Statistical and hydrochemical methods to compare basalt- and basement rock-hosted groundwaters: Atherton Tablelands,north-eastern Australia

Multivariate analysis of physico-chemical and chemical data has enabled differentiation among groundwaters sourced from different lithological formations in the Atherton Tablelands region of north-eastern Australia. The main water resource is stored in basalt, although basement rocks such as granite and metamorphics also contain variable amounts of water. Groundwater in the basalt is mostly Mg-Ca-Na, HCO₃ type, with electrical conductivities less than 300 µS/cm and pH values from 6.5 to 8.5. Some of the other groundwater is quite similar, making the identification of hydrochemical facies difficult. Groundwater samples were grouped based on the results of a principal component factor analysis of the major dissolved constituents H₄SiO₄, Na⁺, Ca²⁺, Mg²⁺ and HCO₃^-, as well as pH and electrical conductivity. Based on this differentiation it was possible to identify the likely host rocks of groundwaters from unidentified lithological units, define the basalt thickness and provide a better understanding of the groundwater resource. Principal component factor analysis has also been useful in identifying the likely hydrochemical processes controlling the composition of these groundwaters, including the production of weak acids in the soil layers, silicate mineral weathering, ion-exchange reactions, evapotranspiration and the leaching of ions from organic matter. Supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s00254-002-0667-z.     

Pyrolysis-combustion C dating of soil organic matter

Radiocarbon (¹⁴C) dating of total soil organic matter (SOM) often yields results inconsistent with the stratigraphic sequence. The onerous chemical extractions for SOM fractions do not always produce satisfactory ¹⁴C dates. In an effort to develop an alternative method, the pyrolysis-combustion technique was investigated to partition SOM into pyrolysis volatile (Py-V) and pyrolysis residue (Py-R) fractions. The Py-V fractions obtained from a thick glacigenic loess succession in Illinois yielded ¹⁴C dates much younger but more reasonable than the counterpart Py-R fractions for the soil residence time. Carbon isotopic composition (δ¹³C) was heavier in the Py-V fractions, suggesting a greater abundance of carbohydrate- and protein-related constituents, and δ¹³C was lighter in the Py-R fractions, suggesting more lignin- and lipid-related constituents. The combination of ¹⁴C dates and δ¹³C values indicates that the Py-V fractions are less biodegradation resistant and the Py-R fractions are more biodegradation resistant. The pyrolysis-combustion method provides a less cumbersome approach for ¹⁴C dating of SOM fractions. With further study, this method may become a useful tool for analyzing unlithified terrestrial sediments when macrofossils are absent.     

Selenium speciation and partitioning within Burkholderia cepacia biofilms formed on α-Al2O3 surfaces

The distribution and speciation of Se within aerobic Burkholderia cepacia biofilms formed on α-Al₂O₃ (1-102) surfaces have been examined using grazing-angle X-ray spectroscopic techniques. We present quantitative information on the partitioning of 10⁻⁶ M to 10⁻³ M selenate and selenite between the biofilms and underlying alumina surfaces derived from long-period X-ray standing wave (XSW) data. Changes in the Se partitioning behavior over time are correlated with microbially induced reduction of Se(VI) and Se(IV) to Se(0), as observed from X-ray absorption near edge structure (XANES) spectroscopy.Selenite preferentially binds to the alumina surfaces, particularly at low [Se], and is increasingly partitioned into the biofilms at higher [Se]. When B. cepacia is metabolically active, B. cepacia rapidly reduces a fraction of the SeO₃²⁻ to red elemental Se(0). In contrast, selenate is preferentially partitioned into the B. cepacia biofilms at all [Se] tested due to a lower affinity for binding to the alumina surface. Rapid reduction of SeO₄²⁻ by B. cepacia to Se(IV) and Se(0) subsequently results in a vertical segregation of Se species at the B. cepacia/α-Al₂O₃ interface. Elemental Se(0) accumulates within the biofilm with Se(VI), whereas Se(IV) intermediates preferentially sorb to the alumina surface.B. cepacia/α-Al₂O₃ samples incubated with SeO₄²⁻ and SeO₃²⁻ when the bacteria were metabolically active result in a significant reduction in the mobility of Se vs. X-ray treated biofilms. Remobilization experiments show that a large fraction of the insoluble Se(0) produced within the biofilm is retained during exchange with Se-free solutions. In addition, Se(IV) intermediates generated during Se(VI) reduction are preferentially bound to the alumina surface and do not fully desorb. In contrast, Se(VI) is rapidly and extensively remobilized.     

