A hafnium isotope and trace element perspective on melting of the depleted mantle

New Hf isotope and trace element data on mid-ocean ridge basalts (MORB) from the Pacific Ocean basin are remarkably uniform (¹⁷⁶Hf/¹⁷⁷Hf≈0.28313–0.28326) and comparable to previously published data [Salters, Earth Planet. Sci. Lett. 141 (1996) 109–123; Patchett, Lithos 16 (1983) 47–51]. Atlantic MORB have ¹⁷⁶Hf/¹⁷⁷Hf ranging from 0.28302 to 0.28335 confirming the wide range originally identified by Patchett and Tatsumoto [Geophys. Res. Lett. 7 (1980) 1077–1080]. Indian MORB define an even wider range, from 0.28277 to 0.28337, but three exotic samples have very unradiogenic Hf isotope compositions. Their very low ¹⁷⁶Hf/¹⁷⁷Hf ratios, together with their trace element characteristics, require the presence of unusual plume-type material beneath the Indian ridge. All other Indian MORB have uniform Hf isotope compositions at about 0.2832, and define a small field displaced to the right of other MORB in Hf–Nd isotope space. The distinct nature of Indian MORB is best explained by the presence in Indian depleted mantle of old recycled oceanic crust and pelagic sediments. Sm/Hf ratios calculated from new high-precision rare earth element and Hf trace element data do not vary in MORB in the same way as in ocean island basalts (OIB): ratios are constant in OIB, but decrease with increasing Sm contents in MORB. The constancy of Sm/Hf in OIB is probably due to an overwhelming influence of residual garnet during melting. By contrast, the decrease of Sm/Hf in MORB is due to the effect of clinopyroxene in the residue of melting beneath ridges, an interpretation confirmed by quantitative modeling of melting. The relationship between Sm/Nd and Lu/Hf ratios in MORB does not require the presence of garnet in the residual mineralogy. The decoupling of Lu/Hf ratios and Hf isotope compositions – the so-called Hf paradox [Salters and Hart, EOS Trans. Am. Geophys. Union 70 (1989) 510] – can be explained by melting dominantly in the spinel field at shallow depths beneath mid-ocean ridges.     

Groundwater—Surface waters interactions at slope and catchment scales: implications for landsliding in clay‐rich slopes

Understanding water infiltration and transfer in soft‐clay shales slopes is an important scientific issue, especially for landsliding. Geochemical investigations are carried out at the Super‐Sauze and Draix‐Laval landslides, both developed in the Callovo‐Oxfordian black marls, with the objective to define the origin of the groundwater. In situ investigations, soil leaching experiments and geochemical modeling are combined to identify the boundaries of the hydrological systems. At Super‐Sauze, the observations indicate that an external water flow occurs in the upper part of the landslide at the contact between the weathered black marls and the overlying formations, or at the landslide basement through a fault network. Such external origin of water is not observed at the local scale of the Draix‐Laval landslide but is detected at the catchment scale with the influence of deep waters in the streamwater quality of low river flows. Hydrogeological conceptual models are proposed emphasizing the role of the interactions between local (slope) and regional (catchment) flow systems. The observations suggest that this situation is a common case in the Alpine area. Expected consequences of the regional flows on slope stability are discussed in term of rise of pore water pressures and physicochemical weathering of the clay shales.     

Postglacial relative sea‐level rise in the Limfjord region,northern Jutland,Denmark

A new core drilled at Nørrekær Enge, Løgstør, Denmark, shows terrestrial lake and bog sediments lying beneath 10 m of marine sediments. Pollen analysis, ¹⁴C dating and sedimentary observations show that these sediments relate to an ancient lake basin that was flooded when the rising sea levels reached 8.0 m b.s.l. This new study has allowed a review of previous data relating to shoreline displacement from the Limfjord region of northern Jutland, Denmark. Here we present a new shoreline displacement curve spanning the period between c. 11 700 and 7700 cal. a BP and built upon the Nørrekær Enge data and data from seven other boreholes and excavations from the Limfjord region. A previous shoreline displacement curve for this region suggested a very rapid relative sea‐level rise of 3 to 5 m 100 a^?1 whereas this new curve suggests a much slower rise of around 1 m 100 a^?1, similar to global rates.     

Water‐level dynamics in natural and artificial pools in blanket peatlands

Perennial pools are common natural features of peatlands, and their hydrological functioning and turnover may be important for carbon fluxes, aquatic ecology, and downstream water quality. Peatland restoration methods such as ditch blocking result in many new pools. However, little is known about the hydrological function of either pool type. We monitored six natural and six artificial pools on a Scottish blanket peatland. Pool water levels were more variable in all seasons in artificial pools having greater water level increases and faster recession responses to storms than natural pools. Pools overflowed by a median of 9 and 54 times pool volume per year for natural and artificial pools, respectively, but this varied widely because some large pools had small upslope catchments and vice versa. Mean peat water‐table depths were similar between natural and artificial pool sites but much more variable over time at the artificial pool site, possibly due to a lower bulk specific yield across this site. Pool levels and pool‐level fluctuations were not the same as those of local water tables in the adjacent peat. Pool‐level time series were much smoother, with more damped rainfall or recession responses than those for peat water tables. There were strong hydraulic gradients between the peat and pools, with absolute water tables often being 20–30 cm higher or lower than water levels in pools only 1–4 m away. However, as peat hydraulic conductivity was very low (median of 1.5 × 10^?5 and 1.4 × 10^?6 cm s^?1 at 30 and 50 cm depths at the natural pool site), there was little deep subsurface flow interaction. We conclude that (a) for peat restoration projects, a larger total pool surface area is likely to result in smaller flood peaks downstream, at least during summer months, because peatland bulk specific yield will be greater; and (b) surface and near‐surface connectivity during storm events and topographic context, rather than pool size alone, must be taken into account in future peatland pool and stream chemistry studies.     

