Modeling on adsorption–desorption of trace metals to suspended particle matter in the Changjiang Estuary

The uptake and release of trace metals (Cu, Ni, Zn, Cd, and Co) in estuaries are studied using river and sea end-member waters and suspended particulate matter (SPM) collected from the Changjiang Estuary, China. The kinetics of adsorption and desorption were studied in terms of environmental factors (pH, SPM loading, and salinity) and metal concentrations. The uptake of the metals studied onto SPM occurred mostly within 10 h and reached an asymptotic value within 40 h in the Changjiang Estuary. As low pH river water flows into the high pH seawater and the water become more alkaline as it approaches to the seaside of estuary, metals adsorb more on SPM in higher pH water, thus, particulate phase transport of metal become increasingly important in the seaward side of the estuary. The percentage of adsorption recovery and the distribution coefficients for trace metals remained to be relatively invariable and a significant reduction only occurred in very high concentrations of metals (>0.1 mg L⁻¹). The general effect of salinity on metal behavior was to decrease the degree of adsorption of Cu, Zn, Cd, Co, and Ni onto SPM but to increase their adsorption equilibrium pH. The adsorption–desorption kinetics of trace metals were further investigated using Kurbatov adsorption model. The model appears to be most useful for the metals showing the conservative behavior during mixing of river and seawater in the estuary. Our work demonstrates that dissolved concentration of trace metals in estuary can be modeled based on the metal concentration in SPM, pH and salinity using a Kurbatov adsorption model assuming the natural SPM as a simple surfaced molecule.     

Emplacement ages and sources of kimberlites and related rocks in southern Africa: U–Pb ages and Sr–Nd isotopes of groundmass perovskite

Groundmass perovskite has been dated by LA-ICPMS in 135 kimberlites and related rocks from 110 localities across southern Africa. Sr and/or Nd isotopes have been analysed by LA-MC-ICPMS in a subset of these and integrated with published data. The age distribution shows peaks at 1,600–1,800, 1,000–1,200, 500–800 and 50–130 Ma. The major “bloom” of Group I kimberlites at ca 90 ± 10 Ma was preceded by a slow build-up in magmatic activity from ca 180 Ma. The main pulse of Group II kimberlites at 120–130 Ma was a distinct episode within this build-up. Comparison of the isotopic data with seismic tomography images suggests that metasomatized subcontinental lithospheric mantle (SCLM) with very low ε _Nd and high ⁸⁷Sr/⁸⁶Sr, (the isotopic signature of Group II kimberlites) was focused in low-Vs zones along translithospheric structures. Such metasomatized zones existed as early as 1,800 Ma, but were only sporadically tapped until the magmatic build-up began at ca 180 Ma, and contributed little to the kimberlitic magmas after ca 110 Ma. We suggest that these metasomatized volumes resided in the deep SCLM and that their low-melting point components were “burned off” by rising temperatures, presumably during an asthenospheric upwelling that led to SCLM thinning and a rise in the ambient geotherm between 120 and 90 Ma. The younger Group I kimberlites therefore rarely interacted with such SCLM, but had improved access to shallower volumes of differently metasomatized, ancient SCLM with low ⁸⁷Sr/⁸⁶Sr and intermediate ε _Nd (0–5). The kimberlite compositions therefore reflect the evolution of the SCLM of southern Africa, with metasomatic-enrichment events from as early as 1.8 Ga, through a major thermal and compositional change at ca 110 Ma, and the major kimberlite “bloom” around 90 Ma.     

Trace‐element signatures of apatites in granitoids from the Mt Isa Inlier,northwestern Queensland

The concentrations of trace elements in apatite from granitoid rocks of the Mt Isa Inlier have been investigated using the laser‐ablation inductively coupled plasma‐mass spectrometry (ICP‐MS) microprobe. The results indicate that the distribution of trace elements (especially rare‐earth elements (REE), Sr, Y, Mn and Th) in apatite strongly reflects the chemical characteristics of the parental rock. The variations in the trace‐element concentrations of apatite are correlated with parameters such as the SiO₂ content, oxidation state of iron, total alkalis and the aluminium saturation index (ASI). The relative enrichment of Y, HREE and Mn and the relative depletion of Sr in the apatites studied reflect the degree of fractionation of the host granite. Apatites from strongly oxidised plutons tend to have higher concentrations of LREE relative to MREE. Manganese concentrations are higher in apatite from reduced granitoids because Mn²⁺substitutes directly for Ca²⁺. The La/Ce ratio of apatite is well‐correlated with the whole‐rock K²O and Na²O contents, as well as with the oxidation state and ASI. Because apatite trace‐element composition reflects the chemistry of the whole rock, it can be a useful indicator mineral for the recognition of mineralised granite suites, where particular mineralisation styles are associated with granitoids that have specific geochemical fingerprints.     

