemistry data, we calculate that 0.20 (±0.04) tetrahedral Al atoms nm⁻² sorb to the silica surface. Once the surface has sorbed roughly half of the total dissolved Al (∼8% site coverage), aluminum hydroxides and aluminosilicates precipitate from solution. These precipitation reactions are dependent upon solution pH and total dissolved silica concentration. We find that the Si:Al stoichiometry of the aluminosilicate precipitate is roughly 1:1 and suggest a chemical formula of NaAlSiO₄ in which Na⁺ acts as the charge compensating cation. For the adsorption of Al, we propose a surface-controlled reaction mechanism where Al sorbs as an inner-sphere coordination complex at the silica surface. Analogous to the hydrolysis of , we suggest that rapid deprotonation by surface hydroxyls followed by dehydration of ligated waters results in four-coordinate (>SiOH)₂Al(OH)₂ sites at the surface of amorphous silica.     

Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O₂ environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O₂, and FeS_(aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O₂ concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O₂ levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P_O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS_(aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.     

The effect of species diversity on metal adsorption onto bacteria

In this study, we measure proton, Pb, and Cd adsorption onto the bacteria Deinococcus radiodurans, Thermus thermophilus, Acidiphlium angustum, Flavobacterium aquatile, and Flavobacterium hibernum, and we calculate the thermodynamic stability constants for the important surface complexes. These bacterial species represent a wide genetic diversity of bacteria, and they occupy a wide range of habitats. All of the species, except for A. angustum, exhibit similar proton and metal uptake. The only species tested that exhibits significantly different protonation behavior is A. angustum, an acidophile that grows at significantly lower pH than the other species of this study. We demonstrate that a single, metal-specific, surface complexation model can be used to reasonably account for the acid/base and metal adsorption behaviors of each species. We use a four discrete site non-electrostatic model to describe the protonation of the bacterial functional groups, with averaged pK_a values of 3.1 ± 0.3, 4.8 ± 0.2, 6.7 ± 0.1, and 9.2 ± 0.3, and site concentrations of (1.0 ± 0.17) × 10⁻⁴, (9.0 ± 3.0) × 10⁻⁵, (4.6 ± 1.8) × 10⁻⁵, and (6.1 ± 2.3) × 10⁻⁵ mol of sites per gram wet mass of bacteria, respectively. Adsorption of Cd and Pb onto the bacteria can be accounted for by the formation of complexes with each of the bacterial surface sites. The average log stability constants for Cd complexes with Sites 1-4 are 2.4 ± 0.4, 3.2 ± 0.1, 4.4 ± 0.1, and 5.3 ± 0.1, respectively. The average log stability constants for Pb complexes with Sites 1-4 are 3.3 ± 0.2, 4.5 ± 0.3, 6.5 ± 0.1, and 7.9 ± 0.5, respectively. This study demonstrates that a wide range of bacteria exhibit similar proton and metal adsorption behaviors, and that a single set of averaged acidity constants, site concentrations, and stability constants for metal-bacterial surface complexes yields a reasonable model for the adsorption behavior of many of these species. The differences in adsorption behavior that we observed for A. angustum demonstrate that genetic differences do exist between the cell wall functional group chemistries of some bacterial species, and that significant exceptions to the typical bacterial adsorption behavior do exist.