Diurnal variations in the isotopic composition of dissolved inorganic carbon in seawater from coral reef environments

The isotopic composition of total dissolved inorganic carbon in seawater was determined as a function of time of day in coral reef environments at Saipan, Abaiang Atoll, Tahiti, Florida and Heron Island on the Great Barrier Reef of Australia. At each locality water collected during the day was enriched in ¹³C with respect to water collected at night. The form and magnitude of the diurnal cycles is dependent upon the ratio of local biomass to local water mass and on the degree of exchange between local water mass and the open ocean reservoir. Comparison of open and closed system models is made using computer generated δ¹³C vs. time curves to illustrate modulation by the tidal cycle of the simple diurnal variation in a closed system. The results are of geochemical significance in that the δ¹³C of CaCO₃ precipitated in certain environments is dependent on the time of crystallization. This must be taken into account in isotope ratio studies of both plant and animal secreted carbonates which are preferentially precipitated during certain periods of the day.     

Geometric assessment of the kodak DCS Pro back

This paper reports on an investigation into the suitability of the Kodak DCS Pro Back for use in close range photogrammetric measurement. The camera back, being used in conjunction with a medium-format non-metric camera, has been assessed with a view to using it for low- to medium-order photogrammetric work in architectural recording. Examinations centred upon the stability of the camera back with respect to the camera body and the effects of the removable infrared filter that is present immediately above the camera's focal plane. Ultimately the camera combination was deemed suitable for application in recording of this kind and is now in active use by the Metric Survey Team at English Heritage.     

The Wilson–Burg method of spectral factorization with application to helical filtering

Spectral factorization is a computational procedure for constructing minimum-phase (stable inverse) filters required for recursive inverse filtering. We present a novel method of spectral factorization. The method iteratively constructs an approximation of the minimum-phase filter with the given autocorrelation by repeated forward and inverse filtering and rearranging of the terms. This procedure is especially efficient in the multidimensional case, where the inverse recursive filtering is enabled by the helix transform. To exemplify a practical application of the proposed method, we consider the problem of smooth two-dimensional data regularization. Splines in tension are smooth interpolation surfaces whose behaviour in unconstrained regions is controlled by the tension parameter. We show that such surfaces can be efficiently constructed with recursive filter preconditioning and we introduce a family of corresponding two-dimensional minimum-phase filters. The filters are created by spectral factorization on a helix.     

Surface charge evolution of mineral-organic complexes during pedogenesis in Hawaiian basalt

Changes in surface charge of soil particles that accompany mineral transformations during soil formation were measured for a humid tropical chronosequence in Hawaiian basalt ranging in lava flow age from 0.3 to 4100 kiloyears (ky). Parent mineralogy is dominated by glass, olivine, pyroxene, and feldspar, whereas poorly crystalline (PC) weathering products (allophane, microcrystalline gibbsite, ferrihydrite) accumulate in early to intermediate weathering stages (through 400 ky), and crystalline secondary minerals (kaolinite, gibbsite, goethite) are dominant in the oldest (1400 and 4100 ky) soils. Detailed characterization of the solid phase was accomplished with chemical extractions, X-ray diffraction analysis, and molecular spectroscopy (FTIR and ¹³C MAS NMR). Simultaneous proton titration and background ion adsorption measurements were made on LiCl saturated soils over a range in pH (2-9) and ionic strength (0.001 and 0.01 M LiCl). Dependence of variable surface charge on solution composition reflects the changing nature of mineral-organic interactions over the course of pedogenesis. Points of zero net proton charge (PZNPC) ranged from 3.4 to 6.2 and 2.0 to 5.8 at 0.001 and 0.01 M ionic strength (I), respectively. Intermediate-aged soils containing the highest mass concentration of humified soil organic matter (SOM) and its complexes with PC minerals gave rise to the steepest charging curves (largest pH dependence) and highest PZNPC values. Surface charge properties of these soils most closely reflected their weakly acidic Al and Fe hydroxide constituents, which is consistent with metal hydroxide saturation of organic functional groups, rather than organic coating of mineral surfaces. Charging curves were less steep and PZNPC values were lower for the older soils, consistent with SOM coating of more crystalline goethite, kaolinite, and gibbsite surfaces in a soil system less impacted by labile Al and Fe.     

