Trace Cations Research Articles

Thermodynamics and kinetics of cation partitioning between plagioclase and trachybasaltic melt in static and dynamic systems: A reassessment of the lattice strain and electrostatic energies of substitution

Most of the solidification history of magmas beneath active volcanoes takes place in chemically and physically perturbed plumbing systems where the growth of crystals is collectively governed by a range of kinetic processes related to the dynamics of crustal reservoirs and eruptive conduits. In this context, we have experimentally investigated the partitioning of major, minor, and trace cations between plagioclase and trachybasaltic melt under conventional static (no physical perturbation) and dynamic (melt stirring) crystallization regimes. Slow interface reaction kinetics are established between the advancing crystal surface and the adjacent melt, as the result of the combined control of a small degree of effective undercooling, prolonged diffusive relaxation, and convective homogenization. The kinetic aspects of plagioclase growth influence the partitioning of trace cations during transport of structural units across the crystal-melt interface, with consequent departure from macroscopic equilibrium in the system. The type and number of charge–balanced and −imbalanced configurations produced by the accommodation of trace cations into the coordination polyhedron can be thermodynamically rationalized in terms of lattice strain and electrostatic partitioning energetics. However, the overall solution energy accompanying trace cation kinetic substitutions cannot be entirely deconvoluted from major component activities in both melt and plagioclase phases. The emerging view that slow interface kinetic processes may lead to strong compositional dependence for the partition coefficient in dynamic subvolcanic environments contrasts markedly with the conventional idea that the energetics of cation partitioning are dominantly controlled by the effect of isothermal changes in the bulk system.

The Effect of Cation Contamination on the Water Transport for PEM Water Electrolysis

Large-scale hydrogen production by PEM water electrolysis (PEMWE) in the energy sector requires a deep understanding of the system behaviour in failure cases and possible recovery procedures. This includes the purification of the anolyte feed water because the contamination with ions can cause the PEMWE stack to breakdown.[1] For instance, the presence of iron trace cations or other metal cations in the feed water leads to a performance loss due to higher ohmic resistance of the cell and higher iR-free voltages.[2] [3] Moreover, cation contamination might influence the water transport in a PEMWE cell. In principle, the transfer of the water molecules to the cathode is proportional to the proton flux from the cathode to the anode. The proportionality factor is defined as water transport coefficient and is also temperature dependent.[4] In case of the mono- and multivalent cations as trace elements in the feed water, the water loading of the membrane, which is expressed by water molecules per sulfonic acid group of the membrane, λ, decreases over time and leads to successive increase in the ohmic resistance. [5] However, the influence of cation contamination on the water transport in PEMWE is poorly understood to date.In this work, we investigated the effect of cation contamination in the anode feed water on the water crossover for PEMWE. Cation contamination experiments were carried out at a constant current density by adding different concentrations such as K2SO4, Na2SO4, etc. to the anode feed water. All electrochemical measurements were carried out in an in-house test bench equipped with a single cell of 5 cm2 geometric electrode area and potentiostat with booster. A commercially available catalyst coated perfluorosulfonic acid membranes (loading of 0.3 mg cm-2 geo Pt/C and 1 mgcm-2 geo IrOx) was used. The anode and cathode compartments were kept at atmospheric pressure and cell temperature of 80°C. To determine the water crossover from anode to cathode at different current densities, the cathode exhaust was cooled in a heat exchanger and measured by a gravimetric method. [4] Firstly, a conditioning procedure was performed with purified feed water until steady cell performance was achieved. The cell performance was evaluated using polarization curves, electrochemical impedance spectroscopy (EIS) and water crossover measurements. The last two are of particular interest, because they provide information about membrane humidification. The Tafel slope and mass transport overvoltage were established from the polarization curves and high frequency resistance (HFR). We observed a significant rise of the cell voltage by adding cations to the anode water feed within few hours. The analysis of Tafel slope and EIS data also reveal an increase of ohmic and mass transport resistances. In these experiments, we were able to correlate the HFR results with the water crossover as a function of the nature of the cation and its concentrations. Our data shows that the specific water crossover per current density decreases as a consequence of cation contamination. The switch back to purified feed water allows us to monitor the dynamics of the performance recovery process obtained from EIS and water crossover measurements. Additional measurements of the polarization curves and HFR were used to distinguish between reversible and irreversible degradation processes due to the cation contamination.Altogether, we present the effect of cation contamination on the water transport processes and provide deeper insights into the mass transport and performance losses for PEMWE.

