Kinematics of throughgoing fractures in jointed rocks

Throughgoing fractures play a major role in subsurface fluid flow yet the kinematics of their formation, which directly impact rock flow properties, are often difficult to establish. We investigate throughgoing fractures in the Monterey Formation of California that developed by the coalescence of pre-existing joints. At Lompoc Landing, throughgoing fractures fall into three main groups: linked, linked with aperture, and breccia zones. The segmented nature of their walls provides numerous piercing points to firmly establish the sense of displacement. Analysis of displacement vectors derived from piercing points demonstrates that the NW–SE trending throughgoing fractures, often interpreted as strike–slip faults, are in fact extensional structures in origin. We suggest that this method may be applied to throughgoing fractures that form by the same mechanism in other geologic settings. Establishing kinematics of throughgoing fractures will lead to a better understanding of their contribution to subsurface fluid flow.     

Measurement and interpretation of molecular-level forces of interaction between the siderophore azotobactin and mineral surfaces

The forces of interaction were measured between the siderophore azotobactin and the minerals goethite (α-FeOOH) and diaspore (α-AlOOH) in aqueous solution using force microscopy. Azotobactin, a pyoverdin-type siderophore, was covalently linked to a hydrazide terminated atomic force microscope tip using a standard active ester protein coupling technique. Upon contact with each mineral surface, the adhesion force between azotobactin and goethite was two to three times the value observed for the isostructural Al-equivalent diaspore. The affinity for the solid iron oxide surface reflected in the force measurements correlates with the specificity of azotobactin for aqueous ferric iron. Further, the adhesion force between azotobactin and goethite significantly decreases (4 nN to 2 nN) when small amounts of soluble iron (0.1 μM FeCl₃ · 6H₂O) are added to the system at pH 3.5 suggesting a significant specific interaction between the chelating reactive center of azotobactin and the mineral surface. Changes in the force signature with pH and ionic strength were fairly predictable when considering mineral solubility, the charge character of the mineral surfaces, the molecular structure of azotobactin, and the intervening solution. For example, azotobactin-goethite adhesion values were consistently smaller at pH 3.5 relative to the forces at pH 7. At the lower pH, the large number of protons and the increase in the mineral solubility provides additional electron acceptors (e.g., H⁺ and Fe³⁺(aq)) that are free to compete for the basic oxygen chelating sites in the azotobactin structure. It is believed that this competition disrupts siderophore affinity for the surface resulting in decreased adhesion values.     

Experimental study of igneous and sedimentary apatite dissolution: Control of pH, distance from equilibrium, and temperature on dissolution rates

Apatite dissolution experiments were conducted using both a fluidized bed and stirred tank reactor over a range of pH, temperature, solution saturation state, and on non-carbonated and carbonated apatite compositions: igneous fluorapatite (FAP) and sedimentary carbonate fluorapatite (CFA), respectively. From 2 <pH <6, the rate of release from dissolution of all apatite components [calcium (Ca), phosphorus (P), and fluoride (F)] increased with decreasing pH for FAP. From 6 < pH < 8.5, the FAP dissolution rate is pH independent. Measuring apatite dissolution rates at pH > 8.5 were not possible due to detection limits of the analytical techniques used in this study and the high insolubility of FAP. For the CFA compositions studied, the dissolution rate decreased with increasing pH from 4 < pH < 7. During early stages of the dissolution reaction for both FAP and CFA, mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P and Ca:F being greater than mineral stoichiometric ratios, suggesting that Ca was preferentially released compared to P and F from the mineral structure during the early stages of dissolution. An increase in reacted solution pH accompanies this early elevated release of Ca. As the dissolution reaction proceeded to steady state, dissolution became congruent. When normalized to BET measured surface area, FAP dissolved faster from 4 < pH < 7 compared to CFA. The apparent Arrhenius activation energy (E_a) of FAP dissolution over the temperature range of 25-55°C at pH = 3.0, I = 0.1, and pCO₂ = 0 is 8.3 ± 0.2 kcal mol⁻¹. Both the apparent exchange of solution H⁺ for solid-bound Ca at low pH in the early stage of dissolution and the E_a of dissolution suggest a surface and not a diffusion controlled dissolution reaction for FAP and CFA. The degree of undersaturation of the solution, ΔG_R, with respect to FAP was important in determining the dissolution rate. At pH = 3.0, I = 0.1, and pCO₂ = 0, the dissolution rate of FAP was ∼ 5× greater in the far-from-equilibrium region compared to the near-equilibrium slope region.A simple apatite weathering model incorporating the experimental results from this study was constructed, and numerical calculations suggest that during the Phanerozoic both the surface area of igneous rock available for weathering and the average global temperature were important factors in determining the P weathering flux from apatite dissolution. It is possible that elevated global temperatures coupled with relatively high surface area of igneous rock during the early- to mid-Paleozoic resulted in elevated P weathering fluxes, which along with climatic evolutionary pressures of the Neoproterozoic, facilitated the radiation of multicellular organisms, large-scale phosphorite deposition, and abundance of calcium phosphate shelled organisms during the early Cambrian.     

