Ir Enrichment Research Articles

Deccan volcanism's influence on Chicxulub impact signatures at the continental Cretaceous-Paleogene boundary in the Sichuan Basin, China

The Cretaceous-Paleogene (K-Pg) extinction is linked to two primary causes: the Chicxulub asteroid impact in Mexico and the Deccan Traps eruptions in India. While substantial geological evidence supporting both events has been found worldwide, to understand their potential interactions, it is crucial to study sites that preserve records of both events simultaneously. The terrestrial K-Pg boundary located in the Sichuan Basin, China (∼15,500 km from the Chicxulub Crater and ∼5,600 km from the Deccan Traps correspond to 66 Ma), preserves evidence of both the Chicxulub impact and the Deccan Traps eruptions, along with the effects of subsequent events on the earlier ones. It offers a new perspective on the K-Pg boundary. Detailed petrological examination and geochemical analyses, including platinum-group element (PGE) and black carbon concentrations, were conducted across a 2 m K-Pg boundary section. The K-Pg boundary layer (∼2.5 cm thick) is composed of very fine-grained, brick-red sandstone and exhibits significant enrichments in Ir (9.050 ppb) and Os (10.72 ppb), along with elevated black carbon (1.10 ‰), strongly indicating contributions from the impact. Intriguingly, another PGE anomaly was detected approximately 50 cm below the K-Pg boundary. The strata surrounding the K-Pg boundary display evidence of alteration by acidic and HSˉ-rich fluids. These fluids likely caused the observed downward migration of PGE within the boundary, resulting in two distinct PGE anomalies - one at the K-Pg boundary itself and another approximately 50 cm below. These fluids resulted in the overlying sandstones exhibiting minimal matrix content and bleached the underlying brick-red sandstones. Volcanic gas emissions from the Deccan Traps after the impact are a potential source for these fluids. Our findings support the hypothesis that the most voluminous Deccan eruptions had occurred close to, but not necessarily immediately after, the Chicxulub impact, potentially lasting 100–131 ka. The hiatus after the impact weakens the possibility of a direct causal link between the Deccan eruptions and the impact.

IGF-1 Combined with OPN Promotes Neuronal Axon Growth in Vitro Through the IGF-1R/Akt/mTOR Signaling Pathway in Lipid Rafts.

This study aims to investigate the effect of insulin-like growth factor 1 (IGF-1) combined with osteopontin (OPN) on the protein expression levels and growth of neuronal axons and its possible mechanism. In this study, IGF-1 combined with OPN promoted neuronal axon growth through the IGF-1R/Akt/mTOR signaling pathway in lipid rafts, and the effect was better than that of either agent alone. This effect was suppressed when given the mTOR inhibitor rapamycin or the lipid raft cholesterol extraction agent methyl-β-cyclodextrin (M-β-CD). Rapamycin could inhibit the expression of phosphorylated ribosomal S6 protein (p-S6) and phosphorylated protein kinase B (p-Akt) and limit axon growth. In addition to the above effects, M-β-CD significantly downregulated the expression of phosphorylated insulin-like growth factor 1 receptor (p-IR). To further investigate the changes in lipid rafts when stimulated by different recombinant proteins, membrane lipid rafts were isolated to observe the changes by western blot. The expression levels of insulin-like growth factor 1 receptor (IR) and P-IR in the IGF-1 combined with OPN group were the highest. When M-β-CD was administered to the lipid rafts of neurons, the enrichment of IR by IGF-1 combined with OPN was weakened, and the p-IR was decreased. Our study found that IGF-1 combined with OPN could promote axon growth by activating the IGF-1R/Akt/mTOR signaling pathway in neuronal lipid rafts.

Earth's Earliest Phaneritic Ultramafic Rocks: Mantle Slices or Crustal Cumulates?