Cation exchange and leakage as dominant processes in controlling salinity and strontium in sandy and argillaceous coastal aquifer: Insights from hydrochemistry and multi-isotopes

Coastal groundwater is crucial for supporting ecosystems and meeting the water needs of coastal communities. However, over-exploitation of groundwater resources, including fresh water and deep brine, leads to groundwater depletion and exacerbates saline intrusion, posing significant challenges to sustainable development. This study focuses on the south bank of Laizhou Bay, a typical area threatened by saline intrusion due to the salt industry’s extraction of deep brine and over-exploitation of fresh groundwater. To assess the impact on salinization processes, we employed hydrochemistry and multi-isotope techniques to study strontium (Sr) distribution and salinization in coastal groundwater, unraveling their origins and explaining hydrochemical processes. The hydrochemical analysis revealed that evaporite dissolution primarily contributes to salinity, especially in deep brine and saline water (TDS > 30 g/L). The relationship between 87Sr/86Sr and chlor-alkali index (CAI) and saturation index (SI) indicated distinct sources of Sr. In fresh and brackish water (<10 g/L), Sr originates from mineral weathering and dissolution (SIs of albite and calcite increase with salinity), while in deep brine and saline water, Sr is influenced by cation exchange (with CAI-Ⅰ and CAI-Ⅱ greater than 0). Additionally, the interplay of anthropogenic input (nitrate), Sr, and EC highlights the differential anthropogenic impact on shallow groundwater, emphasizing the relatively closed environment of deep brine. Multi-isotope analysis showed that the average 87Sr/86Sr of shallow groundwater samples in the cone depression is 0.7112, between that of upstream surface water and shallow groundwater (0.7119) and deep brine and saline water (0.7101), indicating groundwater extraction induces deep brine leakage into shallow groundwater, elevating salinity and Sr concentrations. This poses a direct threat to local water security, including irrigation suitability and health risks of drinking water.In conclusion, we categorized the relationships between 87Sr/86Sr and Sr under different hydrochemical processes into different end-members based on their origins. This offers valuable insights in comparable regions for identifying groundwater salinization and saline intrusion, and the use of Sr and its isotopes can also help trace cation exchange and deep brine leakage in coastal aquifers.

Orange luminescence of α-Al2O3 related to clusters consisting of F centers and divalent cations.

The orange luminescence of α-Al2O3 under UV excitation is characterized by a 2.07-eV orange broadband emission that has not yet been elucidated. This emission is present in natural and synthetic crystals and powders, as well as in Be-treated samples. All orange-luminescent materials have low Fe concentration (mostly <1000 ppm) with traces of divalent cations, mostly Mg, or Be in Be-diffused material (dozens of ppm). Mg2+, Mn2+, and Be2+ cations substitute for trivalent Al. To accommodate the charge deficit, several defects are created, including oxygen vacancies also called F centers. Indeed, our excitation spectra revealed the presence of several different F centers (F, F+, and clustered F2, F2 +, F2 2+) in those samples. However, the thermal stability and the measured luminescence lifetimes do not match with previously reported characteristics of isolated F centers. Based on our experiments, we suggest that a complex aggregate of two F centers (F2 2+) trapped at divalent cations is a major cause of this uncommon microsecond lifetime emission, even if a variety of other defects, including Cr3+, V3+, or interstitial Al3+, are present.

Kinetic partitioning of trace cations between zoned clinopyroxene and a variably cooled-decompressed alkali basalt: Thermodynamic considerations on lattice strain and electrostatic energies of substitution

