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.     

Pennsylvanian carbonate platforms adjacent to deltaic systems in an active marine foreland basin (Escalada Fm., Cantabrian Zone,NW Spain)

The Pennsylvanian marine foreland basin of the Cantabrian Zone (NW Spain) is characterized by the unique development of kilometre‐size and hundred‐metre‐thick carbonate platforms adjacent to deltaic systems. During Moscovian time, progradational clastic wedges fed by the orogen comprised proximal alluvial conglomerates and coal‐bearing deltaic sequences to distal shelfal marine deposits associated with carbonate platforms (Escalada Fm.) and distal clay‐rich submarine slopes. A first phase of carbonate platform development (Escalada I, upper Kashirian‐lower Podolskian) reached a thickness of 400 m, nearly 50 km in width and developed a distal high‐relief margin facing a starved basin, nearly 1000‐m deep. Carbonate slope clinoforms dipped up to 30° and consisted of in situ microbial boundstone, pinching out downslope into calciturbidites, argillaceous spiculites and breccias. The second carbonate platform (Escalada II, upper Podolskian‐lower Myachkovian) developed beyond the previous platform margin, following the basinward progradation of siliciclastic deposits. Both carbonate platforms include: (1) a lower part composed of siliciclastic‐carbonate cyclothems characterized by coated‐grain and ooid grainstones; and (2) a carbonate‐dominated upper part, composed of tabular and mound‐shaped wackestone and algal‐microbial boundstone strata alternating at the decametre scale with skeletal and coated‐grain grainstone beds. Carbonate platforms initiated in distal sectors of the foreland marine shelf during transgressions, when terrigenous sediments were stored in the proximal part, and developed further during highstands of 3rd‐order sequences in a high‐subsidence context. During the falling stage and lowstand systems tracts, deltaic systems prograded across the shelf burying the carbonate platforms. Key factors involved in the development of these unique carbonate platforms in an active foreland basin are: (1) the large size of the marine shelf (approaching 200 km in width); (2) the subsidence distribution pattern across the marine shelf, decreasing from proximal shoreline to distal sectors; (3) Pennsylvanian glacio‐eustacy affecting carbonate lithofacies architecture; and (4) the environmental conditions optimal for fostering microbial and algal carbonate factories.     

Fracture mechanics analysis of multiple cracks in anisotropic media

This paper presents a single‐domain boundary element method (BEM) for linear elastic fracture mechanics analysis in the two‐dimensional anisotropic material. In this formulation, the displacement integral equation is collocated on the un‐cracked boundary only, and the traction integral equation is collocated on one side of the crack surface only. A special crack‐tip element was introduced to capture exactly the crack‐tip behavior. A computer program with the FORTRAN language has been developed to effectively calculate the stress intensity factors of an anisotropic material. This BEM program has been verified having a good accuracy with the previous researches. Furthermore, by analyzing the different anisotropic degree cracks in a finite plate, we found that the stress intensity factors of crack tips had apparent influence by the geometry forms of cracks and media with different anisotropic degrees. Copyright © 2010 John Wiley & Sons, Ltd.     

The use of the exponent K(q) function to delimit homogeneous regions in regional frequency analysis of extreme annual daily rainfall

The regional frequency analysis of extreme annual rainfall data is a useful methodology in hydrology to obtain certain quantile values when no long data series are available. The most crucial step in the analysis is the grouping of sites into homogeneous regions. This work presents a new grouping criterion based on some multifractal properties of rainfall data. For this purpose, a regional frequency analysis of extreme annual rainfall data from the Maule Region (Chile) has been performed. Daily rainfall data series of 53 available stations have been studied, and their empirical moments scaling exponent functions K(q) have been obtained. Two characteristics parameters of the K(q) functions (γ_max and K(0)) have been used to group the stations into three homogeneous regions. Only five sites have not been possible to include into any homogenous regions, being the local frequency analysis of extreme daily rainfall the most appropriate method to be used at these locations. Copyright © 2014 John Wiley & Sons, Ltd.     

Fossil wood

Plants have been making wood (secondary xylem) for more than 370 million years. This familiar material is one of the keys to their massive success. Wood allows plants to attain breathtaking heights and maximize the capture of sunlight for growth. By creating complex, multi‐layered forests, the evolution of wood, has done more to shape life on land than almost any other innovation. Wood is one of the most common terrestrial fossils encountered in the geological record. Whether preserved as huge petrified logs or as minute chunks of charcoal, fossil wood is abundant in rocks of Late Devonian age and younger. It is of enormous scientific importance, shedding light on the identity and stature of ancient trees. As a record of growth over a sustained period, it also tells us much about the climates and environments in which those trees lived. In this article, I explain some aspects of the origin, evolution, preservation, and identification of fossil wood, and emphasise its great significance for geology.     