AbstractWhen plate tectonics initiated remains uncertain, partly because many signals interpreted as diagnostic of plate tectonics can be alternatively explained via hot stagnant‐lid tectonics. One such signal involves the petrogenesis of early Archean phaneritic ultramafic rocks. In the Eoarchean Isua supracrustal belt (Greenland), some phaneritic ultramafic rocks have been dominantly interpreted as subduction‐related, tectonically‐exhumed mantle slices or cumulates. Here, we compared Eoarchean phaneritic ultramafic rocks from the Isua supracrustal belt with mantle peridotites, cumulates, and phaneritic ultramafic samples from the Paleoarchean East Pilbara Terrane (Australia), which is widely interpreted to have formed in non‐plate tectonic settings. Our findings show that Pilbara samples have cumulate and polygonal textures, melt‐enriched trace element patterns, relative enrichment of Os, Ir, and Ru versus Pt and Pd, and chromite‐spinel with variable TiO2 and Mg#, and relatively consistent Cr#. Both, new and existing data show that cumulates and mantle rocks potentially have similar whole‐rock geochemical characteristics, deformation fabrics, and alteration features. Geochemical modeling results indicate that Isua and Pilbara ultramafic rocks have interacted with low‐Pt and Pd melts generated by sequestration of Pd and Pt into sulphide and/or alloy during magmatism. Such melts cannot have interacted with a mantle wedge. Correspondingly, geochemical compositions and rock textures suggest that Isua and Pilbara ultramafic rocks are not tectonically‐exhumed mantle peridotites, but are cumulates that experienced metasomatism by fluids and co‐genetic melts. Because such rocks could have formed in either plate or non‐plate tectonic settings, they cannot be used to differentiate early Earth tectonic settings.

Surface enrichment of Ir on the IrRu alloy for efficient and stable water oxidation catalysis in acid.

Inducing the surface enrichment of active noble metal can not only help to stabilize the catalyst but also modify the catalytic performance of the catalyst through electronic and geometric effects. Herein, we report the in situ surface enrichment of Ir on IrRu alloy during the oxygen evolution reaction (OER). The surface enrichment of Ir was probed by ex situ high-resolution transmission electron microscopy (HRTEM), in situ X-ray absorption spectroscopy (XAS), and electrochemical Cu stripping, leading to complementary characterizations of the dynamic reconstruction of the IrRu alloy during OER. Guided by the density functional theory (DFT), an IrRu alloy with low Ir content (20 wt%) was constructed, which displayed a low overpotential of only 230 mV to deliver an OER current density of 10 mA cm-2 in 0.1 M HClO4 solution and maintained stable performance for over 20 h. To investigate the practical application potential, a proton exchange membrane (PEM) water electrolyzer using the IrRu alloy as the anode catalyst was assembled, which required a low cell voltage of only 1.48 V to generate a current density of 1 A cm-2.

Phase- and Surface Composition-Dependent Electrochemical Stability of Ir-Ru Nanoparticles during Oxygen Evolution Reaction

The increasing scarcity of iridium (Ir) and its rutile-type oxide (IrO2), the current state-of-the-art oxygen evolution reaction (OER) catalysts, is driving the transition toward the use of mixed Ir oxides with a highly active yet inexpensive metal (IrxM1–xO2). Ruthenium (Ru) has been commonly employed due to its high OER activity although its electrochemical stability in Ir-Ru mixed oxide nanoparticles (IrxRu1–xO2 NPs), especially at high relative contents, is rarely evaluated for long-term application as water electrolyzers. In this work, we bridge the knowledge gap by performing a thorough study on the composition- and phase-dependent stability of well-defined IrxRu1–xO2 NPs prepared by flame spray pyrolysis under dynamic operating conditions. As-prepared NPs (IrxRu1–xOy) present an amorphous coral-like structure with a hydrous Ir-Ru oxide phase, which upon post-synthetic thermal treatment fully converts to a rutile-type structure followed by a selective Ir enrichment at the NP topmost surface. It was demonstrated that Ir incorporation into a RuO2 matrix drastically reduced Ru dissolution by ca. 10-fold at the expense of worsening Ir inherent stability, regardless of the oxide phase present. Hydrous IrxRu1–xOy NPs, however, were shown to be 1000-fold less stable than rutile-type IrxRu1–xO2, where the severe Ru leaching yielded a fast convergence toward the activity of monometallic hydrous IrOy. For rutile-type IrxRu1–xO2, the sequential start-up/shut-down OER protocol employed revealed a steady-state dissolution for both Ir and Ru, as well as the key role of surface Ru species in OER activity: minimal Ru surface losses (<1 at. %) yielded OER activities for tested Ir0.2Ru0.8O2 equivalent to those of untested Ir0.8Ru0.2O2. Ir enrichment at the NP topmost surface, which mitigates selective subsurface Ru dissolution, is identified as the origin of the NP stabilization. These results suggest Ru-rich IrxRu1–xO2 NPs to be viable electrocatalysts for long-term water electrolysis, with significant repercussions in cost reduction.

