Measuring Hg Isotopes in Bio-Geo-Environmental Reference Materials

With the emergence of new analytical techniques and the expansion of scientific fields explored by using mercury isotopes, the community needs reference materials (RM) to validate and assure the accuracy of the results. The present work investigates (1) the characterisation of secondary RM in order to validate analytical systems, (2) the effects of two complex matrices on isotopic determination using stannous chloride cold vapour generation coupled to MC-ICP-MS (CV-MC-ICP-MS), (3) the effects of multiple digestion techniques for total Hg extraction and (4) the characterisation of nine geo-bio-environmental RM. Two secondary mono-elemental RMs analysed using two different analytical setups yielded isotopic compositions on δ²⁰²Hg of −3.54 ± 0.27‰ (CRPG-F65A, 2SD, n = 38) and +2.59 ± 0.19‰ (CRPG-RL24H, 2SD, n = 30) relative to the CRM NIST SRM 3133. These two RMs cover the whole range of Hg isotopic fractionation in natural samples and are made available to the scientific community. Complex fly ash and hydroxysulfate green rust matrices were synthesised, spiked with NIST SRM 3133, then digested and finally analysed versus the mono-elemental NIST SRM 3133 to show potential effect of these complex matrices during CV-MC-ICP-MS. Three digestions techniques, including traditional acid digestion, microwave digestion and high pressure-high temperature digestion, were applied to the lichen RM BCR-482 in order to compare advantages and drawbacks of these methods. Finally, the isotopic compositions of nine RMs including soils (NIST SRM 2711; GXR-2; GSS-4), sediment (GSD-10), jasperoid (GXR-1), ore deposit (GXR-3), fly ashes (BCR-176; BCR-176R) and lichen (BCR-482) are reported. These selected materials have δ²⁰²Hg values ranging from −1.75‰ to +0.11‰. Some RMs also presented mass-independent fractionation with Δ¹⁹⁹Hg and Δ²⁰¹Hg of up to −0.6‰.     

Iron Isotope Variations in Coastal Seawater Determined by Multicollector ICP-MS

In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ⁵⁶Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ⁵⁶Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.     

Origin of Pyroxenite-Peridotite Veined Mantle by Refertilization Reactions: Evidence from the Ronda Peridotite (Southern Spain)

The Ronda orogenic peridotite (southern Spain) contains a varietyof pyroxene-rich rocks ranging from high-pressure garnet granulitesand pyroxenites to low-pressure plagioclase–spinel websterites.The ‘asthenospherized’ part of the Ronda peridotitecontains abundant layered websterites (‘group C’pyroxenites), without significant deformation, that occur asswarms of layers showing gradual modal transitions towards theirhost peridotites. Previous studies have suggested that theselayered pyroxenites formed by the replacement of refractoryspinel peridotites. Here, we present a major- and trace-element,and numerical modelling study of a layered outcrop of groupC pyroxenite near the locality of Tolox aimed at constrainingthe origin of these pyroxenites after host peridotites by pervasivepyroxene-producing, refertilization melt–rock reactions.Mg-number [= Mg/(Mg + Fe) cationic ratio] numerical modellingshows that decreasing Mg-number with increasing pyroxene proportion,characteristic of Ronda group C pyroxenites, can be accountedfor by a melt-consuming reaction resulting in the formationof mildly evolved, relatively low Mg-number melts (0·65)provided that the melt fraction during reaction and the time-integratedmelt/rock ratio are high enough (>0·1 and > 1,respectively) to balance Mg–Fe buffering by peridotiteminerals. This implies strong melt focusing caused by melt channellingin high-porosity domains resulting from compaction processesin a partial melted lithospheric domain below a solidus isothermrepresented by the Ronda peridotite recrystallization front.The chondrite-normalized rare earth element (REE) patterns ofgroup C whole-rocks and clinopyroxenes are convex-upward. Numericalmodeling of REE variations in clinopyroxene produced by a pyroxene-forming,melt-consuming reaction results in curved trajectories in the(Ce/Nd)_N vs (Sm/Yb)_N diagram (where N indicates chondrite normalized).Based on (Ce/Nd)_N values, two transient, enriched domains betweenthe light REE (LREE)-depleted composition of the initial peridotiteand that of the infiltrated melt may be distinguished in thereaction column: (1) a lower domain characterized by convex-upwardREE patterns similar to those observed in Ronda group C pyroxenite–peridotite;(2) an upper domain characterized by melts with strongly LREE-enrichedcompositions. The latter are probably volatile-rich, small-volumemelt fractions residual after the refertilization reactionsthat generated group C pyroxenites, which migrated throughoutthe massif—including the unmelted lithospheric spinel-tectonitedomain. The Ronda mantle domains affected by pyroxenite- anddunite- or harzburgite-forming reactions (the ‘layeredgranular’ subdomain and ‘plagioclase-tectonite’domain) are on average more fertile than the residual, ‘coarsegranular’ subdomain at the recrystallization front. Thisindicates that refertilization traces the moving boundariesof receding cooling of a thinned and partially melted subcontinentallithosphere. This refertilization process may be widespreadduring transient thinning and melting of depleted subcontinentallithospheric mantle above upwelling asthenospheric mantle. KEY WORDS: subcontinental mantle; refertilization; pyroxenite; peridotite; websterite; melt–rock reaction; plagioclase; trace elements     

