Pb-Isotope Analyses of USGS Reference Materials

Conventional corrections for thermal ionisation mass spectrometer (TIMS) induced Pb-isotopic fractionation often result in a loss of accuracy because the commonly employed pure Pb reference materials (NIST SRM 981, 982) frequently exhibit markedly different fractionation behaviour to real geological samples. As a result, these SRMs are inappropriate for comparison and/or correction of inter-operator/ laboratory biases. A matrix-matched reference material would be preferable but, as yet, no systematic study has approached this problem. Here we present high quality Pb-isotope ratio determinations, obtained using a double spike procedure, for six USGS reference materials in an attempt to address this deficiency. Our data suggest that most of these rocks could be used as isotopic reference materials comparable, in terms of uncertainty, to the NIST SRMs. However, significant differences in isotopic composition exist between first (e.g. BCR-1) and second (e.g. BCR-2) generation samples. The cause of these differences remains unclear but has significant implications for their use as trace element reference materials.     

Pyrite Oxidation Halts Migration of a Phosphorus Plume

We have established a monitoring record of phosphate (PO₄³⁻) migration in the Long Point, ON campground septic system plume that now spans 26 years. Previously, at year 16 (2006), a P plume 16 m in length was documented and provided a good fit with an analytical advection dispersion model when a P migration velocity of 0.8 m/yr was used (retardation factor of 37) and when P behaved in an otherwise conservative manner (sorption only). However, between years 16 and 26 (2016), the P plume length expanded by only 2 m (0.2 m/yr) and increased in depth by only 0.5 m. The zone of abrupt P depletion at depth occurs close to the zone where SO₄²⁻ concentrations increase in response to NO₃⁻ oxidation of pyrite. Scanning electron microscope images of sand grains from the nose of the P plume reveal abundant authigenic mineral coatings of considerable thickness (∼5 to 20 μm), with Fe as the dominant cation and containing 1 to 3 wt % P. This evidence suggests that P is now being attenuated along a reaction front that coincides with the zone where pyrite oxidation is occurring. P migration may now be controlled by the rate of migration of the pyrite oxidation front and this is several times slower than the previously indicated rate in the shallower, sorption-controlled portion of the plume. Monitoring at Long Point has demonstrated the danger of embracing an overly simplistic conceptual model when attempting to predict wastewater P migration in groundwater and also highlights the unique insight provided by a long-term monitoring record.     

Estimating Preferential Flow in Karstic Aquifers Using Statistical Mixed Models

Karst aquifers are highly productive groundwater systems often associated with conduit flow. These systems can be highly vulnerable to contamination, resulting in a high potential for contaminant exposure to humans and ecosystems. This work develops statistical models to spatially characterize flow and transport patterns in karstified limestone and determines the effect of aquifer flow rates on these patterns. A laboratory‐scale Geo‐HydroBed model is used to simulate flow and transport processes in a karstic limestone unit. The model consists of stainless steel tanks containing a karstified limestone block collected from a karst aquifer formation in northern Puerto Rico. Experimental work involves making a series of flow and tracer injections, while monitoring hydraulic and tracer response spatially and temporally. Statistical mixed models (SMMs) are applied to hydraulic data to determine likely pathways of preferential flow in the limestone units. The models indicate a highly heterogeneous system with dominant, flow‐dependent preferential flow regions. Results indicate that regions of preferential flow tend to expand at higher groundwater flow rates, suggesting a greater volume of the system being flushed by flowing water at higher rates. Spatial and temporal distribution of tracer concentrations indicates the presence of conduit‐like and diffuse flow transport in the system, supporting the notion of both combined transport mechanisms in the limestone unit. The temporal response of tracer concentrations at different locations in the model coincide with, and confirms the preferential flow distribution generated with the SMMs used in the study.     

The eastern French Pyrenees: from mountain belt to foreland basin

The Pyrenees is a young mountain belt formed as part of the larger Alpine collision zone. This excursion explores the development of the Pyrenean Mountain Belt in southern France, from its early extensional phase in the mid‐Cretaceous and subsequent collisional phase, through its uplift and erosion in the Late Cretaceous and again in the Eocene, which led to the development of the Aquitaine‐Languedoc foreland basin. One of the complexities of the Pyrenean Belt is that thrusting, uplift and erosion during the Pyrenean orogeny exposed older Variscan basement rocks in the central core of the mountains, rocks which were metamorphosed during an earlier event in the late Carboniferous. Thus, this orogenic belt also tells the story of an earlier collision between Laurussia in the north and Gondwana in the south at c. 300 Ma, prior to the onset of the Pyrenean events at c. 100 Ma. Here we seek to unravel these two separate orogenic stories.     

