The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

Bromine cycle in subduction zones through in situ Br monitoring in diamond anvil cells

The geochemical partitioning of bromine between hydrous haplogranitic melts, initially enriched with respect to Br and aqueous fluids, has been continuously monitored in situ during decompression. Experiments were carried out in diamond anvil cells from 890 °C to room temperature and from 1.7 GPa to room pressure, typically from high P, T conditions corresponding to total miscibility (presence of a supercritical fluid). Br contents were measured in aqueous fluids, hydrous melts and supercritical fluids. Partition coefficients of bromine were characterized at pressure and temperature between fluids, hydrous melts and/or glasses, as appropriate: D^Br_fluid/melt = (Br)_fluid/(Br)_melt, ranges from 2.18 to 9.2 ± 0.5 for conditions within the ranges 0.66-1.7 GPa, 590-890 °C; and D^Br_fluid/glass = (Br)_fluid/(Br)_glass ranges from 60 to 375 at room conditions. The results suggest that because high pressure melts and fluids are capable of accepting high concentrations of bromine, this element may be efficiently removed from the slab to the mantle source of arc magmas. We show that Br may be highly concentrated in subduction zone magmas and strongly enriched in subduction-related volcanic gases, because its mobility is strongly correlated with that of water during magma degassing. Furthermore, our experimental results suggest that a non negligible part of Br present in the subducted slab may remain in the down-going slab, being transported toward the transition zone. This indicates that the Br cycle in subduction zones is in fact divided in two related but independent parts: (1) a shallower one where recycled Br may leave the slab with a water and silica-bearing “fluid” leading to enriched arc magmas that return Br to the atmosphere. (2) A deeper cycle where Br may be recycled back to the mantle maybe to the transition zone, where it may be present in high pressure water-rich metasomatic fluids.     

Heavy metal pollution in sediments of a typical mariculture zone in South China

The heavy metal inventory and the ecological risk of the estuarine sediments in Hailing Bay, an important maricultural zone along the southern coast of China, were investigated. Results show that the surface sediments were mainly polluted by As (2.17-20.34 mg/kg), Ni (1.37-42.50mg/kg), Cu (1.21-58.84 mg/kg) and Zn (11.69-219.22 mg/kg). Furthermore, the aquafarming zone was significantly more polluted than the non-aquafarming zone, and cluster analysis suggested additional sources of heavy metal input in the aquafarming zone. As, Cr, Cu, Ni, Pb and Zn were mainly present in the non-bioavailable residual form in the surface sediments, whereas Cd was predominantly in the highly mobile acid soluble and reducible fractions. The ecological risk of the polluted sediments stemmed mainly from Cd, and from As, Cu and Pb to less degrees. The highest potential risks occurred near the aquaculture base, indicating the need to control heavy metal inputs from aquafarming activities.     

Evaluating a process‐based model for use in streambank stabilization: insights on the Bank Stability and Toe Erosion Model (BSTEM)

Streambank retreat is a complex cyclical process involving subaerial processes, fluvial erosion, seepage erosion, and geotechnical failures and is driven by several soil properties that themselves are temporally and spatially variable. Therefore, it can be extremely challenging to predict and model the erosion and consequent retreat of streambanks. However, modeling streambank retreat has many important applications, including the design and assessment of mitigation strategies for stream revitalization and stabilization. In order to highlight the current complexities of modeling streambank retreat and to suggest future research areas, this paper reviewed one of the most comprehensive streambank retreat models available, the Bank Stability and Toe Erosion Model (BSTEM), which has recently been integrated with several popular hydrodynamic and sediment transport models including the Hydrologic Engineering Center's River Analysis System (HEC‐RAS). The objectives of this paper were to: (i) comprehensively review studies that have utilized BSTEM and report their findings, (ii) address the limitations of the model so that it can be applied appropriately in its current form, and (iii) suggest directions of research that will help make the model a more useful tool in future applications. The paper includes an extensive overview of peer reviewed studies to guide future users of BSTEM. The review demonstrated that the model needs further testing and evaluation outside of the central United States. Also, further development is needed in terms of accounting for spatial and temporal variability in geotechnical and fluvial erodibility parameters, incorporating subaerial processes, and accounting for the influence of riparian vegetation on streambank pore‐water pressure dynamics, applied shear stress, and erodibility parameters. Copyright © 2016 John Wiley & Sons, Ltd.     