Morphology and sedimentology of a complex debris flow in a clay‐shale basin

Coupling morphological, sedimentological, and rheological studies to numerical simulations is of primary interest in defining debris‐flow hazard on alluvial fans. In particular, numerical runout models must be carefully calibrated by morphological observations. This is particularly true in clay‐shale basins where hillslopes can provide a large quantity of poorly sorted solid materials to the torrent, and thus change both the mechanics of the debris flow and its runout distance. In this context, a study has been completed on the Faucon stream (southeastern French Alps), with the objectives of (1) defining morphological and sedimentological characteristics of torrential watersheds located in clay‐shales, and (2) evaluating through a case study the scouring potential of debris flows affecting a clay‐shale basin. Morphological surveys, grain‐size distributions and petrographic analyses of the debris‐flow deposits demonstrate the granular character of the flow during the first hectometre, and its muddy character from there to its terminus on the debris fan. These observations and laboratory tests suggest that the contributing areas along the channel have supplied the bulk of the flow material. Copyright © 2005 John Wiley & Sons, Ltd.     

Volcanic and solar activity, and atmospheric circulation influences on cosmogenic Be fallout at Vostok and Concordia (Antarctica) over the last 60 years

The cosmogenic nuclide beryllium-10 (¹⁰Be), recovered from ice cores, is often used to study solar activity on long timescales. However, the ¹⁰Be signal is also influenced by factors other than the Sun. To identify and quantify various contributions to the ¹⁰Be signal, two Antarctic snow records from the Vostok and Concordia sites spanning the last 60 years were studied at a sub-annual resolution. Three factors that contribute to the ¹⁰Be signal were identified. First, a significant period of approximately 11 yr that can be associated with the modulation of ¹⁰Be production by solar activity was detected in both records. The solar imprint constitutes 20-35% of the variance within the total signal. The 11-yr ¹⁰Be snow component was attenuated by a factor of ∼0.5 and was delayed by ∼1.4 yr compared to the ¹⁰Be production expected within the polar atmosphere. The result could be interpreted as the composite response of a stratospheric ¹⁰Be reservoir with an 11-yr modulation that was attenuated and delayed (with respect to ¹⁰Be polar production) and to a tropospheric ¹⁰Be reservoir with an 11-yr modulation that was not attenuated or delayed. Then, peaks in ¹⁰Be concentrations that were ∼66% and ∼35% higher than the average concentration were observed during the stratospheric volcanic eruptions of Agung (in 1963) and Pinatubo (in 1991), respectively. In light of these new results, published ¹⁰Be ice core records could be reinterpreted because spikes in ¹⁰Be concentration appear at the time of several stratospheric events. The data indicate that stratospheric volcanic eruptions can impact ¹⁰Be transport and deposition as a result of the roles played by the sedimentation of sulfate aerosols and the formation and rapid settling of polar stratospheric clouds (PSC). Also, an interannual variability of ∼4 yr was determined in both ¹⁰Be records, corresponding to ∼26% of the variance within the signal at Vostok. As with species of marine origin (sodium), this 4-yr variability is interpreted as a tropospheric modulation. The 4-yr variability could be associated with atmospheric circulation associated with the coupled Southern Ocean ocean-atmosphere system. The results presented here, from sites within the high Antarctic plateau, open new possibilities for ice core dating over the last few centuries and for the reconstruction of past solar activity in relation to climate.     