Zoned Laurite from the Merensky Reef, Bushveld Complex, South Africa: “Hydrothermal” in Origin?

Laurite, ideally (Ru,Os)S2, is a common accessory mineral in podiform and stratiform chromitites and, to a lesser extent, it also occurs in placer deposits and is associated with Ni-Cu magmatic sulfides. In this paper, we report on the occurrence of zoned laurite found in the Merensky Reef of the Bushveld layered intrusion, South Africa. The zoned laurite forms relatively large crystals of up to more than 100 µm, and occurs in contact between serpentine and sulfides, such as pyrrhotite, chalcopyrite, and pentlandite, that contain small phases containing Pb and Cl. Some zoned crystals of laurite show a slight enrichment in Os in the rim, as typical of laurite that crystallized at magmatic stage, under decreasing temperature and increasing sulfur fugacity, in a thermal range of about 1300–1000 °C. However, most of the laurite from the Merensky Reef are characterized by an unusual zoning that involves local enrichment of As, Pt, Ir, and Fe. Comparison in terms of Ru-Os-Ir of the Merensky Reef zoned laurite with those found in the layered chromitites of the Bushveld and podiform chromitites reveals that they are enriched in Ir. The Merensky Reef zoned laurite also contain high amount of As (up to 9.72 wt%), Pt (up to 9.72 wt%) and Fe (up to 14.19 wt%). On the basis of its textural position, composition, and zoning, we can suggest that the zoned laurite of the Merensky Reef is “hydrothermal” in origin, having crystallized in the presence of a Cl- and As-rich hydrous solution, at temperatures much lower than those typical of the precipitation of magmatic laurite. Although, it remains to be seen whether the “hydrothermal” laurite precipitated directly from the hydrothermal fluid, or it represents the alteration product of a pre-existing laurite reacting with the hydrothermal solution.

(Invited) Electrochemical Methods for Surface Composition Determination of Alloy and Core/Shell Nanoparticles