We present kinetic partitioning data for trace cations measured in zoned clinopyroxene crystals obtained from a variably cooled and decompressed olivine basalt erupted at Mt. Etna volcano in Italy. Supersaturation effects and compositional heterogeneities at the interface melt lead to the development of sector zoning, concentric zoning, and patchy zoning in clinopyroxene crystals. Apparent partition coefficients between compositionally different growth layers and adjacent melts (Di) for isovalent groups of trace elements are tested for internal consistency on the thermodynamic basis of lattice strain (ΔGstrain) and electrostatic (ΔGelec) energies of substitutions. The excess energy of partitioning (ΔGpartitioning) for trace cations in zoned crystals accounts for a kinetic incorporation control leading to large enthalpic effects through distortion of the lattice and changes in the electrostatic forces. ΔGpartitioning depends upon the complementary relationship between ΔGstrain and ΔGelec, which is the most appropriate thermodynamic description for the accommodation of rare earth elements and high field strength elements in the lattice site of zoned crystals. Polyhedral sectors, skeletal forms, and overgrowth zones have Di values settled by the number of charge-balanced and -imbalanced configurations taking place in the lattice site as a function of aluminium in tetrahedral coordination, and crystal structural changes produced by heterovalent cation substitutions. In an energetically unstable macroscopic system ruled by cooling and decompression, thermodynamic requirements for the crystallochemical control of Di encompass the attainment of local equilibrium at the crystal-melt interface via the establishment of small-volume reaction kinetics. The requisite of local interface equilibrium is however susceptible to the anisotropic growth velocity of each specific clinopyroxene surface, thereby giving reason to different energetic properties of the crystallographic site. This axiomatic control requires that transition metal cations partition also in consideration of electronic effects related to the crystal field stabilization energy. The overriding implication is that Di values for trace cations having different size, charge, and electronic configuration serve as sensitive probes of the different crystal growth mechanisms, surface incorporation sites, and arrangements of atoms at the lattice-scale. In this perspective, fractional crystallization modeling of 2011–2013 bulk rock data from lava fountains indicates that the compositional evolution of magmas erupted at Mt. Etna cannot be described by a unique equilibrium value of Di for a given clinopyroxene-melt interface. The leverage of interface kinetics is distinctively dominant along the subvolcanic plumbing system, thereby requiring that values of Di differ for structurally and compositionally distinct zones in clinopyroxene phenocrysts. To successfully interpret the trace element signature of Etnean magmas, the archetypal constancy of partition coefficient at bulk thermodynamic equilibrium must be in some measure reappraised in favor of the establishment of a local interface equilibrium upon highly dynamic crystallization and growth conditions.

Effects of alternate wetting and drying on oxyanion-forming and cationic trace elements in rice paddy soils: impacts on arsenic, cadmium, and micronutrients in rice.

Rice is a global dietary staple and its traditional cultivation under flooded soil conditions leads to accumulation of arsenic (As) in rice grains. Alternate wetting and drying (AWD) is a widely advocated water management practice to achieve lower As concentrations in rice, water savings, and decreased methane emissions. It is not yet clear whether AWD leads to tradeoffs between concentrations of As and micronutrient elements (e.g., zinc, manganese, molybdenum) in rice grain. We analyzed pore water chemistry and rice grain composition data from a field experiment conducted in Arkansas, USA, in 2017 and 2018 to test the hypothesis that AWD will have diverging effects on oxyanion-forming (arsenic, molybdenum) vs. cationic (cadmium, zinc, manganese, copper) trace elements. This was hypothesized to occur via decreases in soil pH and/or precipitation of iron oxide minerals during oxidizing conditions under AWD. Solubility of all trace elements, except zinc, increased in more reducing conditions. Consistent with our hypothesis, AWD tended to increase grain concentrations of cationic elements while decreasing grain concentrations of oxyanionic elements. Decreases in total As in rice grains under AWD were mainly driven by changes in dimethylarsinic concentrations, with negligible changes in inorganic As. Linear mixed-effects modeling showed that effects of AWD on grain composition were more significant in 2017 compared to 2018. These differences may be related to the timing of dry-downs in the developmental stage of rice plants, with dry-downs during the heading stage of rice development leading to larger impacts on grain composition of certain elements. We also observed significant interannual variability in grain elemental composition from continuously-flooded fields and postulate the warmer temperatures in 2018 may have played a role in these differences.

Preparation and characterization of chemically cross-linked zwitterionic copolymer hydrogel for direct dye and toxic trace metal removal from aqueous medium

In this work, a zwitterionic copolymer hydrogel with adsorption affinity toward anionic dye and cationic trace metal was prepared by a free radical copolymerization of cationic ([3-(methacryloylamino)propyl] trimethylammonium chloride (MPTC)) and anionic (sodium 4-vinylbenzenesulfonate (SVBS)) monomers. Bis[2-(methacryloyloxy)ethyl] phosphate was used as a cross-linker and its effect on the adsorption properties of the prepared hydrogel was evaluated. The prepared materials were characterized by FTIR, XRD, SEM, EDX, and N2 adsorption at 77 K analysis. FTIR and EDX analysis demonstrated the successful preparation of poly(MPTC-co-VBS). XRD and SEM analysis showed that the poly (MPTC-co-VBS) is amorphous and has quasi-honeycomb morphology with large pores. Increasing the amount of the cross-linker enhanced the adsorption of direct blue 71 dye (DB71) and Pb(II) ions. The highest removal of DB71 and Pb(II) was achieved after 2 h using 1.5 g/L of poly(MPTC-co-VBS); however, the optimum solution pH was 3 for DB71 and 5 for Pb(II). The kinetics and isotherm studies illustrated that the surface of poly(MPTC-co-VBS) is heterogenous with small-sized homogenous pitches and the DB71 and Pb(II) adsorption onto poly(MPTC-co-VBS) is favorable. Finally, poly(MPTC-co-VBS) is more efficient in removing DB71 and Pb(II) from aqueous solutions than many other reported adsorbents.