Crustal‐scale fluid flow during the tectonic evolution of the Bighorn Basin (Wyoming,USA)

Stable isotope measurements (O, C, Sr), microthermometry and salinity measurements of fluid inclusions from different fracture populations in several anticlines of the Sevier‐Laramide Bighorn basin (Wyoming, USA) were used to unravel the palaeohydrological evolution. New data on the microstructural setting were used to complement previous studies and refine the fracture sequence at basin scale. The latter provides the framework and timing of fluid migration events across the basin during the Sevier and Laramide orogenic phases. Since the Sevier tectonic loading of the foreland basin until its later involvement into the Laramide thick‐skinned orogeny, three main fracture sets (out of seven) were found to have efficiently enhanced the hydraulic permeability of the sedimentary cover rocks. These pulses of fluid are attested by calcite crystals precipitated in veins from hydrothermal (T > 120 °C) radiogenic fluids derived from Cretaceous meteoric fluids that interacted with the Precambrian basement rocks. Between these events, vein calcite precipitated from formational fluids at chemical and thermal equilibrium with surrounding environment. At basin scale, the earliest hydrothermal pulse is documented in the western part of the basin during forebulge flexuring and the second one is documented in basement‐cored folds during folding. In addition to this East/West diachronic opening of the cover rocks to hydrothermal pulses probably controlled by the tectonic style, a decrease in ^87/86Sr values from West to East suggests a crustal‐scale partially squeegee‐type eastward fluid migration in both basement and cover rocks since the early phase of the Sevier contraction. The interpretation of palaeofluid system at basin scale also implies that joints developed under an extensional stress regime are better vertical drains than joints developed under strike‐slip regime and enabled migration of basement‐derived hydrothermal fluids.     

Pyrite tracks assimilation of crustal sulfur in Pyrenean peridotites

Cobalt-bearing pyrite (0.5?C2.0?wt.% Co) is abnormally abundant (up to 35?vol.% of the total volume of the sulfide phase) in some eastern Pyrenean peridotite massifs, compared to pieces of subcontinental mantle studied so far for sulfides. Pyrite occurs as vermicular intergrowths inside pentlandite and/or chalcopyrite or as coarser, blocky grains in the intergranular pores of host peridotites. Those different pyrites are characterized by different platinum-group element systematics (measured by laser ablation microprobe and ICP-MS). Vermicular pyrite intergrown with pentlandite displays Os-, Ir-, Ru- and Rh-enriched chondrite normalized PGE patterns of Monosulfide solid solution (Mss). In contrast, coarse-grained intergranular (??blocky??) pyrites, are PGE-poor. Chalcophile trace elements (i.e. Zn, Pb, Ag, Au) that are not usually concentrated in mantle-derived sulfides were commonly detected. By contrast, selenium contents are generally low, yielding thus pyrite with high S/Se ratio (>10⁵), consistent with a sedimentary sulfur source. Pyrite microtextures and chalcophile trace element contents support a process of assimilation of crustal sulfur from the metamorphosed sedimentary country rocks. These latter generated highly reactive CO₂-S fluids, which were injected into structural discontinuities of the lherzolitic bodies. Sulfur has reacted at T?=?300?C550°C with pre-existing, mantle-derived, metal-rich sulfide assemblages (pentlandite-chalcopyrite). Addition of crustal sulfur did produce Mss which, on cooling, exsolved the Os-rich pyrite in addition to pentlandite. The coarse-grained pyrite types have crystallized directly from S-rich fluids.     