The surface characteristics of metallic nanoparticles (NPs), especially the atomic percent and distribution of each component, is critical to their catalytic and electrocatalytic behavior. Therefore, efforts are underway to design NP catalysts with full control of their composition, both in the bulk and at the surface. In our work, Pt-Ru and Pt-Ir NPs, either in alloy or core@shell forms, are of great interest, due to their suitability for a wide range of electrocatalytic and sensing applications, such as for the oxidation of formic acid, alcohols, and ammonia, for oxygen evolution and reduction in regenerative fuel cells, in the reduction of hydrogen peroxide, and as an electron mediating matrix in glucose biosensors 1–8. In the present work, PtxIry alloys, Ircore@Ptshell, Rucore@Ptshell, and Rucore@Pt-Irshell NPs were synthesized using the simple and controllable polyol method 9. In the case of PtxIry alloy NPs, two sequential heating steps were employed to minimize the possibility of surface enrichment of Pt or Ir during NP formation. In the case of Ircore@Ptshell and Rucore@Ptshell NPs, the Ptshell, with a coverage of between 0.1 and 2 monolayers (MLs), was controllably deposited on the surface of the Ircore and Rucore NPs, while for the Rucore@Pt-Irshell NPs, one ML of the PtxIry alloy shell, containing different Pt:Ir ratios, was deposited on the Rucore. Wavelength dispersive X-ray spectroscopy (WDS) and energy dispersive X-ray spectroscopy, coupled with high-resolution transmission electron microscopy (EDS/HRTEM) and powder X-ray diffraction (PXRD), were then used to determine the bulk composition and homogeneity of the NPs. To determine the outer surface composition of these NPs, the underpotential deposition/stripping of Cu and oxalic acid oxidation have been used previously, e.g., for Pt-Ru NPs 10–12. However, the effect of NP size, Pt-Ru interactions at the surface, and the degree of Ru oxidation on the catalytic activity have not been determined. In other prior work 13, CO stripping was used to establish the stability of PtRu NPs by tracking the changes in the surface composition. In the present work, several electrochemical fingerprinting methods were developed (underpotential deposition/removal of H atoms, CO stripping, and surface oxide reduction) to determine the precise coverage and thickness (fraction of MLs) of the Ptshell on the Ircore@Ptshell and Rucore@Ptshell, NPs and the Pt:Ir ratio at the surface of the PtxIry alloy and Rucore/Pt-Irshell NPs, as well as the real surface area of the exposed metals. Figure 1 1,14,15 shows the CO stripping voltammetry of the NPs under study here as an example of how the peak potential and splitting correlate with the NP surface composition. A comparison will be given between the surface areas and compositions obtained by each of the electrochemical methods used here, as well as with what can be inferred from TEM imaging methods.

Late Eocene 3He and Ir anomalies associated with ordinary chondritic spinels

During the late Eocene there was an enigmatic enhancement in the flux of extraterrestrial material to Earth. Evidence comes from sedimentary 3He records indicating an increased flux of interplanetary dust during ca. 2Myr, as well as two very large impact structures, Popigai (100km diameter) and Chesapeake Bay (40–85km), that formed within 10–20kyr at the peak of the 3He delivery. The Massignano section in Italy has one of the best sedimentary records of these events, including a well-defined 3He record, an Ir-rich ejecta bed related to the Popigai impact event, and two smaller Ir anomalies. Recently we showed that the Popigai ejecta is associated with a significant enrichment of chromite grains (>63μm) with an H-chondritic elemental composition (17 grains in 100kg of rock). Most likely these grains are unmelted fragments from the impactor. Slightly higher up (ca. 20cm) in the section, where a small Ir anomaly possibly related to the Chesapeake Bay impact has been measured, we found a weak enrichment in L-chondritic grains (8 grains in 208kg of rock). Here we report an extended data set increasing the total amount of sediment dissolved in acid and searched for extraterrestrial chromite grains from 658 to 1168kg. In altogether 760kg of background sediment from 17 levels over 14m of strata outside the interval corresponding to the Popigai and Chesapeake Bay impacts, we only found 2 extraterrestrial chromite grains. Both grains have L-chondritic compositions and were found in a 100kg sample from the ca. 10.25m level in the section where the second of the smaller Ir anomalies has been reported. A correlation appears to exist between Ir, 3He and chromite from ordinary chondrites. We also report oxygen three-isotope measurements of the extraterrestrial chromite grains associated with the Popigai ejecta and confirm an H-chondritic composition.The new results strengthen our scenario that the upper Eocene 3He and Ir enrichments originate from the asteroid belt rather than the Oort cloud as originally proposed when the 3He anomaly was discovered. The generally low background concentrations of extraterrestrial chromite through the section speak against any major single asteroid breakup event such as in the mid-Ordovician after the break-up of the L-chondrite parent body. Instead the data reconcile with a small, possibly a factor of 2–3, increase in the flux of extraterrestrial material to Earth, but of both H- and L-chondritic composition. We also report the composition of all the 2310 terrestrial chrome spinel grains recovered, and show that their chemical composition indicates a dominantly regional ophiolitic source. Four anomalous chrome spinel grains with high Ti and V concentrations were found in the Popigai ejecta. These grains originate from Siberian Traps basalts in the Popigai crater at the time of impact.