Colloids in Thermokarst Lakes along a Permafrost and Climate Gradient of Permafrost Peatlands in Western Siberia Using In Situ Dialysis Procedure

Thermokarst lakes in the Western Siberian Lowland (WSL) are major environmental factors controlling organic carbon and trace metal storage in inland waters and greenhouse gas emissions to the atmosphere. In contrast to previously published research devoted to lake hydrochemistry, hydrobiology, sedimentary carbon, and processes controlling the lake total dissolved (&lt;0.45 μm) solute composition, the colloidal forms of organic carbon (ОC), and related elements remain poorly known, especially across the permafrost gradient in this environmentally important region. Here we sampled 38 thermokarst lakes in the WSL, from the continuous to the permafrost-free zone, and we assessed both the total (&lt;0.45 μm) and low-molecular-weight (&lt;1 kDa) concentrations of 50 major and trace elements using conventional filtration and in situ dialysis. We aimed at quantifying the relationships between the colloidal content of an element and the lake surface area, permafrost coverage (absent, sporadic, isolated, discontinuous, and continuous), pH, and the concentrations of the main colloidal constituents, such as OC, Fe, and Al. There was a positive correlation between the lake area and the contents of the colloidal fractions of DOC, Ni, rare earth elements (REE), and Hf, which could be due to the enhanced mobilization of OC, trace metals, and lithogenic elements from silicate minerals in the soil porewater within the lake watershed and peat abrasion at the lake border. In all permafrost zones, the colloidal fractions of alkalis and alkaline-earth metals decreased with an increase in lake size, probably due to a decrease in the DOC concentration in large lakes. There was an increase in the colloidal fractions of DOC, Fe, Al, trivalent and tetravalent trace cations, Mn, Co, Ni, As, V, and U from the southern, permafrost-free zone to the northern, permafrost-bearing zones. This observation could be explained by an enhanced feeding of thermokarst lakes by suprapermafrost flow and the thawing of dispersed peat ice in the northern regions. Considering the large permafrost gradient of thermokarst lakes sampled in the present study, and applying a space-for-time substitution approach, we do not anticipate sizable changes in the colloidal status of DOC or major or trace elements upon climate warming and the permafrost boundary shifting northwards. For incorporating the obtained results into global biogeochemical models of OC, metal micronutrients, and toxicant migration in the permafrost regions, one has to consider the connectivity among lakes, soil waters, and rivers. For this, measurements of lake colloids across the main hydrological seasons, notably the winter period, are necessary.

Effect of calcium and trace metals (Cd, Cu, Mn, Ni, Zn) on root iron uptake in relation to chemical properties of the root-excreted ligands.

Interferences of major cations (Ca2+, Mg2+) and trace metals (TM, i.e. Cd2+, Cu2+, Mn2+, Ni2+ and Zn2+) in root Fe uptakewere evaluated. Root Fe uptake was modelled including the reactions of the root exuded ligand with the soil major and trace cations. Fe uptake was simulated with different ligands representing various affinities for the cations, the latter varying in concentration. The stability constant of Fe complexes (KFeL) does not influence Fe uptake, contrarily to the ligand parameters for Fe-hydroxide dissolution. Fe uptake decreases when KCaL or Ca2+ in solution increases. Presence of TM has nearly no influence on Fe uptake when the TM complexes have low stability constants (KML), as in the case of oxalate and citrate complexes. When ligands have high KML, like EDTA, DFO-B or mugineic acid (MA), TM reduces Fe uptake by 51-55%, and much more in the case of TM contamination. Exudation of Fe ligands with low KML has no negative effect on TM uptake, which can increase if the dissociation rate is high, as for Cu complexes. Ligands with high KML (EDTA, DFO-B, MA) greatly reduce TM uptake, only if their hydrated cations can be absorbed. Calcium does not significantly reduce Fe uptake when Ca-complexes have KCaL < 104. Consequently, ligands like oxalate or MA should be efficient in most soils. TM should perturbate Fe uptake mediated by ligands with high KML such as MA, but not oxalate. Plants exuding phytosiderophores should also absorb TM complexes to avoid micronutrient deficiencies.