Permo–Triassic unconformity-related Au-Pd mineralisation, South Devon, UK: new insights and the European perspective

An integrated mineralogical-geochemical study of unconformity-related Au-Pd occurrences within and around the Permo–Triassic basins of southwest England, UK, has confirmed the importance of low temperature (86±13°C), hydrothermal carbonate veins as hosts for the mineralisation. Fluid inclusion data for the carbonate gangue, supported by stable isotope (¹³C and ¹⁸O) and radiogenic (⁸⁷Sr/⁸⁶Sr) data, have identified three principal fluids: (1) a reducing calcic brine [>25 wt% salinity, <0.5 NaCl/(NaCl+CaCl₂)] originating in the sub-unconformity basement and an expression of advanced mineral–fluid interaction; (2) an oxidising sodic brine [~16 wt% salinity, >0.9 NaCl/(NaCl+CaCl₂)] originating in the post-unconformity red beds under evaporitic conditions, and (3) an oxygenated, low salinity groundwater (<3 wt% salinity). The sodic brine is reasoned to be the parent metalliferous fluid and to have acquired its enrichment in Au and Pd by the leaching of immature sediments and intra-rift volcanic rocks within the local Permo–Triassic basins. Metal precipitation is linked to the destabilisation of Au and Pd chloride complexes by either mixing with calcic brines, dilution by groundwaters or interaction with reduced lithologies. This explains the diversity of mineralised settings below and above the unconformity and their affinity with red bed brines. The paucity of sulphide minerals, the development of selenides (as ore minerals and as mineral inclusion in gold grains), the presence of rhodochrosite and manganoan calcites (up to 2.5 wt% Mn in calcite) and the co-precipitation of hematite and manganese oxides are consistent with the overall high oxidation state of the ore fluids. A genetic model is proposed linking Permo–Triassic red beds, the mixing of oxidising and reducing brines, and the development of unconformity-related precious metal mineralisation. Comparison with other European Permo–Triassic basins reveals striking similarities in geological setting, mineralogy and geochemistry with Au, Au-Pd and selenide occurrences in Germany (Tilkerode, Korbach-Goldhausen), Poland (Lubin) and the Czech Republic (Svoboda nad Úpou and Stupná). Though the known Au-Pd occurrences are sub-economic, several predictive criteria are proposed for further exploration.Editorial handling: B. Lehmann     

A Preliminary Appraisal of Seven Natural Zircon Reference Materials for In Situ Hf Isotope Determination

There is a growing need for new zircon reference materials for in situ Hf-isotope analysis by laser ablation-multicollector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS). In this contribution we document the results of a preliminary investigation of seven natural zircons, conducted in order to test their suitability in this regard. Solution MC-ICP-MS data on separated Lu and Hf fractions provided reference compositional data while the results of ca. 750 in situ LA-MC-ICP-MS analyses allowed assessment of potential micrometre-scale heterogeneity. On the basis of these analyses and additional relevant considerations such as availability, size and (Lu)Yb/Hf ratio, we suggest that, of the currently available zircons, Temora-2 and Mud Tank are most likely to provide robust reference materials for Hf isotope determinations both at the present time and into the future. The former has the advantage of also being well-characterised for U-Th-Pb systematics and suitable for in situ age determination, while the latter is the most readily available and is of very large grain size. Additional materials such as BR266, and 91500, although limited in supply, show more consistent Lu/Hf ratios and are thus of use in monitoring elemental fractionation during ICP-MS analysis.     

