Raman spectroscopic studies of carbonates part I: High-pressure and high-temperature behaviour of calcite,magnesite, dolomite and aragonite

The room-temperature Raman spectra of aragonite, magnesite and dolomite have been recorded up to 30 GPa and 25 GPa, respectively and no phase changes were observed during compression, unlike calcite. The effect of temperature on the room-pressure Raman spectra of calcite, aragonite, magnesite and dolomite is reported up to 800–1100 K. The measured relative pressure and temperature-shifts of the Raman lines are greater for the lattice modes than for the internal modes of the CO₃ groups. These shifts are used to calculate the mode anharmonic parameters of the observed Raman modes; they are negative and their absolute values are smaller (close to 0) for the internal CO₃ modes than for the lattice modes (4–17 10^?5 K^?1). The temperature shifts of the lattice modes in calcite are considerably larger than those for dolomite and magnesite, and a marked non-linear increase in linewidth is observed above 400° C for calcite. This is consistent with an increasing relaxational component to the libration of the CO₃ groups about their threefold axes, premonitory to the rotational order-disorder transition at higher temperature. This behaviour is not observed for the other calcite structured minerals in this study. We examine systematic variations in the lattice mode frequencies and linewidths with composition, to begin to understand these differences in their anharmonic behaviour. Finally, we have used a simple Debye-Waller model to calculate atomic displacements in calcite, magnesite and dolomite with increasing temperature from the vibrational frequency data, to provide a direct comparison with atomic positional data from high-temperature structure refinements.     

Diamond in Oceanic Peridotites and Chromitites: Evidence for Deep Recycled Mantle in the Global Ophiolite Record

Diamonds have been discovered in mantle peridotites and chromitites of six ophiolitic massifs along the 1300 km‐long Yarlung‐Zangbo suture (Bai et al., 1993; Yang et al., 2014; Xu et al., 2015), and in the Dongqiao and Dingqing mantle peridotites of the Bangong‐Nujiang suture in the eastern Tethyan zone (Robinson et al., 2004; Xiong et al., 2018). Recently, in‐situ diamond, coesite and other UHP mineral have also been reported in the Nidar ophiolite of the western Yarlung‐Zangbo suture (Das et al., 2015, 2017). The above‐mentioned diamond‐bearing ophiolites represent remnants of the eastern Mesozoic Tethyan oceanic lithosphere. New publications show that diamonds also occur in chromitites in the Pozanti‐Karsanti ophiolite of Turkey, and in the Mirdita ophiolite of Albania in the western Tethyan zone (Lian et al., 2017; Xiong et al., 2017; Wu et al., 2018). Similar diamonds and associated minerals have also reported from Paleozoic ophiolitic chromitites of Central Asian Orogenic Belt of China and the Ray‐Iz ophiolite in the Polar Urals, Russia (Yang et al., 2015a, b; Tian et al., 2015; Huang et al, 2015). Importantly, in‐situ diamonds have been recovered in chromitites of both the Luobusa ophiolite in Tbet and the Ray‐Iz ophiolite in Russia (Yang et al., 2014, 2015a). The extensive occurrences of such ultra‐high pressure (UHP) minerals in many ophiolites suggest formation by similar geological events in different oceans and orogenic belts of different ages. Compared to diamonds from kimberlites and UHP metamorphic belts, micro‐diamonds from ophiolites present a new occurrence of diamond that requires significantly different physical and chemical conditions of formation in Earth's mantle. The forms of chromite and qingsongites (BN) indicate that ophiolitic chromitite may form at depths of >150‐380 km or even deeper in the mantle (Yang et al., 2007; Dobrthinetskaya et al., 2009). The very light C isotope composition (δ13C ‐18 to ‐28‰) of these ophiolitic diamonds and their Mn‐bearing mineral inclusions, as well as coesite and clinopyroxene lamallae in chromite grains all indicate recycling of ancient continental or oceanic crustal materials into the deep mantle (>300 km) or down to the mantle transition zone via subduction (Yang et al., 2014, 2015a; Robinson et al., 2015; Moe et al., 2018). These new observations and new data strongly suggest that micro‐diamonds and their host podiform chromitite may have formed near the transition zone in the deep mantle, and that they were then transported upward into shallow mantle depths by convection processes. The in‐situ occurrence of micro‐diamonds has been well‐demonstrated by different groups of international researchers, along with other UHP minerals in podiform chromitites and ophiolitic peridotites clearly indicate their deep mantle origin and effectively address questions of possible contamination during sample processing and analytical work. The widespread occurrence of ophiolite‐hosted diamonds and associated UHP mineral groups suggests that they may be a common feature of in‐situ oceanic mantle. The fundamental scientific question to address here is how and where these micro‐diamonds and UHP minerals first crystallized, how they were incorporated into ophiolitic chromitites and peridotites and how they were preserved during transport to the surface. Thus, diamonds and UHP minerals in ophiolites have raised new scientific problems and opened a new window for geologists to study recycling from crust to deep mantle and back to the surface.     