Compositional zoning of fluid inclusions in the Archaean Junction gold deposit,Western Australia: A process of fluid ‐ wall‐rock interaction?

The Junction gold deposit, in Western Australia, is an orogenic gold deposit hosted by a differentiated, iron‐rich, tholeiitic dolerite sill. Petrographic, microthermometric and laser Raman microprobe analyses of fluid inclusions from the Junction deposit indicate that three different vein systems formed at three distinct periods of geological time, and host four fluid‐inclusion populations with a wide range of compositions in the H₂O–CO₂–CH₄–NaCl ± CaCl₂ system. Pre‐shearing, pre‐gold, molybdenite‐bearing quartz veins host fluid inclusions that are characterised by relatively consistent phase ratios comprising H₂O–CO₂–CH₄ ± halite. Microthermometry suggests that these veins precipitated when a highly saline, >340°C fluid mixed with a less saline ≥150°C fluid. The syn‐gold mineralisation event is hosted within the Junction shear zone and is associated with extensive quartz‐calcite ± albite ± chlorite ± pyrrhotite veining. Fluid‐inclusion analyses indicate that gold deposition occurred during the unmixing of a 400°C, moderately saline, H₂O–CO₂ ± CH₄ fluid at pressures between 70 MPa and 440 MPa. Post‐gold quartz‐calcite‐biotite‐pyrrhotite veins occupy normal fault sets that slightly offset the Junction shear zone. Fluid inclusions in these veins are predominantly vapour rich, with CO₂?CH₄. Homogenisation temperatures indicate that the post‐gold quartz veins precipitated from a 310 ± 30°C fluid. Finally, late secondary fluid inclusions show that a <200°C, highly saline, H₂O–CaCl₂–NaCl–bearing fluid percolated along microfractures late in the deposit's history, but did not form any notable vein type. Raman spectroscopy supports the microthermometric data and reveals that CH₄–bearing fluid inclusions occur in syn‐gold quartz grains found almost exclusively at the vein margin, whereas CO₂–bearing fluid inclusions occur in quartz grains that are found toward the centre of the veins. The zonation of CO₂:CH₄ ratios, with respect to the location of fluid inclusions within the syn‐gold quartz veins, suggest that the CH₄ did not travel as part of the auriferous fluid. Fluid unmixing and post‐entrapment alteration of the syn‐gold fluid inclusions are known to have occurred, but cannot adequately account for the relatively ordered zonation of CO₂:CH₄ ratios. Instead, the late introduction of a CH₄–rich fluid into the Junction shear zone appears more likely. Alternatively, the process of CO₂ reduction to CH₄ is a viable and plausible explanation that fits the available data. The CH₄–bearing fluid inclusions occur almost exclusively at the margin of the syn‐gold quartz veins within the zone of high‐grade gold mineralisation because this is where all the criteria needed to reduce CO₂ to CH₄ were satisfied in the Junction deposit.     

Geology and petroleum potential of the Fairway Basin in the Tasman Sea

The Fairway Basin is a large, generally north – south-trending, sediment-filled structure in water 1500 – 3000 m deep, on the eastern slope of the Lord Howe Rise in the Tasman Sea, and is partly within Australian jurisdiction. It was poorly known until a few years ago, when seismic profiling and piston coring cruises were carried out. The basin, about 1100 km long and 120 – 200 km wide, can be divided into three segments—north, central and south—that trend northwest, north and north-northwest, respectively. All three segments probably formed by thinning of continental crust during breakup of Lord Howe Rise and surrounding aseismic continental ridges in the Late Cretaceous and Paleocene. Normal faulting, large inputs of terrigenous sediment and subsidence to bathyal marine depths occurred during that time. A period of compression, perhaps related to overthrusting on New Caledonia, occurred in the Eocene, leading to uplift (and in parts, erosion) of northern Lord Howe Rise, and reversal of faulting in the basin. By the Oligocene, the area was again in bathyal depths, and pelagic ooze and some turbidites accumulated. The basinal sequence is generally 2000 – 4000 m thick, with 1200 – 3200 m of Cretaceous to Eocene sediment concentrated in depocentres, capped by 500 – 800 m of Oligocene and younger sediment. In the depocentres, numerous sedimentary diapirs pierce sedimentary sequences. The sedimentary diapirs appear to be fed by Cretaceous muds deposited during rifting. Often, these diapirs are overlain by faults extending to the seafloor, and hummocky bathymetry is possibly caused by fluid escape. The overall geology suggests that the Fairway Basin may be a large frontier hydrocarbon province. Seismic profiles display a bottom-simulating reflector above many depocentres, 500 – 700 m below the seafloor. The bottom-simulating reflector has positive polarity, which could result from a diagenetic phase transformation, a thin gas hydrate layer with a sharp top, or from the sharp base of a gas layer (probably beneath gas hydrates). Standard piston cores taken above diapirs and apparent fluid-escape features have recovered little gas. Other than drilling, the next steps in assessing petroleum potential are to clearly document fluid-escape structures, and to sample any fluids emitted for hydrocarbons.     