Radarclinometry of the sand seas of Africa’s Namibia and Saturn’s moon Titan

Radarclinometry is a powerful technique for estimating heights of landforms in synthetic aperture radar (SAR) images of planetary surfaces. In particular, it has been used to estimate heights of dunes in the sand seas of Saturn’s moon Titan (Lorenz, R.D., and 39 colleagues [2006]. Science 312, 724-727). In this work, we verify the technique by comparing dune heights derived from radarclinometry to known topography of dune fields in the Namib sand sea of western Africa. We compared results from three different image grid spacings, and found that 350 m/pixel (the same spacing at which the Cassini RADAR data was processed) is sufficient to determine dune height for dunes of similar morphometry to those of the Namib sand sea. At this grid spacing, height estimates derived from radarclinometry are largely representative of, though may underestimate by as much as 30%, or overestimate by as much as 40%, true dune height. Applying the technique to three regions on Titan, we estimate dune heights of 45-180 m, and dune spacings of 2.3-3.3 km. Obtaining accurate heights of Titan’s dunes will help to constrain the total organic inventory on Titan.     

The Manicouagan impact structure as a terrestrial analogue site for lunar and martian planetary science

The 90 km diameter, late Triassic Manicouagan impact structure of Québec, Canada, is a well-preserved, undeformed complex crater possessing an anorthositic central uplift and a 55 km diameter melt sheet. As such, it provides a valuable terrestrial analogue for impact structures developed on other planetary bodies, especially the Moon and Mars, which are currently the focus of exploration initiatives. The scientific value of Manicouagan has recently been enhanced due to the production, between 1994 and 2006, of ∼18 km of drill core from 38 holes by the mineral exploration industry. Three of these holes are in excess of 1.5 km deep, with the deepest reaching 1.8 km. Here we combine recent field work, sampling and the drill core data with previous knowledge to provide insight into processes occurring at Manicouagan and, by inference, within extraterrestrial impact structures. Four areas of comparative planetology are discussed: impact melt sheets, central uplifts, impact-generated hydrothermal regimes and footwall breccias. Human training and instrument testing opportunities are also considered. The drill core reveals that the impact melt and clast-bearing impact melts in the centre of the structure reach thicknesses of 1.4 km. The 1.1 km thick impact melt has undergone differentiation to yield a lower monzodiorite, a transitional quartz monzodiorite and an upper quartz monzonite sequence. This calls into question the previous citing of Manicouagan as an exemplar of a relatively large crater possessing an undifferentiated melt sheet, which was used as a rationale for assigning different composition lunar impact melts and clast-bearing impact melts to separate cratering events. The predominantly anorthositic central uplift at Manicouagan is comparable to certain lunar highlands material, with morphometric analogies to the King, Tycho, Pythagoras, Jackson, and Copernicus impact structures, which have similar diameters and uplift structure. Excellent exposure of the Manicouagan uplift facilitates mapping and an appraisal of its formation and collapse mechanisms, enhanced by drill core data from the centre of the structure. Recent field studies at the edge of the central island at Manicouagan, and multiple drill core sections through footwall lithologies, provide insight into allochthonous (clastic and suevitic) and autochthonous breccia formation, as well as shock effects. The hydrothermal regimes developed at Manicouagan are akin to systems proposed for Noachian (>3.5 Ga) Mars that involve alteration of impact melts via meteoritic and surface waters, with the generation of phyllosilicates, zeolites, hematite, sulfates and sulfides that can contribute to martian soil formation and sedimentation processes.     

Low temperature hydrolysis of laboratory tholins in ammonia-water solutions: Implications for prebiotic chemistry on Titan

Laboratory tholins react rapidly in 13 wt% ammonia-water at low temperature, producing complex organic molecules containing both oxygen and altered nitrogen functional groups. These reactions display first-order kinetics with half-lives between 0.3 and 14 days at 253 K. The reaction timescales are much shorter than the freezing timescales of impact melts and volcanic sites on Titan, providing ample time for the formation of oxygenated, possibly prebiotic, molecules on its surface. Comparing the rates of the hydrolysis reactions in ammonia-water to those measured in pure water [Neish, C.D, Somogyi, A., Imanaka, H., Lunine, J.I., Smith, M.A., 2008a. Astrobiology 8, 273-287], we find that incorporation of oxygen into the tholins is faster in the presence of ammonia. The rate increases could be due to the increased pH of the solution, or to the availability of new reaction pathways made possible by the presence of ammonia. Using labeled ¹⁵NH₃ water, we find that ammonia does incorporate into some products, and that the reactions with ammonia are largely independent of those with water. A related study in confirms water as the source of the oxygen incorporated into the oxygen containing products.     

