Flat rare earth element patterns as an indicator of cumulate processes in the Lesser Qinling carbonatites, China

The Lesser Qinling carbonatite dykes are mainly composed of calcites. They are characterized by unusually high heavy rare earth element concentrations (HREE; e.g. Yb > 30 ppm) and flat to weakly light rare earth element (LREE) enriched chondrite-normalized patterns (La/Yb_n = 1.0–5.5), which is in marked contrast with all other published carbonatite data. The trace element contents of calcite crystals were measured in situ by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Some crystals show reduced LREE from core to rim, whereas their HREE compositions are relatively constant. The total REE contents and chondrite-normalized REE patterns from the cores of carbonate crystals are similar to those of the whole rock. The carbon and oxygen isotopic compositions of calcites fall within the range of primary, mantle-derived carbonatites. The initial Sr isotopic compositions (0.70480–0.70557) of calcites are consistent with an EM1 source or mixing between HIMU and EM1 mantle sources. However these sources cannot produce carbonatite parental magmas with a flat or slightly LREE enrichment pattern by low degrees of partial melting. Analyses of carbonates from other carbonatites show that carbonates have nearly flat REE pattern if they crystallize from a LREE enriched carbonatite melt. This implies that when carbonates crystallize from a carbonatite melt the calcite/melt partition coefficients (D) for HREE are much greater than the D for the LREE. The nearly flat REE patterns of the Lesser Qinling carbonatites can be explained if they are carbonate cumulates that contain little trapped carbonatite melt. Strong enrichment of HREE in the carbonatites may require their derivation by small degrees of melting from a garnet-poor source.     

Symphurus civitatium (Pleuronectiformes: Cynoglossidae), a second estuarine-occurring tonguefish off the Southeastern United States and Northern Gulf of Mexico

Two species of tonguefishes,Symphurus plagiusa (Linnaeus 1766) andSymphurus civitatium Ginsburg 1951, occur sympatrically and sometimes syntopically in shallow water habitats in North Carolina and Louisiana estuaries. In North Carolina, approximately 2% of 430 small (<75 mm SL) tonguefishes collected wereS. civitatium, while in Barataria Bay, Louisiana, this species was more abundant and cosmopolitan in distribution than wasS. plagiusa, comprising over 82% of 3,564 tonguefishes collected with a small beam trawl over a 2-yr period. Historical literature has regardedS. plagiusa as the only tonguefish species inhabiting inshore waters in both regions. Presence of a secondSymphurus species in shallow estuaries has been overlooked, most probably due to difficulties in identifying early post-settlement juveniles because both species have similar morphologies and overlapping dorsal-fin and anal-fin ray counts. Juveniles can be readily recognized by differences in number of caudal-fin rays (10 inS. plagiusa versus 12 inS. civitatium), especially when used in combination with pigmentation patterns and posterior extent of the jaws relative to the posterior margin of the lower eye. The most distinctive pigmentation difference between juveniles of these two species (allowing for accurate identifications of over 98% of juveniles) is the absence inS. civitatium (12–61 mm SL) of a series of melanophores overlying pterygiophore regions of the dorsal and anal fins on the blind side. This feature contrasts markedly with that of juvenileS. plagiusa (12–65 mm SL), which are characterized by two interrupted, diagonal series of dark chromatophores converging, but not merging, with posterior tapering of the body. Occurrence of two sympatric species of tonguefishes in estuarine environments in the northcentral Gulf of Mexico and southeastern U.S. potentially compromises results of earlier ecological and distributional studies that assumed presence of only a single tonguefish species in these regions.     

Reaction mechanism of uranyl in the presence of zero-valent iron nanoparticles

The current study provides an investigation of abiotic reduction of an oversaturated uranyl solution driven by iron nanoparticle oxidation. The reactivity of nano-scale zero-valent iron (ZVI) under mildly oxic conditions (1.2% O₂ and 0.0017% CO₂) was studied in 1000 ppm uranyl solution in the pH range 3-7, at reaction times from 10 min to 4 h. Reductive precipitation of UO₂ was observed as the main process responsible for the removal of uranium from solution with the kinetics of reaction becoming increasingly favourable at higher pH. Despite working with an oversaturated uranium solution, the precipitation of UO₂ occurred in preference to precipitation of UO₃·2H₂O (metaschoepite) at reaction times between 1 and 4 h and for uranyl solutions initially set up at pH ?5. Characterisation of both solid and solution phases was performed using X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) imaging, X-ray diffraction (XRD) and inductively coupled plasma atomic emission spectroscopy (ICP-AES).     

The significance of organic matter degradation in the interpretation of historical pollution trends in depth profiles of estuarine sediment

The quantitative significance of organic matter degradation in bringing about the early diagenetic mobility of anthropogenic trace metals (Cu, Zn, Pb) is assessed specifically in relation to the use of estuarine sediments as historical records of pollution. A 1,500 mm salt-marsh sediment depth profile from Tites Point, Severn Estuary, England, was sampled at 10-mm intervals. Organic carbon determinations were carried out by a wet oxidation technique, and ‘organic fraction’ metals were separated by sequential leaching. Results demonstrated that organic phase metals are quantitatively significant in Severn Estuary sediments, particularly Cu and Zn (Cu>Zn), and that metals are probably released from this fraction during early diagenesis. The degree of release, and the apparent loss of the released trace metals from the sediment, would suggest that the use of estuarine sediments as historical records of pollution requires qualification.     