Effects of Mn or Al incorporation on the structure, composition, and As(III) adsorption of oxidized green rust

The trace cations could incorporate into the structure of oxidized green rust (Ox-GR), a layered reactive Fe(III) oxyhydroxide formed from rapid oxidation of GR, but the effects of cation incorporation on the mineralogical properties and surface reactivity of Ox-GR remain unknown. Here, we synthesized Mn- or Al-incorporated Ox-GR by oxidation of sulfate-bearing GR and determined their structure, elemental composition and distribution, and As(III) adsorption using macroscopic batch experiments and spectroscopic analyses. The presence of Mn or Al favored sulfate accumulation in Ox-GR, with some sulfate being homogeneously distributed in the interlayer, others adsorption on the mineral edge sites. Majority of Mn and Al entered the layer structure of Ox-GR as Mn(III) and Al(III) through isomorphous substitution, leading to the increased d-spacing of (001) plane but slightly decreased d-spacing of a-b planes. The Al incorporation remarkably reduced the structural ordering degree and Fe octahedral layers of Ox-GR through inhibiting the crystal-growth of GR. Compared with the Mn incorporation, the Al incorporation led to a more pronounced structural variation of Ox-GR, ascribed to its higher isomorphic substitution amount. The incorporation of Mn or Al both promoted As(III) adsorption per mineral mass, predominantly due to the increase of sulfate content and/or specific surface area, and the incorporated Mn(III) could oxidize As(III). As(III) adsorption on Ox-GR involved both surface sulfate and > Fe-OH/OH2 groups exchange, forming a bidentate-binuclear inner-sphere surface complexation. These new insights into the structure and reactivity of Ox-GR are essential to understanding environmental behavior of GR and its derivative Ox-GR in artificial and environmental settings.

Evaluation of the Water Quality Parameters in Surface Water of Iyesi Stream, Ogun State, Nigeria

The quality of surface water could have positive or negative impact on its consumption and use. This study is aimed at examining the quality of surface water of Iyesi Stream. In achieving this, sixteen (16) samples were taken at four different periods (four samples per batch) from October, 2017 to May, 2018 and analyzed for selected water quality parameters namely pH, alkalinity, BOD, COD, TDS, some anions (PO43-, NO3-, SO42-) and trace cations (Fe, Cr and Ni) according to APHA (1992) methods of analysis. The trace metals were analyzed using UNICAM AAS after sample digestion. An average pH range of 5.90±0.86 to 6.85±0.19 was recorded for the samples. SWR-2 had highest average levels of alkalinity, TH, BOD, COD, TDS, SO42-, Fe, Cr and Ni. The higher values at SWR-2 could be attributable to the fact that it is in close proximity to the effluent discharge point of the industrial estate in its environ. It was observed from this study that SWR-3 had higher nitrate and phosphate levels of 4.01±1.95mg\L and 0.19±0.04mg\L respectively. Overall, the water source is grossly organically polluted and could require suitable treatment options like coagulation with Alum or Ferric chloride.

Using groundwater in the hyper-arid Atacama Desert to discover buried hydrothermal mineral deposits

ABSTRACT Epithermal deposits occur in many metallogenic belts globally and are economically important sources of precious and base metals. However, post-mineral cover (both transported and younger deposits) also occurs in many prospective districts and hinders exploration efforts. Hydrogeochemistry is a potentially useful exploration tool in these environments, with water–rock interaction shown from other studies to produce large hydrogeochemical footprints. Groundwaters from in and around the Vaquillas (Au-Ag) epithermal deposit in the pre-cordillera of northern Chile are typically Ca-SO4 2- type with meteoric upflow groundwaters interacting with the ore body and producing a significant downflow (down hydraulic head) mobility (up to 3 km) of (oxy)anions of arsenic and molybdenum, which contrasts with proximal trace cation anomalies. Multiple sulphur endmembers contribute to the dissolved sulphate concentrations, including evaporites, primary hypogene sulphide minerals, and a single δ34S(SO4) value of 30.1 ‰ which is potentially associated with disproportionated sulphur in sulphate. This study reports anomalism from one of the most dilute endmember groundwater compositions from Chile reported to date. The sub-alkaline and weakly oxygenated groundwaters are common in many aquifers globally, making the results applicable to many other metallogenic belts. It is also the first hydrogeochemical case study of an intermediate-sulfidation epithermal deposit. Despite the highly dilute groundwaters recharging aquifers at Vaquillas, we conclude hydrogeochemistry to be a highly effective exploration tool for epithermal and porphyry deposits in areas of significant post-mineral cover.