The charge-density distribution, its multipole refinement and the antiferromagnetic structure of dioptase, Cu6[Si6O18]·6H2O

 The chemical bonding in the ring silicate mineral dioptase is investigated on the basis of accurate single-crystal X-ray diffraction data. A multipole model is used in the refinements. Static deformation electron density is mapped for the silicon tetrahedron, Cu-octahedron and water molecule in different sections. The silicon tetrahedron exhibits peaks resulting from σ-bonds between Si–sp³ hybrid orbitals and O–p orbitals. The excess density is located on bonds between the Si atom and bridge (in ring) O(1)-, O(1′)-oxygens and across the interior of the Si–O–Si angle. In the Jahn-Teller distorted Cu octahedron, in addition to peaks which result from single Cu–O σ-bonds, there are peaks which are due to 3d electrons. The analysis of crystal-field influence on the Cu charge distribution is made using the tetragonal D _{4 d} approximation for the low-symmetry (C1) Cu octahedron. The calculation of the occupancies of the 3d atomic orbitals shows that the Cu non-bonding orbitals are most populated (˜20%) and the bonding orbitals least populated (14%), as is typical for the Jahn-Teller octahedron. The effective atomic charge on the Cu atom in dioptase determined from the multipoles is +1.23e: closer to the Cu⁺¹ than to the Cu⁺² state. The charge on the Si atom has a value +1.17e, which is in the range typical for Si atoms already determined by this method. The accumulation of density on bridge oxygens and across the interior of the Si–O–Si angle may be explained by additional strain in the bond with the decrease of the Si–O–Si angle in dioptase to 132°. The same effect was found earlier in coesite. A single-crystal neutron diffraction study shows that dioptase becomes antiferromagnetic below a Néel temperature of 15.9(1) K, in contrast to the previously reported specific heat anomaly at 21 K. The magnetic propagation vector is (0, 0, 3/2) on the hexagonal triple cell or (1/2, 1/2, 1/2) in rhombohedral indices. The relation between the antiferromagnetic and the charge-density models for dioptase is discussed. The less occupied Cu d _x2−y2 orbitals are responsible for the magnetic properties. These lie in the Cu–O squares, which are approximately perpendicular to c _hex, but which are alternately inclined to it by a small angle. The magnetic moments of 0.59(1)μ _B on the Cu ions in the same level are ordered ferromagnetically, but between ions in alternate levels the coupling is antiferromagnet. Within experimental error the magnetic moments are perpendicular to the square planes, which make an angle ±13(3)° to the triad axis. Received: 8 June 2001 / Accepted: 10 January 2002     

Direct effect of ice sheets on terrestrial bicarbonate, sulphate and base cation fluxes during the last glacial cycle: minimal impact on atmospheric CO2 concentrations

Chemical erosion in glacial environments is normally a consequence of chemical weathering reactions dominated by sulphide oxidation linked to carbonate dissolution and the carbonation of carbonates and silicates. Solute fluxes from small valley glaciers are usually a linear function of discharge. Representative glacial solute concentrations can be derived from the linear association of solute flux with discharge. These representative glacial concentrations of the major ions are 25% of those in global river water. A 3-D thermomechanically coupled model of the growth and decay of the Northern Hemisphere ice sheets was used to simulate glacial runoff at 100-year time steps during the last glacial cycle (130 ka to the present). The glacially derived fluxes of major cations, anions and Si over the glaciation were estimated from the product of the glacial runoff and the representative glacial concentration. A second estimate was obtained from the product of the glacial runoff and a realistic upper limit for glacial solute concentrations derived from theoretical considerations. The fluxes over the last glacial cycle are usually less than a few percent of current riverine solute fluxes to the oceans. The glacial fluxes were used to provide input to an oceanic carbon cycling model that also calculates changes in atmospheric CO₂. The potential change in atmospheric CO₂ concentrations over the last glacial cycle that arise from perturbations in glacial solute fluxes are insignificant, being <1 ppm.     