The effects of mid-Phanerozoic environmental stress on bryozoan diversity, paleoecology, and paleogeography

Evidence of sustained environmental degradation associated with the end-Guadalupian, end-Permian, and end-Triassic extinctions has been inferred from numerous geochemical and sedimentological studies, but the long-term impacts of this extinction-associated stress on the evolutionary trajectories of marine invertebrates have not been explored. An examination of the diversity, extinction, paleoenvironmental range, and geographical distribution of marine stenolaemate bryozoans during the Permian to Jurassic interval provides striking new evidence of the taxonomic and ecological influence of these mid-Phanerozoic extinctions on one of the most abundant components of the Paleozoic Fauna. Elevated bryozoan extinction rates during the Late Permian and Late Triassic were coupled with major changes in their habitats. Bryozoans gradually disappeared from deep-water offshore settings during the Late Permian and from nearshore and offshore settings during the Late Triassic. Re-colonization of these environments in the wake of each crisis was delayed but coupled with increases in global generic diversity. The taxonomic effects of the end-Guadalupian extinction were milder than previously described, even though ecologically bryozoans were becoming restricted to nearshore settings. The end-Permian mass extinction remained the largest for bryozoans, drastically reducing global and assemblage generic diversity and triggering a permanent change in their paleoenvironmental preferences from nearshore to mid-shelf settings. The 285 Myr dominance of stenolaemate bryozoans ended during the Late Triassic when all but one order (Cyclostomata) became extinct, initiating a taxonomic switch between stenolaemate and gymnolaemate bryozoans. Moreover, spatio-temporal variations in the paleoenvironmental history of bryozoans imply that Late Permian and Late Triassic marine environmental instability resulted largely from some stressful deep-water phenomenon. High extinction rates in nearshore environments in the Late Permian provide a link between marine and terrestrial/atmosphere extinction-related perturbations.     

Uncertainty of gas saturation estimates in a subbituminous coal seam

To assess the commercial viability of a coalbed methane prospect two of the key geological parameters measured are gas content (desorbed gas) and gas holding capacity (adsorption capacity). These two measures, together with reservoir pressure, give an estimate of the gas saturation of the reservoir. Typically gas saturation has been assessed by collecting one adsorption isotherm sample and assuming it is representative of the whole seam reservoir conditions. This study addresses that assumption.To understand the level of variation, and thus the inherent uncertainty in saturation, one core (Jasper-1) from the Huntly coalfield in New Zealand was analysed in detail. Ten samples (representing the whole coal seam) were placed into gas desorption canisters and desorbed for ten days and then analysed for adsorption capacity. Desorption analyses for total measured gas content (average in-situ basis) ranged from 2.32 to 2.89 m³/t (standard deviation (sd) = 0.18) and gas adsorptive capacity at 4 MPa (average in-situ basis) from 2.11 to 3.51 m³/t (sd = 0.38) resulting in saturations ranging from 66% to 120% (sd = 15).Determination of how many samples are required to make a realistic assessment of average reservoir properties requires a consideration of: (i) the level of accuracy desired, (ii) the limit of accuracy possible, which is governed by the magnitude of experimental error, and (iii) the innate variability of the seam. It was found that a minimum of five samples each for adsorption and desorption were required in order to significantly decrease the uncertainty in gas saturation estimates for a subbituminous coal.     

LIBS analysis of geomaterials: Geochemical fingerprinting for the rapid analysis and discrimination of minerals

Laser-induced breakdown spectroscopy (LIBS) is a simple atomic emission spectroscopy technique capable of real-time, essentially non-destructive determination of the elemental composition of any substance (solid, liquid, or gas). LIBS, which is presently undergoing rapid research and development as a technology for geochemical analysis, has attractive potential as a field tool for rapid man-portable and/or stand-off chemical analysis. In LIBS, a pulsed laser beam is focused such that energy absorption produces a high-temperature microplasma at the sample surface resulting in the dissociation and ionization of small amounts of material, with both continuum and atomic/ionic emission generated by the plasma during cooling. A broadband spectrometer-detector is used to spectrally and temporally resolve the light from the plasma and record the intensity of elemental emission lines. Because the technique is simultaneously sensitive to all elements, a single laser shot can be used to track the spectral intensity of specific elements or record the broadband LIBS emission spectra, which are unique chemical ‘fingerprints’ of a material. In this study, a broad spectrum of geological materials was analyzed using a commercial bench-top LIBS system with broadband detection from ∼200 to 965 nm, with multiple single-shot spectra acquired. The subsequent use of statistical signal processing approaches to rapidly identify and classify samples highlights the potential of LIBS for ‘geochemical fingerprinting’ in a variety of geochemical, mineralogical, and environmental applications that would benefit from either real-time or in-field chemical analysis.