Simultaneous removal of Pb2+ and direct red 31 dye from contaminated water using N-(2-hydroxyethyl)-2-oxo-2H-chromene-3-carboxamide loaded chitosan nanoparticles.

This study reports the preparation of a new material that can remove synthetic dyes and trace metals simultaneously. A new coumarin derivative was synthesized and its chemical structure was inferred from spectral data (FT-IR, 1H-NMR, 13C-NMR). Meanwhile, chitosan nanoparticles (CsNPs) were prepared then used as a carrier for two different concentrations of the coumarin derivative (C1@CsNPs and C2@CsNPs). The TEM, SEM and DLS findings illustrated that the prepared nanocomposites exhibited spherical shape and small size (less than 200 nm). The performance of the prepared material for the removal of an anionic dye (direct red 31, DR31) and cationic trace metal (Pb2+) was evaluated in unary and binary systems. The results revealed that complete removal of 10 mg L−1 of DR31 and Pb2+ in unary system was achieved at pHo 3.0 and 5.5 using 0.5 and 2.0 g L−1, respectively, of C2@CsNPs. The adsorption of DR31 and Pb2+ followed different mechanisms as deduced from the effect of pHo, kinetic, isotherm and binary adsorption studies. The adsorption of DR31 followed the Langmuir isotherm model and the pseudo-first-order kinetic model. While, the adsorption of Pb2+ followed Freundlich isotherm model and Elovich kinetic model. In the binary system, the co-presence of DR31 and Pb2+ did not affect the adsorption of each other's. Overall, the prepared material showed promising results for the removal of anionic dyes and cations trace metals from contaminated water.

Decoding multiple zoning patterns in clinopyroxene phenocrysts at Vulcano Island: A record of dynamic crystallization through interconnected reservoirs

Here we document how the different growth features and intracrystalline distributions of both major and trace cations in clinopyroxene phenocrysts are important recorders of the intricate magma dynamics at Vulcano Island (Aeolian Arc, Italy). The compositions of clinopyroxene phenocrysts from products erupted over the last ~54 ka cluster at different degrees of evolution, paralleling the polybaric-polythermal differentiation of mantle-derived mafic magmas into more evolved silicic melts. The hotter lower crust is the most favorable location for the storage of mafic magmas and the early crystallization of diopsidic (Mg#91) clinopyroxene (Pmax ≈ 750 MPa and Tmax ≈ 1220 °C). Diopsidic phenocrysts are depleted in both rare earth elements (REE) and high field strength elements (HFSE) but are enriched in transition elements (TE). The transfer and accumulation of primitive magmas in the colder upper crustal regions lead to the formation of an interconnected series of more differentiated magmatic reservoirs (P ≈ 100–450 MPa and T ≈ 1100–1180 °C) hosting discrete populations of clinopyroxene (Mg#84–85) with a broad spectrum of zonations and dissolution features. Recharge bands in clinopyroxene are markers of multiple inputs of primitive REE-HFSE-poor, TE-rich magmas from depth. Augitic phenocrysts (Mg#82) with strong negative Eu anomaly and REE + HFSE enrichments crystallizes from highly differentiated trachytic and rhyolitic melts stored at very shallow crustal conditions (P ≤ 50 MPa and T ≤ 1100 °C). These silicic reservoirs represent residual melts trapped-extracted from crystal-dominated mush regions in the uppermost part of the plumbing system. The residence time of clinopyroxene increases from ∼0.1 to ∼44 years from basalt to rhyolite, together with an increasing number of recharge bands. The mineral assemblage in more silicic and viscous mush melts is sufficiently resilient to record numerous mafic injections and high degrees of magma mixing, hybridization, and crystallization before eruption. Overall, the compositional zoning pattern of clinopyroxene presents a picture of plumbing system that extends through the crust and is characterized by distributions of melts and crystals which are progressively more evolved and heterogeneous in both space and time.

Kinetic partitioning of major and trace cations between clinopyroxene and phonotephritic melt under convective stirring conditions: New insights into clinopyroxene sector zoning and concentric zoning