Trace element distribution in primary sulfides and Fe–Ti oxides from the sulfide-rich pods of the Lac des Iles Pd deposits, Western Ontario, Canada: Constraints on processes controlling the composition of the ore and the use of pentlandite compositions in exploration

There is an on-going debate as to whether the Lac des Iles Pd deposits (Ontario, Canada) are of magmatic or hydrothermal origin. An aspect of the deposits that has not yet been documented is the presence of sulfide-rich pods which occur throughout the host intrusion (the Mine Block Intrusion). The ore mineralogy of the sulfide-rich pods consists of pyrrhotite, pentlandite, chalcopyrite, ±pyrite, magnetite and ilmenite. We present the trace element concentrations of pyrrhotite, pentlandite, chalcopyrite, magnetite, and ilmenite from the pods and compare these results with results from other Ni–Cu–platinum-group element (PGE) deposits. The low concentrations of Si and Ca and high concentrations of V, Ni, and Cr in magnetite are consistent with a magmatic origin of the magnetite. Variations in the V and Cr concentrations indicate that magnetite crystallized from a magmatic sulfide liquid during crystal fractionation of the sulfide liquid. The enrichments in Ni, Co, Os, Ir, Ru, and Rh and depletions in Cu, Ag, Cd, and Zn in pentlandite and pyrrhotite relative to chalcopyrite are also consistent with the formation of the pods by crystallization of a magmatic sulfide liquid. Comparison of pyrrhotite and pentlandite compositions from Lac des Iles with those from other Ni–Cu–PGE deposits shows that pyrrhotite and pentlandite derived from evolved magmas have distinct compositions relative to those derived from more primitive magmas. In addition, this comparison shows that pentlandites from PGE-dominated deposits are richer in Pd and Rh than pentlandites from Ni–Cu sulfide deposits. A plot of Pd vs Rh appears to be effective at distinguishing pentlandites of PGE-dominated deposits from those of Ni–Cu sulfide deposits and could possibly be used to adapt exploration strategies.

Distribution of iridium and associated geochemistry across the Triassic–Jurassic boundary in sections at Kuhjoch and Kendlbach, Northern Calcareous Alps, Austria

Samples from strata spanning the Triassic–Jurassic boundary at the GSSP at Kuhjoch and at Kendlbachgraben were studied by NAA, XRF and combustion analysis to determine Ir levels and associated geochemistry. The results are compared to previously determined carbon isotope stratigraphy at these sections. Ir concentrations in the limestones of the Kössen Formation at Kuhjoch are very low (<10pg/g) below the top of the formation, rising to 26pg/g, in the T-bed at the top of the Eiberg Member. The Tiefengraben Member of the Kendlbach Formation exhibits higher concentrations of Ir in general relative to the strata below. The shift to higher levels is abrupt at the base of the member, coinciding with a decrease in carbonate content. Concentrations of 60 to 80pg/g are typical through the entire thickness of the Schattwald Beds and into the gray Tiefengraben Member strata, peaking at 145pg/g. Concentrations decline to 30–40pg/g above 680cm from the formation base, coinciding with increasing carbonate content. The analyses from the Kendlbachgraben section compare well with those from Kuhjoch, with similar difference in Ir concentration between the Kössen and Kendlbach formations. In both sections, the initial increase in Ir corresponds to the initial carbon isotope excursion. Concentrations of redox-sensitive elements indicate transient reducing conditions during deposition of the uppermost Kössen Formation, but oxidizing conditions during Tiefengraben Member deposition. The Al/Ti ratio indicates more intense weathering during deposition of the lowermost 20cm of the Tiefengraben Member, but otherwise consistently humid to sub-humid climate prevailed during deposition. The primary control on Ir concentration in the sampled section is formation lithology, although there are variations within the Tiefengraben Member that are independent of carbonate content. Enrichment of Ir at the top of the T-bed is associated with a redox boundary, but the cause of other variations is undetermined.