The lateglacial Quercus expansion in the southern European Alps: rapid vegetation response to a late Allerød climate warming?

A pollen‐inferred vegetation shift, from pioneer birch–pine woodland to mixed pine–summergreen oak forests, in the southern Alpine forelands, is commonly attributed to a centennial‐scale warming that occurred between the Gerzensee Oscillation (GO) and the Younger Dryas. Two microtephra layers bracketing the Younger Dryas onset (the Laacher See Tephra and the Vedde Ash) improve the chronology at Lago Piccolo di Avigliana (northern Italy) and allowed accurate correlation with Central European records where the GO is clearly detected. We used pollen percentages, pollen accumulation rates (PARs) and plant macrofossils to assess the population dynamics of Quercus, and leaf‐cuticle analysis for a better taxonomic identification of Quercus. Our results indicate that the species that was locally present was probably Quercus robur. PARs suggest that the population expansion started as early as the Bølling and followed an exponential increase through time. We attribute this gradual shift to increasing summer temperatures and longer growing seasons which contrast with a gradually decreasing temperature trend as recorded in Greenland ice cores and in Central Europe. Breaks or set‐backs in the PAR record may indicate the biotic response to minor Lateglacial cooling events of different life‐history stages in the Quercus population. Copyright © 2011 John Wiley & Sons, Ltd.     

Fluid generation and evolution during exhumation of deeply subducted UHP continental crust: Petrogenesis of composite granite–quartz veins in the Sulu belt,China

Composite granite–quartz veins occur in retrogressed ultrahigh pressure (UHP) eclogite enclosed in gneiss at General's Hill in the central Sulu belt, eastern China. The granite in the veins has a high‐pressure (HP) mineral assemblage of dominantly quartz+phengite+allanite/epidote+garnet that yields pressures of 2.5–2.1 GPa (Si‐in‐phengite barometry) and temperatures of 850–780°C (Ti‐in‐zircon thermometry) at 2.5 GPa (~20°C lower at 2.1 GPa). Zircon overgrowths on inherited cores and new grains of zircon from both components of the composite veins crystallized at c. 221 Ma. This age overlaps the timing of HP retrograde recrystallization dated at 225–215 Ma from multiple localities in the Sulu belt, consistent with the HP conditions retrieved from the granite. The ε_Hf(t) values of new zircon from both components of the composite veins and the Sr–Nd isotope compositions of the granite consistently lie between values for gneiss and eclogite, whereas δ¹⁸O values of new zircon are similar in the veins and the crustal rocks. These data are consistent with zircon growth from a blended fluid generated internally within the gneiss and the eclogite, without any ingress of fluid from an external source. However, at the peak metamorphic pressure, which could have reached 7 GPa, the rocks were likely fluid absent. During initial exhumation under UHP conditions, exsolution of H₂O from nominally anhydrous minerals generated a grain boundary supercritical fluid in both gneiss and eclogite. As exhumation progressed, the volume of fluid increased allowing it to migrate by diffusing porous flow from grain boundaries into channels and drain from the dominant gneiss through the subordinate eclogite. This produced a blended fluid intermediate in its isotope composition between the two end‐members, as recorded by the composite veins. During exhumation from UHP (coesite) eclogite to HP (quartz) eclogite facies conditions, the supercritical fluid evolved by dissolution of the silicate mineral matrix, becoming increasingly solute‐rich, more ‘granitic’ and more viscous until it became trapped. As crystallization began by diffusive loss of H₂O to the host eclogite concomitant with ongoing exhumation of the crust, the trapped supercritical fluid intersected the solvus for the granite–H₂O system, allowing phase separation and formation of the composite granite–quartz veins. Subsequently, during the transition from HP eclogite to amphibolite facies conditions, minor phengite breakdown melting is recorded in both the granite and the gneiss by K‐feldspar+plagioclase+biotite aggregates located around phengite and by K‐feldspar veinlets along grain boundaries. Phase equilibria modelling of the granite indicates that this late‐stage melting records P–T conditions towards the end of the exhumation, with the subsolidus assemblage yielding 0.7–1.1 GPa at <670°C. Thus, the composite granite–quartz veins represent a rare example of a natural system recording how the fluid phase evolved during exhumation of continental crust. The successive availability of different fluid phases attending retrograde metamorphism from UHP eclogite to amphibolite facies conditions will affect the transport of trace elements through the continental crust and the role of these fluids as metasomatic agents interacting with the mantle wedge in the subduction channel.