Temporal variability of suspended sediment sources in an alpine catchment combining river/rainfall monitoring and sediment fingerprinting

Influence of the rainfall regime on erosion and transfer of suspended sediment in a 905‐km² mountainous catchment of the southern French Alps was investigated by combining sediment monitoring, rainfall data, and sediment fingerprinting (based on geochemistry and radionuclide concentrations). Suspended sediment yields were monitored between October 2007 and December 2009 in four subcatchments (22–713 km²). Automatic sediment sampling was triggered during floods to trace the sediment origin in the catchment. Sediment exports at the river catchment outlet (330 ± 100 t km^‐2 yr^‐1) were mainly driven (80%) by widespread rainfall events (long duration, low intensities). In contrast, heavy, local and short duration storms, generated high peak discharges and suspended sediment concentrations in small upstream torrents. However, these upstream floods had generally not the capacity to transfer the sediment down to the catchment outlet and the bulk of this fine sediment deposited along downstream sections of the river. This study also confirmed the important contribution of black marls (up to 70%) to sediment transported in rivers, although this substrate only occupies c. 10% of the total catchment surface. Sediment exports generated by local convective storms varied significantly at both intra‐ and inter‐flood scales, because of spatial heterogeneity of rainfall. However, black marls/marly limestones contribution remained systematically high. In contrast, widespread flood events that generate the bulk of annual sediment supply at the outlet were characterized by a more stable lithologic composition and by a larger contribution of limestones/marls, Quaternary deposits and conglomerates, which corroborates the results of a previous sediment fingerprinting study conducted on riverbed sediment. Copyright © 2012 John Wiley & Sons, Ltd.     

A preliminary study of habitat and resource partitioning among co-occurring tropical dolphins around Mayotte, southwest Indian Ocean

Mayotte in the southwest Indian Ocean is characterized by high dolphin diversity. They may coexist within a fairly small area around the island because they exploit neither the same preferential habitats nor the same resources. This preliminary study aimed to investigate ecological niche segregation among these delphinid communities: the Indo-Pacific bottlenose dolphin, Tursiops aduncus, the pantropical spotted dolphin, Stenella attenuata, the spinner dolphin, Stenella longirostris, and the melon-headed whale, Peponocephala electra. Two approaches were used. Habitat preferences were investigated by analysing dolphin sighting data and associated physiographical characteristics. Resource partitioning was explored by analysing C and N stable isotopes in skin and blubber biopsies. Only T. aduncus, which showed clear association with coastal habitats in the lagoon, differed from the others in terms of habitat preferences, characterised by shallow depth and slope, and proximity to the coast. All other species shared similar oceanic habitats immediately outside the lagoon, these being of higher depth and slope, greater distance from the coast and were not discernable by discriminant analysis. The two Stenella species and the melon-headed whale displayed very high overlap in habitat physiographic variables. The analysis of stable isotopes confirmed the ecological isolation of T. aduncus and revealed a clear segregation of P. electra compared to the two Stenella that was not apparent in the habitat analysis. This may reflect ecological differences that were not observable from diurnal surface observations.     

Information content of snow hydrological signatures based on streamflow,precipitation and air temperature

Hydrological signatures that represent snow processes are valuable to gain insights into snow accumulation and snow melt dynamics. We investigated five snow signatures. Considering inter-annual average of each calendar day, two slopes derived from the relation between streamflow and air temperature for different periods and streamflow peak maxima are used as signatures. In addition, two different approaches are used to compute inter-annual average and yearly snow storage estimates. We evaluated the ability of these signatures to characterize average (a) snow melt dynamics and (b) snow storage. They were applied in 10 Critical Zone Observatory catchments of the Southern Sierra mountains (USA) characterized by a Mediterranean climate. The relevance and information content of the signatures are evaluated using snow depth and snow water equivalent measurements as well as inter-catchment differences in elevation. The slopes quantifying the relations between streamflow and air temperature and the date of streamflow peak were found to characterize snow melt dynamics in terms of snow melt rates and snow melt affected areas. Streamflow peak dates were linked to the period of highest snow melt rates. Snow storage could be estimated both on average, considering all years, and for each year. Snow accumulation dynamics could not be characterized due to the lack of streamflow response during the snow accumulation period. The signatures were found potentially valuable to gain insights into catchment scale snow processes. In particular, when comparing catchments or observed and simulated data, they could provide insights into differences in terms of (a) snow melt rate and/or snow melt affected area over the snow melt season and (b) average or yearly snow storage. Requiring only widely available data, these hydrological signatures can be valuable for snow processes characterization, catchment comparison/classification or model development, calibration or evaluation.