Within subvolcanic plumbing systems, along volcanic conduits and post-eruptive emplacement, mineral textures and compositions are governed by complex kinetic (undercooling) and dynamic (convective) processes that deviate from theoretical models and equilibrium criteria. In this perspective, we have investigated the partitioning of major and trace cations between clinopyroxene and phonotephritic melt under convective stirring conditions at high degrees of undercooling (−ΔTnominal = 30–60 °C) and atmospheric pressure. We have integrated this novel data set with conventional static (no physical perturbation) clinopyroxene-melt compositions obtained under interface- and diffusion-controlled growth regimes. Results show that clinopyroxene growth kinetics and diffusion boundary layers caused by melt supersaturation are partly mitigated by the homogenizing effects of stirring. Because of continuous supply of fresh melt to the advancing crystal surface, the partitioning of major and trace cations is governed by local equilibrium effects, which are interpreted as the extension of equilibrium thermodynamic principles to non-equilibrium bulk systems. Major cations are incorporated into the clinopyroxene structure via the coupled substitution [M1Mg, TSi] ↔ [M1Ti, TAl] and in conformity with the thermodynamic mixing properties of CaMgSiO2, CaAl2SiO6, and CaTiAl2O6 components. The complementary relationship between lattice strain (ΔGstrain) and electrostatic (ΔGelectrostatic) energies of heterovalent substitutions is the most appropriate thermodynamic description for the accommodation of trace cations in the clinopyroxene lattice site (i.e., ΔGpartitioning = ΔGstrain + ΔGelectrostatic). The excess energy of partitioning ΔGpartitioning changes principally with Al in tetrahedral coordination and determines the type and number of charge-balanced and -imbalanced configurations taking place in the structural sites of clinopyroxene. An important outcome from dynamic stirring experiments is that superimposition of convective mass transfer on melt supersaturation phenomena causes the formation of Cr-rich concentric zones under closed system crystallization conditions. However, these Cr-rich zones do not correlate with enrichment in other compatible elements and depletion in incompatible elements, as would be expected in natural open systems characterized by input of more primitive magmas. While the convective transport acts to reduce the diffusive length scale of chemical species in the experimental melt, fresh Cr cations are more easily incorporated into the concentric zones due to crystal field effects. Together, our findings reveal that during magma ascent and emplacement, convective stirring may promote clinopyroxene crystallization and minimize kinetic effects on clinopyroxene zoning.

Competitive Effects of Cations on the Diffusion Properties of Strongly Sorbing Trace Cations in Compacted Illite and Opalinus Clay

Competitive Effects of Cations on the Diffusion Properties of Strongly Sorbing Trace Cations in Compacted Illite and Opalinus Clay

Using stable isotopes of Cu, Mo, S, and 87Sr/86Sr in hydrogeochemical mineral exploration as tracers of porphyry and exotic copper deposits

Groundwaters collected from the undisturbed Picaron Cu–Mo porphyry and exotic prospect (Atacama region, Chile) were analyzed for major and trace elements, along with isotopes of Cu, Mo, S, and 87Sr/86Sr. Sulfide minerals at Picaron have undergone oxidation by meteoric waters, resulting in the generation of acid and the lateral and downward migration of dissolved trace cations (Cd, Co, Cu, Ni, Pb, and Zn) and (oxy)anions (As, Mo, Sb, and Se). This paper presents a case study utilizing stable metal isotopes in hydrogeochemical mineral exploration to ascertain the possible hydrogeochemical footprints that can be detected around known mineralization. The groundwaters are weakly brackish (TDS < 3500 mg/L), reflected in relatively low trace metal concentrations. Despite this, the groundwaters reflect the dissolution of ore, as well as alteration and wall rock minerals proximal to porphyry mineralization with elevated dissolved concentrations of Ca, Mg, HCO3−, and SO42−. δ65Cu values range from 0.41 to 2.80‰, with values above 1‰ proximal to porphyry mineralization reflecting Cu fractionation during sulfide oxidation and the highest values (up to 2.80‰) proximal to exotic mineralization likely from Cu desorption. Downgradient, δ65Cu values decrease; possibility resulting from adsorption of the heavier 65Cu onto reactive surfaces or mixing with other sources. δ98Mo values proximal to porphyry mineralization (2.41 and 2.42‰) are much higher than the regional average for molybdenite reported in previous studies (0.11‰), suggesting acid neutralization and isotopic fractionation related to adsorption may be occurring close to the source. Much lower δ98Mo values downgradient (<1.0‰) are likely indicative of Mo input from surrounding country rocks. The hydrogeochemical trends observed in the Picaron groundwaters highlight the chemical processes of mineral dissolution, precipitation, and recharge pathways and indicate that the leaching of the porphyry mineralization could be the source of exotic mineralization. Ultimately, the results indicate the need for a multiple isotope approach to hydrogeochemical mineral exploration.