The effects of pH, ionic strength, and iron-fulvic acid interactions on the kinetics of non-photochemical iron transformations. II. The kinetics of thermal reduction

A combination of flow-injection analysis and kinetic analysis was used to examine the speciation of iron(II) and iron(III) in fulvic acid solutions as a function of pH, ionic strength, and time. This methodology was used to follow a shift in iron speciation from faster to slower reacting species over a timescale of several days. This speciation data shows that both iron(II) and iron(III)-fulvic acid complexes are important iron species in humic-containing natural waters and that their amounts and their rates of transformation to colloidal iron are controlled primarily by the kinetics of thermal (dark) reduction and iron(II) oxidation. The kinetic analysis methodology also yielded the rate constants for the thermal reduction of iron by the fulvic acid. These rate constants decrease with increasing pH and are independent of ionic strength. While thermal reduction was found to be too slow to produce large amounts of steady state iron(II) at circumneutral pH, it does provide a mechanism for iron redox cycling in the absence of photochemical or biochemical processes.     

Oxygen isotope systematics in Diploastrea heliopora: new coral archive of tropical paleoclimate

Diploastrea heliopora forms dense, robust, dome-shaped coral colonies throughout the reef ecosystems of the tropical Pacific and Indian Oceans. This slow-growing (2 to 6 mm/yr) coral has the potential to yield continuous paleoclimate records spanning up to 1000 yr for the warmest waters on Earth, the Indo-Pacific Warm Pool, and has a long fossil history as a single recognizable species. Despite the potential of Diploastrea to be an important new paleoclimate archive, little is known about the systematics of geochemical tracers incorporated into its skeleton. To fill this knowledge gap, we compared skeletal δ¹⁸O signatures in live Diploastrea and Porites colonies from Southwest Lagoon, near Amédée Lighthouse, New Caledonia (at the southern latitudinal limit for Diploastrea) and Alor, Indonesia (in the core area of the Indo-Pacific Warm Pool). We designed a new microsampling technique to minimize smoothing and distortion of the isotopic records due to the complex calyx architecture and slow growth of Diploastrea. High-resolution isotope profiles from the septal portion of the Diploastrea corallite are attenuated, whereas those restricted to the central columella are similar in quality to those extracted from the well-established Porites coral archive. The δ¹⁸O-temperature relationship for the columellar portion of Diploastrea (−0.18‰/°C) is in good agreement with that derived for a nearby Porites (−0.19‰/°C; Quinn et al., 1996), on the basis of comparison with an in situ sea surface temperature record from Amédée Lighthouse. There is a measurable difference of 0.3 ± 0.1‰ between the kinetic/biological disequilibrium offsets from seawater δ¹⁸O composition for Diploastrea and Porites. Despite this offset in mean δ¹⁸O, Diploastrea accurately records the regional differences in mean temperature and salinity between New Caledonia and the Indo-Pacific Warm Pool. Additional tests show that Diploastrea records El Niño-Southern Oscillation (ENSO) interannual variability in sea surface temperature and salinity across the southwestern Pacific, indicating that it should yield dependable paleo-ENSO records. Based on these results, we propose that D. heliopora has the potential to provide an important new coral archive of tropical paleoclimate.     

Nonracemic isovaline in the Murchison meteorite: chiral distribution and mineral association

The enantiomeric and carbon-isotopic composition of the amino acid isovaline have been analyzed in several samples of the Murchison meteorite and one sample of the Murray meteorite. l-Enantiomeric excesses of the amino acid were found to range from 0 to 15.2%, varying significantly both between meteorite stones and at short distances within a single stone. The upper limit of this range is the largest enantiomeric excess measured to date for a biologically rare meteoritic amino acid and raises doubts that circularly polarized light irradiation could have been the sole cause of amino acids chiral asymmetry in meteorites. Individual d- and l-isovaline δ¹³C values ware found to be about +18‰, with no significant differences between the two enantiomers to suggest terrestrial contamination. The amino acid relative abundance also varied between samples, with isovaline/alanine ratios of 0.5 to 6.5. X-ray diffraction analyses of contiguous meteorite fragments suggest a possible correlation between isovaline and hydrous silicates abundances.     

Mid-holocene climate change in Lake Bosumtwi, Ghana

Lake Bosumtwi is one of the most widely studied palaeoclimate archives in West Africa. Results from numerous AMS ¹⁴C dates of samples from four piston cores from Lake Bosumtwi show that an abrupt sedimentary transition from a mid-Holocene sapropel to calcareous laminated muds occurred at about 3200 cal yr B.P. High-resolution analyses of the nitrogen isotopic composition of organic matter across this transition confirm its abrupt nature, and suggest that the change may signal a step toward increased aridity and intensified surface winds that affected western equatorial Africa from Ghana to the Congo basin. Northern and Eastern Africa experienced a similar abrupt shift toward aridity during the late Holocene, but at about 5000 cal yr B.P., a difference in timing that illustrates the regional nature of climate changes during the Holocene and the importance of feedback mechanisms in regulating Holocene climate variability. Furthermore, an abrupt change at about 3000 cal yr B.P. occurs at several sites adjacent to the tropical and subtropical Atlantic, which may hint at major changes in the surface temperatures of the tropical Atlantic and/or Pacific at this time.