Genesis and tectonic setting of ophiolitic chromitites from the Dehsheikh ultramafic complex (Kerman, southeastern Iran): Inferences from platinum-group elements and chromite compositions

Chromitite bodies of various sizes associated with dunite envelopes have been found in the Dehsheikh ultramafic massif, in the southeastern part of the outer Zagros ophiolite belt. The chromitites occur as layered and lenticular bodies, and show both magmatic and deformational textures, including massive, disseminated, banded and nodular types. The Dehsheikh chromitites display a variation in Cr# [100×Cr/(Cr+Al)] from 69 to 78, which is typical of high-Cr chromitites. The Al2O3 and TiO2 contents of chromites range from 10.3wt.% to 16.9wt.% and 0.12wt.% to 0.35wt.%, respectively. The Al2O3, TiO2, and FeO/MgO values calculated for parental melts of Dehsheikh chromitites are within the range of boninitic melts. Chondrite-normalized distribution patterns of platinum-group elements show relative enrichments in Ru, Ir, and Os, and depletions in Rh, Pd, and Pt that are typical of chromitites associated with ophiolites formed by high degrees of mantle partial melting. The presence of Na-rich amphibole inclusions in chromite grains, together with the mineralogical and chemical composition of the chromitites and estimates of their parental melt compositions are used to help establish the tectono-magmatic setting. It is shown that the Dehsheikh massif is an ophiolite formed in a suprasubduction zone setting. We suggest that the composition of the rocks in this section was influenced by hydrous partial melts which might be formed in the subduction zone. Variable melt/rock interaction produced melt channel networks in the dunite which allowed the parental melt of the chromitite to percolate through them. Similar characteristics have been observed in other ophiolite complexes from the outer Zagros Iranian ophiolitic belt; these are believed to be the product of magmatism in a fore-arc environment.

Using platinum-group elements and Au geochemistry to constrain the genesis of podiform chromitites and associated peridotites from the Soghan mafic–ultramafic complex, Kerman, Southeastern Iran

The podiform chromite deposit of the Soghan mafic–ultramafic complex is one of the largest chromite deposits in south-east Iran (Esfandagheh area). The Soghan complex is composed mainly of dunite, harzburgite, lherzolite, pyroxenite, chromitite, wehrlite and gabbro. Olivine, orthopyroxene, and to a lesser extent clinopyroxene with highly refractory nature, are the primary silicates found in the harzburgites and dunites. The forsterite content of olivine is slightly higher in dunites (Fo94) than those in harzburgites (Fo92) and lherzolites (Fo89). Chromian spinel mainly occurs as massive chromitite pods and as thin massive chromitite bands together with minor disseminations in dunites and harzburgites. Chromian spinels in massive chromitites show very high Cr-numbers (80–83.6), Mg-numbers (62–69) and very low TiO2 content (averaging 0.17wt.%) for which may reflect the crystallization of chromite from a boninitic magma. The Fe3+-number is very low, down to <0.04wt.%, in the chromian spinel of chromitites and associated peridotites of the Soghan complex.PGE contents are variable and range from 80 to 153pbb. Chromitites have strongly fractionated chondrite-normalized PGE patterns, which are characterized by enrichments in Os, Ir and Rh relative to Pt and Pd. Moreover, the Pd/Ir value which is an indicator of PGE fractionation ranges from <0.08 to 0.24 in chromitite of the Soghan complex. These patterns and the low PGE abundances are typical of ophiolitic chromitites and indicating a high degree of partial melting (about 20–24%) of the mantle source. Moreover, the PdN/IrN ratios in dunites are unfractionated, averaging 1.2, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru and Pd anomaly, and their PdN/IrN ratio averages 1.98 and 2.15 respectively.The mineral chemistry data and PGE geochemistry, along with the calculated parental melts in equilibrium with chromian spinel of the Soghan chromitites indicate that the Soghan complex was generated from an arc-related magma with boninitic affinity above a supra-subduction zone setting.