Fine scale measurements in Belgian coastal sediments reveal different mobilization mechanisms for cationic trace metals and oxyanions

Belgian coastal sediment serves as an important sink for trace elements, yet a systematic study covering a wide range of elements including redox-sensitive metals (Fe, Mn, and Co), cationic trace metals (Cd, Pb, Ni, Cu, and Zn), oxyanions (P, V, As, and Mo), and sulfide has not been performed and the mechanisms controlling their mobilization were not investigated. Here, a passive sampling technique, Diffusive Gradients in Thin-films (DGT), was used in situ to obtain high resolution concentration profiles of these elements in the sediment porewater. Our results revealed two mobilization mechanisms of cationic trace metals and oxyanions in Belgian coastal sediments, both strongly linked to the cycling of Fe. Mobilization of Co, Pb, Ni, and Cu is controlled by electrogenic sulfur oxidation, acidification of the porewater and dissolution of FeS, while that of oxyanions (P, V, and As) is controlled by reductive dissolution of Fe oxyhydroxides. Constant cationic trace metal to Fe molar ratios were established in FeS, while the oxyanion to Fe ratios in Fe oxyhydroxides differ significantly between sampling stations, which is primarily caused by competing effects. We found no evidence that cationic trace metal mobilization was related to Fe oxyhydroxides, or oxyanion mobilization to FeS. This suggests that particulate organic matter forms the major pathway for cationic trace metal input in coastal sediments and that oxyanions will not be incorporated in FeS but form their own oxyanion-sulfide compound. These findings will contribute to a better understanding of the mobilization mechanisms of cationic trace metals and oxyanions in coastal sediments, and of their biogeochemical cycling in coastal ecosystems.

Fundamental Aspects of Contamination during the Hydrogen Evolution/Oxidation Reaction in Alkaline Media

This work discusses the experimental pitfalls and challenges for activity benchmarking of hydrogen evolution/oxidation reactions (HER/HOR) for Pt-based catalysts in alkaline media. For identifying the source of impurities, we systematically analyzed our electrochemical set-up like cell material, hydrogen gas, and electrolyte solutions. Commonly used 0.1 M electrolyte solutions like LiOH, NaOH, and KOH were tested. We could mainly eliminate the glass cell and hydrogen gas as a main source of contamination for poly-Pt during HER/HOR in alkaline media. Long-term chronoamperometric experiments in different electrolyte solutions were applied to accumulate the impurities at the electrode surface. X-ray photoelectron spectroscopy (XPS) data enable clear identification of the observed contamination after HER/HOR. Thereby, we showed that traces of metal cations in the electrolyte solution can be electro-deposited on the electrode surface during HER and leads to strong catalyst poisoning. We have developed an electrochemical purification step to reduce these impurities stemmed from the electrolyte solution. The use of purified electrolyte solutions provides reliable and reproducible studies for HER/HOR activity benchmarking of Pt-based catalysts which is essential to underderstand HER/HOR kinetics and mechanism in alkaline media.

Reactive alteration of a Mt. Simon Sandstone due to CO2-rich brine displacement

We report a series of acidified brine flow-through experiments designed to quantify the coupled alteration of geochemical, structural and fluid transport properties of a Mt. Simon sandstone core recovered at a depth of 2110.5 m as part of the Illinois Basin Decatur Project (IBDP). Flow-through experiments were completed at representative in-situ conditions to isolate the stages of initial CO2 injection: first, a single-phase (CO2–saturated brine, Stage 1) followed by a second multi-phase (CO2–saturated brine and supercritical CO2, Stage 2) experiment. During both stages, effluent major and trace cation concentrations were tracked through time. Two imaging methods were employed to analyze the structural alterations of the rock core induced by the percolation of CO2-saturated brine and supercritical CO2: (1) scanning electron microscopy-petrography before Stage 1 and after Stage 2 and (2) computed tomography (CT) scans before and after Stage 2.The time series of Stage 1 effluent solutes were used to constrain a reactive transport simulation of the system. Modeling results suggest the evolution of the solute composition is a result of coupled dissolution of K-feldspar, calcite, illite and pyrite, and precipitation of montmorillonite, mesolite, alunite, diaspore, goethite and muscovite. The model predicted a net opening of pore space and associated increased permeability at the inlet. However, across the whole core, an overall decrease in permeability of approximately 23% ± 0.01 after Stage 1 was determined experimentally. CT analysis confirmed a corresponding decrease in porosity. A comparable permeability decrease was directly measured during Stage 2, concurrent with a decrease in the volume of macro-pores based on multiple CT-resolution methods. In total, this coupled approach demonstrates that geochemical alterations exert a first order control on the evolution of fluid transport properties through time at the earliest stages of in-situ CO2 injection and suggest that chemical dynamics ultimately influence both the magnitude and timing of alterations to the physical integrity of Mt. Simon reservoir over these timescales.