<Superscript>10</Superscript>Be, <Superscript>18</Superscript>O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands,New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO₂) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and εHf ? 0 CHUR in detrital zircons, sourced from the volcanics. ¹⁰Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.     

深水沉积层序特点及构成要素

本文在回顾当前国际上深水沉积研究热点的基础上,结合在墨西哥湾深水研究的成果系统描述了深水沉积的定义、形成机理、深水沉积层序及深水沉积构成要素的特点.深水沉积主要是在重力流作用下深水环境的沉积,主要形成于相对水平面下降和早期上升的时期,主要分布在低位体系域中.深水层序以凝缩段为边界,块状搬运沉积最早形成并直接位于层序界面上,其上被河道-天然堤沉积所覆盖.典型深水沉积的要素主要由河道、天然堤及越岸沉积、板状砂、块状搬运沉积等构成,这些沉积要素时空上有序地分布.深水河道是物源的主要通道和沉积的重要场所,从上游至下游河道弯曲度增加,能量逐渐减弱.侧向迁移明显,垂向上由富砂的顺直河道演化为相对富泥的弯曲河道.天然堤及越岸沉积以泥质为主,天然堤沿河道呈楔状分布,其近端砂岩含量高,地层厚且倾角较陡;远端砂岩含量低,地层薄且平缓,侧向连续性好但垂向连续性差.板状砂主要为深水扇前缘非限制性沉积,可分为块型和层型.块型侧向连续性好,同时垂向连通性高.层型侧向连续性好,垂向连通性差.块状搬运沉积主要是低水位期坡上沉积物失稳形成的各类滑塌体及碎屑流,其对下伏地层侵蚀明显,分布广泛,变形构造常见,可作为油气良好的封盖层.     

Geology of the Victor Kimberlite, Attawapiskat, Northern Ontario, Canada: cross-cutting and nested craters

The pipe shapes, infill and emplacement processes of the Attawapiskat kimberlites, including Victor, contrast with most of the southern African kimberlite pipes. The Attawapiskat kimberlite pipes are formed by an overall two-stage process of (1) pipe excavation without the development of a diatreme (sensu stricto) and (2) subsequent pipe infilling. The Victor kimberlite comprises two adjacent but separate pipes, Victor South and Victor North. The pipes are infilled with two contrasting textural types of kimberlite: pyroclastic and hypabyssal-like kimberlite. Victor South and much of Victor North are composed of pyroclastic spinel carbonate kimberlites, the main features of which are similar: clast-supported, discrete macrocrystal and phenocrystal olivine grains, pyroclastic juvenile lapilli, mantle-derived xenocrysts and minor country rock xenoliths are set in serpentine and carbonate matrices. These partly bedded, juvenile lapilli-bearing olivine tuffs appear to have been formed by subaerial fire-fountaining airfall processes.

The Victor South pipe has a simple bowl-like shape that flares from just below the basal sandstone of the sediments that overlie the basement. The sandstone is a known aquifer, suggesting that the crater excavation process was possibly phreatomagmatic. In contrast, the pipe shape and internal geology of Victor North are more complex. The northwestern part of the pipe is dominated by dark competent rocks, which resemble fresh hypabyssal kimberlite, but have unusual textures and are closely associated with pyroclastic juvenile lapilli tuffs and country rock breccias±volcaniclastic kimberlite. Current evidence suggests that the hypabyssal-like kimberlite is, in fact, not intrusive and that the northwestern part of Victor North represents an early-formed crater infilled with contrasting extrusive kimberlites and associated breccias. The remaining, main part of Victor North consists of two macroscopically similar, but petrographically distinct, pyroclastic kimberlites that have contrasting macrodiamond sample grades. The juvenile lapilli of each pyroclastic kimberlite can be distinguished only microscopically. The nature and relative modal proportion of primary olivine phenocrysts in the juvenile lapilli are different, indicating that they derive from different magma pulses, or phases of kimberlite, and thus represent separate eruptions. The initial excavation of a crater cross-cutting the earlier northwestern crater was followed by emplacement of phase (i), a low-grade olivine phenocryst-rich pyroclastic kimberlite, and the subsequent eruption of phase (ii), a high-grade olivine phenocryst-poor pyroclastic kimberlite, as two separate vents nested within the original phase (i) crater. The second eruption was accompanied by the formation of an intermediate mixed zone with moderate grade. Thus, the final pyroclastic pipe infill of the main part of the Victor North pipe appears to consist of at least three geological/macrodiamond grade zones.

