A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

Dating fluvial erosion: fluvial response to climate change in the Moselle catchment (France,Germany) since the Late Saalian

This paper focuses upon the youngest terraces of the Moselle and its tributary the Meurthe (NE France and SW Germany). It includes research on several sections, in particular the key sections of Golbey‐Pré Droué and Thörnich‐Hochrech (located in the vicinity of the Vosges Massif and in the Rhenish Massif, respectively), and the use of the Optically Stimulated Luminescence (OSL) dating method. Our investigations made it possible to obtain a more robust chronostratigraphical framework and to update the previous model of fluvial response to climate change. The results demonstrate that the Moselle terrace M3 (first terrace formed after the capture of the Upper Moselle by the Palaeo‐Meurthe) has the same age from the Vosges to the Rhenish Massif. The formation of this terrace included two main periods of sedimentation attributed to the Late Saalian (MIS 6) and the Early Weichselian (MIS 5), respectively. They were separated by a major episode of fluvial erosion that may be allocated to the MIS 6–5 transition on the basis of chronological and sedimentological evidence. This erosion led to the removal of most of the MIS 6 deposits, whereas the MIS 5 deposits have been widely preserved following the subsequent (MIS 5–4) terrace incision. This evolution somewhat contrasts with that observed in the Sarre valley, the main tributary of the Moselle, and with many fluvial systems in western Europe, which show better preservation of deposits from cold periods. This atypical behaviour is explained by the relationship between the fluvial evolution and the glaciers covering the upper Moselle catchment (Vosges Massif) during the Pleistocene cold periods.     

Gaseous drag and planetary formation by accretion

We have made numerical experiments of the collisional and gravitational interaction of a planetesimal swarm in the early Solar System. In particular we study the dynamical evolution of an initial population of kilometer-size planetesimals subject to collisions (accretion, rebound, cratering, and catastrophic fragmentation). This study is based on a Monte-Carlo statistical method and provides the mass and velocity distributions of the planetesimal swarm as a function of time as well as their distribution in heliocentric distance. Several experiments have been performed and three of them are presented here. They simulate the accretional growth of numerous planetesimals in the absence (or presence) of gaseous drag, with (or without) one larger embryo among them, and with (or without) a size gradient. The results show that (i) for a population of planetesimals submitted to a negative gradient in size as the heliocentric distance increases, the outer planetesimals spiral toward the Sun faster than inner ones, leading after some time to an accumulation of bodies inside the cloud which allows the formation of an embryo; (ii) the growth of one embryo among a population of planetesimals is accelerated by the presence of gas and is warranted as long as its feeding zone is fed by the inward flow of planetesimals due to gas drag. These results offer some complementary new insights in the understanding of the accretional formation of 4–5 terrestrial planets instead of the numerous Moon-size planets generally found in numerical experiments.     

Delineation of Microscale Regimes of Fully-Developed Drainage and Implications for Continuum Models

Despite significant progress made in recent years, a fundamental understanding of immiscible displacements at the macroscale is lacking. In this paper we use a version of percolation theory, based on invasion percolation in a gradient, to connect drainage processes at the pore-network scale with the displacement at the macroscale. When the mobility ratio M is sufficiently small, the displacement is stabilized and can be described by invasion percolation in a stabilizing gradient. In the opposite case, it has common features with invasion percolation in a destabilizing gradient. A diagram delineating the regimes of fully developed drainage is developed. The transition between stabilized displacement and fingering is controlled by the change of the sign of the gradient of the percolation probability, and the transition boundary is described by a scaling law involving the capillary number and the viscosity ratio. We review recent work for random networks and extend the method to correlated pore networks. As the regimes of stabilized displacement are also those for which conventional theories (such as the Buckley–Leverett equation) are expected to apply, the phase diagram helps to delineate their validity.     