Peridotitic mantle xenoliths from kimberlites on the Ekati Diamond Mine property, N.W.T., Canada: major element compositions and implications for the lithosphere beneath the central Slave craton

The composition, structure and thermal state of the lithosphere beneath the Slave craton have been studied by analysing over 300 peridotitic mantle xenoliths or multiphase xenocrysts entrained within kimberlites in the Lac de Gras area. These xenoliths are derived from seven kimberlites located on the Ekati Diamond Mine™ property and define a detailed stratigraphic profile through the central Slave lithosphere from less than 120 km down to 200 km. Two dominant peridotite types are present, namely garnet-bearing harzburgite and lherzolite with rare occurrences of chromite-facies peridotite, websterite and wehrlite. The pressures and temperatures (P–T's) defined by the entire data-set range from 28 to 62 kbar and 650 to 1250 °C, respectively, and approximately intersect the diamond stability field at 900 °C and 42 kbar. There is no apparent change in the geotherm with depth that is discernable beyond the resolution of the various thermobarometers. The peridotites can be divided into two compositional zones—a shallow layer dominated by garnet harzburgite that straddles the diamond–graphite boundary and a deeper layer that is strongly dominated by garnet lherzolite. Compositionally, the harzburgites (and to a lesser extent, the shallow lherzolites) are ultra-depleted relative to the more fertile deeper layer, irrespective of whether they reside within the graphite or diamond stability field. This ultra-depleted layer beneath Ekati continues to 150 km.     

Late Cenozoic magmatism of the Bolivian Altiplano

Small basalt to dacite volcanic centers are distributed sparsely over the Bolivian Altiplano, behind the Andean volcanic front. Most are Pliocene to Recent in age, and are characterized by textural and mineralogical disequilibrium with abundant xenoliths and xenocrysts. True phenocrysts are rare in the more mafic samples. Compared with Recent volcanic rocks from Andean stratovolcanoes, the Bolivian centers overlap in major element trends. Incompatible element contents tend to be higher, particularly in the eastern Altiplano. The ranges of isotopic compositions reflect ubiquitous crustal contamination. Pb isotope compositions are dominated by Pb from isotopically heterogeneous basement, resulting in a wide scatter of data lying between inferred crustal compositions and showing little overlap with possible mantle sources in the region. Rocks sampled from the Bolivian Altiplano were probably derived from asthenospheric mantle and subjected to extensive open system differentiation during ascent through the 70 km thick crust of the region. Major element trends are largely controlled by the fractionating phase assemblage (olivine, clinopyroxene and amphibole). Trace element and isotope systematics, however, defy realistic attempts at modeling due to the geographic scatter of samples, the uniformity of compositions at a given center, and the heterogeneity of the contaminant. Nevertheless, there are first order systematic trace element variations that appear to relate to the geometry of the subduction zone. In particular, LIFE/HFSE (exemplified by Ba/Nb), and Zr/Nb ratios decrease from the arc front eastward into the Altiplano. These variations are not easily reconciled with control by crustal contamination alone. A model is proposed in which the asthenospheric source is fluxed by high Ba/Nb slab-derived fluid to induce melting. Beneath the arc, high fluid flux increases the Ba/Nb ratio of the asthenosphre and leads to high degrees of partial melting (high Zr/Nb). To the east, lower or no fluid flux leads to low Ba/Nb and low degrees of partial melting (low Zr/Nb). Melting in the back arc region of the Altiplano may be facilitated by lithospheric delamination that leads to decompression melting of counter-flowing asthenosphere. There is no unequivocal evidence that requires a significant role for the lithospheric mantle.     

A Systematic Approach to Designing a Multiphase Unsaturated Zone Monitoring Network

A systematic approach is presented for the design of a multiphase vadose zone monitoring system recognizing that, as in ground water monitoring system design, complete subsurface coverage is not practical. The approach includes identification and prioritization of vulnerable areas: select ion of cost-effective indirect monitoring methods that will provide early warning of contaminant migration: selection of direct monitoring methods for diagnostic confirmation; identification of background monitoring locations; and identification of an appropriate temporal monitoring plan. An example of a monitoring system designed for a solid waste landfill is presented and utilized to illustrate the approach and provide details of system implementation. The example design described incorporates the use of neutron moisture probes deployed in both vertical and horizontal access tubes beneath the lcachate recovery collection system of the landfill. Early warning of gaseous phase contaminant migration is monitored utilizing whole-air active soil gas sampling points deployed in gravel- filled trenches beneath the subgrade. Diagnostic confirmation of contaminant migration is provided utilizing pore- liquid samplers. Conservative tracers can be used to distinguish between chemical species released by a landfill from those attributable to other (e.g. off-site) sources or present naturally in the subsurface. A discussion of background monitoring point location is also presented.