Origin of the Mt Ashmore structural dome,west Bonaparte Basin,Timor Sea

New insights into the 3D structure, composition and origin of the Mt Ashmore dome, west Bonaparte Basin, Timor Sea, are enabled by reprocessed seismic-reflection data and by optical microscopic, X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive spectrometry (EDS) and transmission electron microscopy (TEM) analyses of drill cuttings. The structural dome, located below a major pre-Oligocene post-Late Eocene unconformity and above a ～6 km-deep-seated basement high indicated by marked gravity and magnetic anomalies, displays chaotic deformation at its core and a centripetal kinematic deformation pattern. A study of drill cuttings of Lower Oligocene to Lower Jurassic sedimentary rocks intersected by the Mt Ashmore 1B petroleum-exploration well reveals microbrecciation and extreme comminution and flow-textured fluidisation of altered sedimentary material. The microbreccia is dominated by aggregates of poorly diffracting micrometre to tens of micrometres-scale to sub-millimetre particles, including relic subplanar fractured quartz grains, carbonate, barite, apatite and K-feldspar. A similar assemblage occurs in fragments in basal Oligocene sediments, probably derived from the eroded top section of the dome, which protrudes above the unconformity. SEM coupled with EDS show the micrometre to tens of micrometres-scale particles are characterised by very low totals and non-stoichiometric compositions, including particles dominated by Si, Al–Si, Si–Ca–Al, Si–Al–Ca, Si–Mg, Fe–Mg–Ca, Fe–Mg and carbonate. XRD analysis identifies a high proportion of amorphous poorly diffracting material. TEM indicates internally heterogeneous, fragmented and recrystallised structure of the amorphous grains, which accounts for the low totals in terms of the high-volatile and porous nature of the particles. Another factor for the low totals is the uneven thin-section surfaces which affect the totals. No volcanic material or evaporites were encountered in the drillcore, militating against interpretations of the structure in terms of magmatic intrusion or salt diapirism. Such models are also inconsistent with the strong gravity and magnetic anomalies, which signify a basement high below the dome. An interpretation of the dome in terms of a central rebound uplift of an impact structure can not be proven due to the lack of shock metamorphic effects such as planar deformation features, impact melt or coesite. However, an impact model is consistent with the chaotic structure of the domal core, centripetal sense of deformation, microbrecciation, comminution and fluidisation of the Triassic to Eocene rocks. In this respect, an analogy can be drawn between the Mt Ashmore structural dome and likely but unproven impact structures formed in volatile (H₂O, CO₂)-rich sediments where shock is attenuated by high volatile pressure, such as Upheaval Dome, Utah. In terms of an impact hypothesis the Mt Ashmore dome is contemporaneous with a Late Eocene impact cluster (Popigai: D = 100 km, 35.7 ± 0.2 Ma; Chesapeake Bay: D = 85 km, 35.3 ± 0.1 Ma).     

Holocene cool‐water carbonate and terrigenous sediments from southern Spencer Gulf,South Australia

Holocene sediments from southern Spencer Gulf are cool‐water carbonate‐rich gravels and sands, dominated by molluscs and Bryozoa. Five sedimentary fades are recognized: (i) molluscan gravel; (ii) branching coralline‐algal gravel, associated with shallow partially protected environments; (iii) molluscan‐biyozoan sand; (iv) mixed bioclastic sand, representative of the deeper central region of the lower gulf; and (v) bryozoan gravel, an isolated fades developed in a semi‐protected micro‐environment. The southern gulf is characterized by complex oceanographic conditions together with variations in water depth and substrate. The sediments share the characteristics of both the southern shelf and upper Spencer Gulf. Grain‐size distribution and sedimentary facies are controlled by a combination of all the above processes. Past sea level fluctuations are recognized from sea floor strand‐line deposits. The relic component of the palimpsest sediments has eroded from the Pleistocene aeolianite dunes. The sediments, therefore, reflect both the modern marine and past environments.     