In conclusion, the Victor kimberlite was formed by several eruptive events resulting in adjacent and cross-cutting craters that were infilled with either pyroclastic kimberlite or hypabyssal-like kimberlite, which is now interpreted to be of probable extrusive origin. Within the pyroclastic kimberlites of Victor North, there are two nested vents, a feature seldom documented in kimberlites elsewhere. This study highlights the meaningful role of kimberlite petrography in the evaluation of diamond deposits and provides further insight into kimberlite emplacement and volcanism.     

Multi‐stage Melting Processes of Ophiolitic Chromitites from Purang Peridotite,the Western Yarlung‐Zangbo Suture Zone,Tibet

The Purang ophiolite, which crops out over an area of about 600 km2 in the western Yarlung‐Zangbo suture zone, consists chiefly of mantle peridotite, pyroxenite and gabbro. The mantle peridotites are mostly harzburgite and minor lherzolite that locally host small pods of dunite. Some pyroxenite and gabbro veins of variable size occur in the peridotites, and most of them strike NW. On the basis of their mineral chemistry podiform chromitites are divided into high‐alumina (Cr# = 20‐60) (Cr# = 100*Cr/(Cr+Al)) and high‐chromium (Cr# = 60‐80) varieties (Thayer, 1970). Typically, only one type occurs in a given peridotite massif, although some ophiolites contain several massifs which can have different chromitite compositions. However, the Purang massif contains both high chrome and high alumina chromitites within a single mafic‐ultramafic body. Seven small, lenticular bodies of chromitite ore have been found in the harzburgite, with ore textures ranging from massive to disseminated to sparsely disseminated; no nodular ore has been observed. Individual ore bodies are 2‐6 m long, 0.5‐2 m wide and strike NW, parallel to the main structure of the ophiolite. Ore bodies 1 and 6 consist of Al‐rich chromitite (Cr# = 52‐55), whereas orebodies 2, 3, 4 and 5 are Cr‐rich varieties (Cr # = 63 to 89). In addition to magnesiochromite, all of the orebodies contain minor olivine, amphibole and serpentine. Mineral structures show that the peridotites experienced plastic deformation and partial melting. On the basis of magnesiochromite and olivine/clinopyroxene compositions two stages of partial melting are identified in the Purang peridotites, an early low‐partial melting event (about 8%), and a later high‐partial melting event (about 40%). We interpret the Al‐rich chromitites as the products of early MORB magmas, whereas the Cr‐rich varieties are thought to have been generated by the later SSZ melts..     

Impact of single-point GPS integrated water vapor estimates on short-range WRF model forecasts over southern India

Specifying physically consistent and accurate initial conditions is one of the major challenges of numerical weather prediction (NWP) models. In this study, ground-based global positioning system (GPS) integrated water vapor (IWV) measurements available from the International Global Navigation Satellite Systems (GNSS) Service (IGS) station in Bangalore, India, are used to assess the impact of GPS data on NWP model forecasts over southern India. Two experiments are performed with and without assimilation of GPS-retrieved IWV observations during the Indian winter monsoon period (November–December, 2012) using a four-dimensional variational (4D-Var) data assimilation method. Assimilation of GPS data improved the model IWV analysis as well as the subsequent forecasts. There is a positive impact of ～10 % over Bangalore and nearby regions. The Weather Research and Forecasting (WRF) model-predicted 24-h surface temperature forecasts have also improved when compared with observations. Small but significant improvements were found in the rainfall forecasts compared to control experiments.     