Vertical accretion rates and heavy metal chronologies in wetland sediments of the Tijuana Estuary

This study represents the first report on sediment accretion rates using¹³⁷Cs dating for a southern California salt marsh. Vertical accretion rates ranged from 0.7 to 1.2 cm yr⁻¹, which is at the high end of sediment accretion values for coastal wetlands. This has lead to increases in elevation within the estuary from 18 to 35 cm over the last 35 years. Depth profiles of metal concentrations were converted to time-based profiles using vertical accretion rates. Chronologies for most cores indicate a consistent peak in sediment lead (Pb) concentrations in the early to mid 1980s, corresponding to the historic decline in Pb use, which was completed in the U.S. by the early 1980s, but not begun in Mexico until 1991. Sediment Pb levels ranged from about 6–56 μg g⁻¹. Other metals did not show any consistent trends in sediment chronology, except for a single core from a mid-marsh site (east-mid 2), which showed a 2–3-fold increase in levels of Cu, Ni, and Zn during the past two decades. Sediment levels of copper (Cu), nickel (Ni), and zinc (Zn) ranged from 6–34 μg g⁻¹, 11–27 μg g⁻¹, and 42–122 μg g⁻¹, respectively. Despite rapid industrial development of the watershed, a comparison of the sediment metal concentrations in the Tijuana Estuary to other anthropogenically-impacted estuaries in the United States and Europe, shows that metal levels in sediments of the north arm of the estuary are relatively low.     

Geodynamic evolution of Korea: A view

Abstract Evidence for South Korean Palaeozoic geodynamic evolution is restricted to the Ogcheon Belt, which is a complex polycyclic domain forming the boundary between the Precambrian Gyeonggi Block to the northwest and the Ryeongnam Block to the southeast. Two independent sub-zones can be distinguished: the Taebaeksan Zone to the northeast and the Ogcheon Zone sensu stricto. The Taebaeksan Zone and Ryeongnam Block display characteristic features of the North China palaeocontinent. This domain remained relatively stable during the Palaeozoic. In contrast, the Ogcheon Belt s. s. is a highly mobile zone that belongs to the South China palaeocontinent and corresponds to a rift that opened during the Early Palaeozoic. In lowermost Devonian times, the rift basin was closed and the Ogcheon Belt was structured in a pile of nappes. From the lack of suture in the Ogcheon Belt it can be inferred that the Gyeonggi Block belongs to the South China palaeocontinent. Thus, the boundary between the North China and South China blocks should be located to the north of Gyeonggi Block, that is, in the Palaeozoic Imjingang Belt. From the Middle Carboniferous, sedimentation started again on a weakly subsiding paralic platform located in the hinterland of the Late Palaeozoic orogen of southwest Japan. In the Late Carboniferous, increasing subsidence recorded extensional tectonics related to the opening of the Yakuno Oceanic Basin (southwest Japan). In the Middle Permian, the end of marine influences in the platform and emplacement of terrestrial coal measures, may be correlated with the closure of the oceanic area and subsequent ophiolite obduction. In Late Permian to Early Triassic times, the Honshu Block (the eastern palaeomargin of the Yakuno Basin) collided with Sino-Korea. Post-collisional intracontinental tectonics reached the Ogcheon Belt in the Middle Triassic (Songnim tectonism). Ductile dextral shear zones associated with synkinematic granitoids were emplaced in the southwest of the belt. In the Upper Triassic, the late stages of the intracontinental transcurrent tectonics generated narrow intramontane troughs (Daedong Supergroup). The Daedong basins were deformed during two tectonic events, in the Middle (?) and Late Jurassic. The Upper Jurassic to Lower Cretaceous basins (Gyeongsang Supergroup), that are controlled by left-lateral faults, may have resulted from the same tectonic event.     

Estimating airborne heavy metal concentrations in Dunkerque (northern France)

This work aims to estimate the levels of lead (Pb), nickel (Ni), manganese (Mn), vanadium (V) and chromium (Cr) corresponding to a 3-month PM₁₀ sampling campaign conducted in 2008 in the city of Dunkerque (northern France) by means of statistical models based on partial least squares regression (PLSR), artificial neural networks (ANNs) and principal component analysis (PCA) coupled with ANN. According to the European Air Quality Directives, because the levels of these pollutants are sufficiently below the European Union (EU) limit/target values and other air quality guidelines, they may be used for air quality assessment purposes as an alternative to experimental measurements. An external validation of the models has been conducted, and the results indicate that PLSR and ANNs, with comparable performance, provide adequate mean concentration estimations for Pb, Ni, Mn and V, fulfilling the EU uncertainty requirements for objective estimation techniques, although ANNs seem to present better generalization ability. However, in accordance with the European regulation, both techniques can be considered acceptable air quality assessment tools for heavy metals in the studied area. Furthermore, the application of factor analysis prior to ANNs did not yield any improvements in the performance of the ANNs.