Neogene basin development around Söke-Kuşadası (western Anatolia) and its bearing on tectonic development of the Aegean region

The AMS study has been performed on various types of the basement – Variscan granitic and surrounding – Mesozoic sedimentary rocks in the Velká Fatra Mountains, Tatric Superunit of the Central Western Carpathians. The Velká Fatra Mts. provides good opportunity for AMS study because of composite S-type and I-type granite character of pluton and clear relations to Mesozoic sedimentary rocks in the cover and nappe positions. The granitic massif consists of the three types of weakly magnetic peraluminous granites (350 – 340 Ma in age), ranging from two-mica granites to biotite granodiorites in composition and carrying accessory monazite and ilmenite; whereby they resemble common S-type and/or Ilmenite Series granite. This pre-existing granitic body was intruded by relatively young (304 Ma old) metaluminous to subaluminous, strongly magnetic (due to magnetite) tonalitic intrusion of the I-type and/or Magnetite Series granite. In all S-types investigated as well as in the I-type tonalite body, the magnetic fabrics are not uniform, but slightly variable within a body and differing from body to body. The magnetic fabrics in all granitic rocks can be classified as mostly magmatic in origin, only subordinately affected by ductile deformation. The Alpine overprint of the magnetic fabric of the Variscan granite frequent in the central areas of the Central Western Carpathians was only weak in the Velká Fatra Mts. and the magnetic fabrics of these granites thus mostly comprise the original Variscan magmatic fabrics. On the other hand, in the marginal parts of the Velká Fatra Mts. the magnetic fabrics in granites are locally conformable to the deformational magnetic fabrics in surrounding sedimentary rocks (Mesozoic in age) thus indicating at least local effects of the Alpine deformation. The magnetic fabrics in Mesozoic sedimentary rocks covering the crystalline basement are partially (Cover Formation) to entirely (Nappe Units) deformational in origin.     

Meso‐scale particle modeling of concrete deterioration caused by alkali‐aggregate reaction

A meso‐scale particle model is presented to simulate the expansion of concrete subjected to alkali‐aggregate reaction (AAR) and to analyze the AAR‐induced degradation of the mechanical properties. It is the first attempt to evaluate the deterioration mechanism due to AAR using the discrete‐element method. A three‐phase meso‐scale model for concrete composed of aggregates, mortar and the interface is established with the combination of a pre‐processing approach and the particle flow code, PFC2D. A homogeneous aggregate expansion approach is applied to model the AAR expansion. Uniaxial compression tests are conducted for the AAR‐affected concrete to examine the effects on the mechanical properties. Two specimens with different aggregate sizes are analyzed to consider the effects of aggregate size on AAR. The results show that the meso‐scale particle model is valid to predict the expansion and the internal micro‐cracking patterns caused by AAR. The two different specimens exhibit similar behavior. The Young's modulus and compressive strength are significantly reduced with the increase of AAR expansion. The shape of the stress–strain curves obtained from the compression tests clearly reflects the influence of internal micro‐cracks: an increased nonlinearity before the peak loading and a more gradual softening for more severely affected specimens. Similar macroscopic failure patterns of the specimens under compression are observed in terms of diagonal macroscopic cracks splitting the specimen into several triangular pieces, whereas localized micro‐cracks forming in slightly affected specimens are different from branching and diffusing cracks in severely affected ones, demonstrating different failure mechanisms. Copyright © 2012 John Wiley & Sons, Ltd.     

Quantifying Barrovian metamorphism in the Danba Structural Culmination of eastern Tibet

The Danba Structural Culmination is a tectonic window into the late Triassic to early Jurassic Songpan‐Garzê Fold Belt of eastern Tibet, which exposes an oblique section through a complete Barrovian‐type metamorphic sequence. Systematic analysis of a suite of metapelites from this locality has enabled a general study of Barrovian metamorphism, and provided new insights into the early thermotectonic history of the Tibetan plateau. The suite was used to create a detailed petrographic framework, from which four samples ranging from staurolite to sillimanite grade were selected for thermobarometry and geochronology. Pseudosection analysis was applied to calculate P–T path segments and determine peak conditions between staurolite grade at ～5.2 kbar and 580 °C and sillimanite grade at ～6.0 kbar and 670 °C. In situ U–Pb monazite geochronology reveals that staurolite‐grade conditions were reached at 191.5 ± 2.4 Ma, kyanite‐grade conditions were attained at 184.2 ± 1.5 Ma, and sillimanite‐grade conditions continued until 179.4 ± 1.6 Ma. Integration of the results has provided constraints on the evolution of metamorphism in the region, including a partial reconstruction of the regional metamorphic field gradient. Several key features of Barrovian metamorphism are documented, including nested P–T paths and a polychronic field gradient. In addition, several atypical features are noted, such as P–T path segments having similar slopes to the metamorphic field gradient, and T_max and P_max being reached simultaneously in some samples. These features are attributed to the effects of slow tectonic burial, which allows for thermal relaxation during compression. While nested, clockwise P–T–t loops provide a useful framework for Barrovian metamorphism, this study shows that the effects of slow burial can telescope this model in P–T space. Finally, the study demonstrates that eastern Tibet experienced a significant phase of crustal thickening during the Mesozoic, reinforcing the notion that the plateau may have a long history of uplift and growth.