Astronomical constraints on nebular temperatures: Implications for planetesimal formation

Abstract— Motivated by recent observations of T-Tauri stars and the interpretation of these observations in terms of the properties of circumstellar disks, we derive internal (midplane) temperatures for disks around mature (age ～1 Ma) T-Tauri stars. The estimates are obtained by combining published results for disk masses, sizes, accretion rates, and surface temperatures. For 26 stars (for which adequate data are available), we derive midplane temperatures at 1 AU primarily in the range 200–800 K, and 100–400 K at 2.5 AU. It is likely that the solar nebula, at the same stage of evolution, contained planetesimals and objects destined to become meteorite parent bodies. Observations of young stellar objects at earlier stages of evolution (age ～0.1 Ma) imply that accretion rates were, on the average, at least two orders of magnitude greater than the 10^?8 M_⊙/year rates typical for mature T-Tauri stars. Such high values would result in midplane temperatures at or near the silicate vaporization temperature in the terrestrial planet region. If cooling of the solar nebula from such a hot epoch was responsible for establishing the pervasive elemental fractionation patterns found in chondritic meteorites, then objects in the asteroid belt must have grown rapidly (within 0.1 Ma) to sizes of ～1 km, a conclusion consistent with current theories of planetesimal formation. However, the fact that primitive meteorite parent bodies escaped being melted by the decay of ²⁶Al then implies that further growth of at least some objects was essentially delayed for 2 Ma or more. Such a diminished growth rate appears to be consistent with simulations of the dynamics of solid bodies in the asteroid belt. Other hypotheses seem less attractive. One might assume that the final cooling occurred only after the decay of ²⁶Al (i.e., more than a million years after calcium-aluminum rich inclusion formation), or that ²⁶Al was not ubiquitous in the early solar system. But the first of these conjectures is incompatible with astronomical observations of T-Tauri systems, and the second appears to be contradicted by the evidence for ²⁶Al in diverse meteoritic components. The remaining alternative would then appear to be that, despite a lack of supporting evidence, chondritic fractionation patterns reflect the net effect of many local heating and cooling events and have nothing to do with global nebular cooling. We conclude that the most plausible hypothesis is that both nebular cooling and coagulation of solids to kilometer-sized objects occurred rapidly and that a substantial number of planetesimals in the asteroid belt remained smaller than a few kilometers in radius for at least 2 Ma.     

Late quaternary speleogenesis and landscape evolution in the northern Apennine evaporite areas

Gypsum beds host the majority of the caves in the north‐eastern flank of the Apennines, in the Emilia Romagna region (Italy). More than six hundred of these caves have been surveyed, including the longest known epigenic gypsum cave systems in the world (Spipola‐Acquafredda, ~11 km). Although this area has been intensively studied from a geological point of view, the age of the caves has never been investigated in detail. The rapid dissolution of gypsum and uplift history of the area have led to the long‐held view that speleogenesis commenced only during the last 130 000 years. Epigenic caves only form when the surface drainage system efficiently conveys water into the underground. In the study area, this was achieved after the dismantling of most of the impervious sediments covering the gypsum and the development of protovalleys and sinkholes. The time necessary for these processes can by constrained by understanding when caves were first formed. The minimum age of karst voids can be indirectly estimated by dating the infilling sediments. U–Th dating of carbonate speleothems growing in gypsum caves has been applied to 20 samples from 14 different caves from the Spipola‐Acquafredda, Monte Tondo‐Re Tiberio, Stella‐Rio Basino, Monte Mauro, and Castelnuovo systems. The results show that: (i) caves have been forming since at least ~600 kyr ago; (ii) the peak of speleogenesis was reached during relatively cold climate stages, when rivers formed terraces at the surface and aggradation caused paragenesis in the stable cave levels; (iii) ~200 000 years were necessary for the dismantling of most of the sediments covering the karstifiable gypsum and the development of a surface mature drainage network. Besides providing a significant contribution to the understanding of evaporite karst evolution in the Apennines, this study refines our knowledge on the timescale of geomorphological processes in a region affected by rapid uplifting. Copyright © 2016 John Wiley & Sons, Ltd.     

U‐Pb Detrital Zircon Analysis – Results of an Inter‐laboratory Comparison

Inter‐laboratory comparison of laser ablation ICP‐MS and SIMS U‐Pb dating of synthetic detrital zircon samples provides an insight into the state‐of‐the art of sedimentary provenance studies. Here, we report results obtained from ten laboratories that routinely perform this type of work. The achieved level of bias was mostly within ± 2% relative to the ID‐TIMS U‐Pb ages of zircons in the detrital sample, and the variation is likely to be attributed to variable Pb/U elemental fractionation due to zircon matrix differences between the samples and the reference materials used for standardisation. It has been determined that ~ 5% age difference between adjacent age peaks is currently at the limit of what can be routinely resolved by the in situ dating of detrital zircon samples. Precision of individual zircon age determination mostly reflects the data reduction and procedures of measurement uncertainty propagation, and it is largely independent of the instrumentation, analytical technique and reference samples used for standardisation. All laboratories showed a bias towards selection of larger zircon grains for analysis. The experiment confirms the previously published estimates of the minimum number of grains that have to be analysed in order to detect minor zircon age populations in detrital samples.