Scale of pluton/wall rock interaction near May Lake,Yosemite National Park,CA, USA

Interaction of magma with wall rock is an important process in igneous petrology, but the mechanisms by which interactions occur are poorly known. The western outer granodiorite of the Cretaceous Tuolumne Intrusive Suite of Yosemite National Park, California, intruded a variety of metasedimentary and igneous wall rocks at 93.1 Ma. The May Lake metamorphic screen is a metasedimentary remnant whose contact zone exhibits a variety of interaction phenomena including xenolith incorporation, disaggregation, and partial melting. The chemical contrast of these metasedimentary rocks with the invading pluton provides an excellent measure of pluton/wall rock interactions. Wall rock xenoliths (mostly pelitic quartzite) are predominantly located in an elongate horizon surrounded by a hybridized fine-grained granodiorite. Initial Sr and Nd isotopic ratios of the hybridized granodiorite indicate significant local incorporation of crustal material. Major- and trace-element geochemical data indicate that contamination of the granodiorite occurred via selective assimilation of both high-K and low-K, high-silica partial melts derived from pelitic quartzite. Although the hybridized granodiorite shows significant amounts of contamination, adjacent to xenoliths the proportion of contamination is undetectable more than a meter away. These results indicate that the chemical and isotopic variability of the Tuolumne Intrusive Suite is not caused by magma contamination via in situ wall rock assimilation.     

Timing and setting of skarn and iron oxide formation at the Smältarmossen calcic iron skarn deposit, Bergslagen, Sweden

Abundant iron oxide deposits including banded iron formations, apatite iron oxide ores, and enigmatic marble/skarn-hosted magnetite deposits occur in the Palaeoproterozoic Bergslagen region, southern Sweden. During the last 100 years, the latter deposit class has been interpreted as contact metasomatic skarn deposits, metamorphosed iron formations, or metamorphosed carbonate replacement deposits. Their origin is still incompletely understood. At the Smältarmossen mine, magnetite was mined from a ca. 50-m-thick calcic skarn zone at the contact between rhyolite and stratigraphically overlying limestone. A syn-volcanic dacite porphyry which intruded the footwall has numerous apophyses that extend into the mineralized zone. Whole-rock lithogeochemical and mineral chemical analyses combined with textural analysis suggests that the skarns formed by veining and replacement of the dacite porphyry and rhyolite. These rocks were added substantial Ca and Fe, minor Mg, Mn, and LREE, as well as trace Co, Sn, U, As, and Sr. In contrast, massive magnetite formed by pervasive replacement of limestone. Tectonic fabrics in magnetite and skarn are consistent with ore formation before or early during Svecokarelian ductile deformation. Whereas a syngenetic–exhalative model has previously been suggested, our results are more compatible with magnetite formation at ca. 1.89 Ga in a contact metasomatic skarn setting associated with the dacite porphyry.     

Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure

This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO₃ into calcite can be described by the kinetic parameters (E?=?231.7 kJ/mol and A _o ?=?22.69 h^?1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (<1 Ky). On the other hand, the extrapolation of the rate to prograde metamorphic conditions reveals that the Mg-calcite formed from dolomitic marble in the absence of metamorphic fluid may not reach Mg-saturation until temperatures corresponding to high-grade metamorphism (e.g., >340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68?×?10^?14 m²/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.     

Metallogenesis in the Harlech Dome,North Wales: A fluid inclusion interpretation

A regional fluid inclusion study of Cu-Au (+Zn-Pb) mineralisation in the Harlech Dome area, North Wales, gives support to the concept of two distinct metallogenic episodes. The inclusion assemblages associated with the porphyry copper mineralisation at Coed-y-Brenin are consistent with a genetic model of early potassic-propylitic alteration overprinted by later phyllic alteration. High salinity fluids, normally characteristic of potassic alteration, are confined to the host rock quartz. The meteoric/hydrothermal system is closely linked to the emplacement of late-Cambrian diorites. Integrated fluid inclusion and mineralogical studies of the Gold-belt veins suggest that the mineralising fluids were probably dehydration waters released from weakly metamorphosed Cambrian and perhaps Precambrian sediments during hydraulic fracturing in a tensional zone at the close of the Caledonian orogeny. Localisation of economic concentrations of gold in veins at the level of the Clogau Formation is ascribed to a destabilisation of metal complexes caused by a change in fluid buffering from a pyrite-magnetite assemblage in the Lower Cambrian sediments to a pyrite-pyrrhotite-graphite assemblage in the Upper Cambrian sediments. Veining associated with the Coed-y-Brenin porphyry copper deposit and related breccia pipes can be distinguished from the copper-gold veins of the coextensive Dolgellau Gold-belt by the presence in the former of inclusions notably richer in CO₂. Furthermore the Gold-belt fluids have a distinctive low CO₂/CH₄+N₂+H₂ ratio.