Fingerprinting of the Atlantic meridional overturning circulation in climate models to aid in the design of proxy investigations

It is desirable to design proxy investigations that target regions where properties reconstructed from calibrated parameters potentially carry high-fidelity information concerning changes in large-scale climate systems. Numerical climate models can play an important role in this task, producing simulations that can be analyzed to produce spatial “fingerprints” of the expected response of various properties under a variety of different scenarios. We will introduce a new method of fingerprinting the Atlantic meridional overturning circulation (AMOC) that not only provides information concerning the sensitivity of the response at a given location to changes in the large-scale system, but also quantifies the linearity, monotonicity and symmetry of the response. In this way, locations that show high sensitivities to changes in the AMOC, but that exhibit, for example, strongly nonlinear behavior can be avoided during proxy investigations. To demonstrate the proposed approach we will use the example of the response of seawater temperatures to changes in the strength of the AMOC. We present results from an earth-system climate model which has been perturbed with an idealized freshwater forcing scenario in order to reduce the strength of the AMOC in a systematic manner. The seawater temperature anomalies that result from the freshwater forcing are quantified in terms of their sensitivity to the AMOC strength in addition to the linearity and monotonicity of their response. A first-order reversal curve (FORC) approach is employed to investigate and quantify the irreversibility of the temperature response to a slowing and recovering AMOC. Thus, FORCs allow the identification of areas that are unsuitable for proxy reconstructions because their temperature versus AMOC relationship lacks symmetry.     

Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH

Structural changes and surface oxidation state were examined following the reaction of hematite (0 0 1), (0 1 2), and (1 1 0) with aqueous Fe(II). X-ray reflectivity measurements indicated that Fe(II) induces changes in the structure of all three surfaces under both acidic (pH 3) and neutral (pH 7) conditions. The structural changes were generally independent of pH although the extent of surface transformation varied slightly between acidic and neutral conditions; no systematic trends with pH were observed. Induced changes on the (1 1 0) and (0 1 2) surfaces include the addition or removal of partial surface layers consistent with either growth or dissolution. In contrast, a <1 nm thick, discontinuous film formed on the (0 0 1) surface that appears to be epitaxial yet is not a perfect extension of the underlying hematite lattice, being either structurally defective, compositionally distinct, or nanoscale in size and highly relaxed. Resonant anomalous X-ray reflectivity measurements determined that the surface concentration of Fe(II) present after reaction at pH 7 was below the detection limit of approximately 0.5-1 μmol/m² on all surfaces. These observations are consistent with Fe(II) oxidative adsorption, whereby adsorbed Fe(II) is oxidized by structural Fe(III) in the hematite lattice, with the extent of this reaction controlled by surface structure at the atomic scale. The observed surface transformations at pH 3 show that Fe(II) oxidatively adsorbs on hematite surfaces at pH values where little net adsorption occurs, based on historical macroscopic Fe(II) adsorption behavior on fine-grained hematite powders. This suggests that Fe(II) plays a catalytic role, in which an electron from an adsorbed Fe(II) migrates to and reduces a lattice Fe(III) cation elsewhere, which subsequently desorbs in a scenario with zero net reduction and zero net adsorption. Given the general pH-independence and substantial mass transfer involved, this electron and atom exchange process appears to be a significant subsystem within macroscopic pH-dependent Fe(II) adsorption.     

Sorption behaviour of pentachlorophenol in sub-Saharan tropical soils: soil types sorption dynamics

In order to predict exposure risks as well as appropriate remediation strategies for pesticides in soils, knowledge of pesticides sorption processes onto various representative soils is vital. Hence, laboratory batch experiments were carried out to study sorption of a pesticide, pentachlorophenol (PCP), on five soils obtained from different sub-Saharan agro-ecological zones (AEZs) in order to understand sorption equilibrium, kinetics, and thermodynamics. Experimental data showed that sorption equilibrium was attained within 24 h. The fitting of kinetic results and equilibrium data to different models suggested partly surface adsorption and partly partitioning of PCP within voids of the various soil components. Sorption was mainly attributed to sharing or exchange of valence electrons between negatively charged PCP molecules and positively charged soil sorption sites. The sorption process was spontaneous and accompanied by decreased entropy, but was pH and temperature dependent, reducing with increase in pH and temperature. The various soils’ PCP sorption capacities were directly proportional to their cation exchange capacities. The low PCP sorption observed in these soils suggested high risk of PCP being present in soil water solution, especially at higher temperatures, which can lead to contamination of the aquifer. This risk may be higher for soils obtained from AEZs with warmer natural temperatures.