The effect of thermal treatment on the 57Fe Mössbauer spectrum of beryl

Mössbauer spectra (MS) of blue, green and yellow beryl (ideally Be₃Al₂Si₆O₁₈) containing approximately 1% of iron were obtained at 295 and 500 K. Room temperature (RT) spectra of both blue and green samples showed the presence of an asymmetric Fe²⁺ doublet (ΔE _Q~2.7 mm/s, δ~1.1 mm/s), with a very broad low-velocity peak. There is no clear evidence for the presence of a ferric component. The MS of the yellow sample at RT consists of an intense central absorption with parameters typical for Fe³⁺ (ΔE _Q~0.4 mm/s, δ~0.29 mm/s), plus an apparently symmetrical Fe²⁺ doublet. This sample acquires a light-blue shade upon heating in air at about 620 K. Thermal treatments at high temperatures caused no significant changes in the MS, but the green and yellow beryl acquire a blue colour. All these results are interpreted in relation to the existence of channel water and the distribution of iron among the available crystallographic sites.     

Competitive Sorption of Antimony with Zinc,Nickel, and Aluminum in a Seaweed Based Fixed‐bed Sorption Column

The removal of heavy metals such as Ni(II), Zn(II), Al(III), and Sb(III) from aqueous metal solutions was investigated using novel, cost effective, seaweed derived sorbents. Studies with a laboratory scale fixed‐bed sorption column, using a seaweed waste material (referred to as waste Ascophyllum product (WAP)) from the processing of Ascophyllum nodosum as biosorbent, demonstrated high removal efficiencies (RE) for a variety of heavy metals including Ni(II), Zn(II) and Al(III), with 90, 90 and 74% RE achieved from initial 10 mg/L metal solutions, respectively. The presence of Sb(III) in multi component metal solutions suppressed the removal of Ni(II), Zn(II) and Al(III), reducing the RE to 28, 17 and 24%, respectively. The use of Polysiphonia lanosa as a biosorbent showed a 67% RE for Sb(III), both alone and in combination with other metals. Potentiometric and conductometric titrations, X‐ray photoelectron and mid‐infrared spectroscopic analysis demonstrated that carboxyl, alcohol, sulfonate and ether groups were heavily involved in Sb(III) binding by P. lanosa. Only carboxyl and sulfonate groups were involved in Sb(III) binding by WAP. Furthermore, a greater amount of weak acidic groups (mainly carboxylic functions) were involved in Sb(III) binding by P. lanosa, compared to WAP which involved a greater concentration of strong acidic groups (mainly sulfonates).     

Multimodel analysis on the response of the AMOC under an increase of radiative forcing and its symmetrical reversal

Climate Dynamics - The response of the Atlantic meridional overturning circulation (AMOC) to an increase of radiative forcing (ramp-up) and a subsequent reversal of radiative forcing (ramp-down) is...     

Density-Stratified Flow Events in Great Salt Lake,Utah, USA: Implications for Mercury and Salinity Cycling

Density stratification in saline and hypersaline water bodies from throughout the world can have large impacts on the internal cycling and loading of salinity, nutrients, and trace elements. High temporal resolution hydroacoustic and physical/chemical data were collected at two sites in Great Salt Lake (GSL), a saline lake in the western USA, to understand how density stratification may influence salinity and mercury (Hg) distributions. The first study site was in a causeway breach where saline water from GSL exchanges with less saline water from a flow restricted bay. Near-surface-specific conductance values measured in water at the breach displayed a good relationship with both flow and wind direction. No diurnal variations in the concentration of dissolved (<0.45 μm) methylmercury (MeHg) were observed during the 24-h sampling period; however, the highest proportion of particulate Hg_total and MeHg loadings was observed during periods of elevated salinity. The second study site was located on the bottom of GSL where movement of a high-salinity water layer, referred to as the deep brine layer (DBL), is restricted to a naturally occurring 1.5-km-wide “spillway” structure. During selected time periods in April/May, 2012, wind-induced flow reversals in a railroad causeway breach, separating Gunnison and Gilbert Bays, were coupled with high-velocity flow pulses (up to 55 cm/s) in the DBL at the spillway site. These flow pulses were likely driven by a pressure response of highly saline water from Gunnison Bay flowing into the north basin of Gilbert Bay. Short-term flow reversal events measured at the railroad causeway breach have the ability to move measurable amounts of salt and Hg from Gunnison Bay into the DBL. Future disturbance to the steady state conditions currently imposed by the railroad causeway infrastructure could result in changes to the existing chemical balance between Gunnison and Gilbert Bays. Monitoring instruments were installed at six additional sites in the DBL during October 2012 to assess impacts from any future modifications to the railroad causeway.