Retrograde processes in migmatites and granulites revisited

Many migmatites and granulites preserve evidence of a clockwise P–T evolution involving decompression (decrease in P) while close to the thermal peak. The extent of post‐thermal peak reaction is influenced by several factors, including: (1) the P–T path in relation to invariants in the system and the Clapeyron slopes of the equilibria; (2) the rate of cooling; and (3) the availability of fluid (H₂O‐rich volatile phase or melt) for fluid‐consuming reactions. Reaction may occur between products of a prograde (increasing T) fluid‐generating reaction as the same equilibrium is re‐crossed in the retrograde (decreasing T) sense. In general, reaction reversal or ‘back reaction’ requires the P–T path to approximate isobaric heating and cooling, without significant decompression, and evolved fluid to remain within the equilibration volume. The larger the decompression segment in the P–T evolution, the more chance there is of crossing different reactions along the retrograde segment from those crossed along the prograde segment. For common pelite compositions, we may generalize by considering three pressure regimes separated by the [Spl, Ms, H₂O] invariant in KFMASH (approximately 9 kbar) and the intersection of muscovite breakdown with the H₂O‐rich volatile phase‐saturated solidus (approximately 4 kbar). Reaction reversal cannot occur along P–T paths that traverse around one of these points, but may occur along P–T paths confined to one of the three regimes in between. Additionally, above the solidus, melt segregation and loss potentially change the composition of the equilibration volume; and, the size of the equilibration volume shrinks with decreasing T. Since the proportion of melt to residue in the equilibration volume may change with decreasing size, the composition of the equilibration volume may change throughout the supra‐solidus part of the retrograde segment of the P–T evolution. If melt has been lost from the equilibration volume, reaction reversal may not be possible or may be only partial; indeed, the common preservation of close‐to‐peak mineral assemblages in migmatite and granulite demonstrates that extensive reaction with melt is uncommon, which implies melt isolation or loss prior to crossing potential melt‐consuming reactions. Water dissolved in melt is transported through the crust to be exsolved on crystallization at the solidus appropriate to the intrinsic a(H₂O). This recycled water causes retrogression at subsolidus conditions. Consideration of the evidence for supra‐solidus decompression‐dehydration reactions, and review of microstructures that have proven controversial, such as corona and related microstructures, selvage microstructures and ‘late’ muscovite, leads to the conclusion that there is more than one way for these microstructures to form and reminds us that we should always consider multiple working hypotheses!     

Feldspar–fluid interactions in braid microperthites: pleated rims and vein microperthites

Braid microperthitic alkali feldspars in the Klokken, South Greenland and Coldwell, Ontario syenite intrusions have bulk-compositional variations along grain boundaries called pleated rims. These, together with vein microperthites in aplites which cross-cut the syenites, have been investigated by SEM and TEM. We distinguish two main types of pleated rims, “arched ” and “parallel-sided ”, consisting of alternating Ab- and Or-rich areas on (001), which are 0.5–300 μm in length normal to (010) and 0.2–20 μm in width along (010). The smallest pleats, which occur on intracrystalline boundaries in Klokken feldspars, are fully coherent and composed of low albite and low microcline. Above the heads of some of the coarser pleats, braid microperthite grades into a film crypto- and micro-perthite and antiperthite microtexture called a “transitional zone” containing roughly planar lamellae of low albite and tweed orthoclase. During pleat development, local alternating volumes form in which the proportions of the phases differ ( phase separation) and the morphology of the intergrowths changes from braided to straight in response to this change in local bulk composition. Straightening is also accompanied by transformation of low microcline to tweed orthoclase. The coarsest pleats, which occur along grain boundaries in feldspars from the Coldwell syenite, are semi- or in-coherent and have a thick coherent and semicoherent transitional zone. Coarsening of pleats and development of the transitional zone has been facilitated by diffusion of “water” into grain interiors. In many cases, pleated rims have suffered deuteric alteration, by dissolution–reprecipitation processes, through the action of a water-rich fluid from the grain boundary, in which tweed orthoclase was transformed into irregular microcline and micropores developed. Vein microperthites in aplites from Klokken, and by extension the vein microperthites almost universal in most alkali granites, are interpreted to have formed by propagation of pleat heads across entire crystals during pervasive interaction with water. Received: 10 June 1996 / Accepted: 12 December 1996