Iridium enrichment and poor fractionation from gold, platinum and palladium in clausthalite (PbSe), Tilkerode, eastern Harz, Germany

Enrichments in platinum-group elements were found in clausthalite, PbSe, which occurs in carbonate–hematite veins hosted in black shale of Upper Wenlockian age in the eastern Harz, Germany. Spot measurements by laser ablation–quadrupole inductively coupled plasma mass spectrometry (LA–QICPMS) show that the clausthalite has Pt contents that average 0.459 ppm and range from 0.003 to 2.83 ppm. Other noble metals quantified in the present work include Au (0.226 ppm, 0.109–0.451 ppm), Ru (0.061 ppm, 0.006–0.264 ppm), Ir (0.071 ppm, 0.010–0.185 ppm), Pd (0.046 ppm, 0.017–0.107 ppm) and Os (0.010 ppm, <0.003–0.024 ppm). Elemental ratios of Au/Ir, Pd/Ir and Pt/Ir, the average values of which are respectively 4.6, 0.8, and 4.9, suggest that Au, Pd and Pt are poorly fractionated from Ir. The resulting Ir enrichment is unusual and should reflect a particularly soluble (and stable) aqueous complex of Ir in a highly oxidizing, low-temperature, Se-rich solution.

Enrichment of Rh, Ru, Ir and Os in Cr spinels from oxidized magmas: Evidence from the Ambae volcano, Vanuatu

Experimental studies, performed under oxidized conditions ( fO 2 > QFM + 2, where QFM is quartz–fayalite–magnetite oxygen buffer), have shown that Rh, Ru, Ir and Os are strongly compatible with Cr spinel, whereas empirical studies of Cr spinels from ultramafic–mafic rocks suggest that the experimental results may overestimate the partition coefficients. We report laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of platinum-group elements (PGE), Au and Re abundances in Cr spinels from the Ambae volcano, Vanuatu ( fO 2 = QFM + 2.5), the Jimberlana layered intrusion, western Australia, and the Bushveld complex, South Africa ( fO 2 ∼ QFM). The results show that Rh and IPGEs (Iridium-group PGE; Ru, Ir, Os) partition strongly into the Cr spinels that crystallized from the oxidized Ambae lavas whereas most of the Cr spinels from the more reduced Jimberlana layered intrusion and the Bushveld complex contain no detectable PGE, Au or Re, with exception of ∼10 ppb of Ir in some Jimberlana Cr spinels. In the Ambae Cr spinels, Rh, Ru and, to lesser extent Os, are positively correlated with Fe 3+, Ni and V. The homogeneous distribution of Rh and IPGEs in LA-ICP-MS time-resolved spectra indicates that these elements are in solid solution in Cr spinels. Pt–Fe alloys occur as inclusions within the Ambae Cr spinels, which indicate that the Ambae melt was saturated with Pt. Our results show that partitioning of Rh, Ru and Ir into Cr spinels increases with increasing oxygen fugacity, which suggests that the high concentrations of these elements in the Ambae Cr spinels are due to the high oxygen fugacity of the host magma. Therefore, Cr spinels may play an important role in controlling the concentrations of Rh and IPGEs during fractional crystallization of oxidized ultramafic–mafic magmas and during partial melting of oxidized arc mantle.

Iridium in the Bering Sea and Arctic Ocean studied by neutron activation analysis

Neutron activation analysis combined with pretreatment based on anion-exchange was applied to the determination of Ir in the Bering Sea and Arctic Ocean seawaters. Separation and enrichment of Ir from seawater by a simple anion-exchange resin Bio-Rad AG1×8 was carried out prior to neutron activation. Ir concentrations in the vertically distributed Bering Sea and Arctic Ocean seawater samples were in range of 0.85–3.58 pg/l and 1.26–1.97 pg/l, respectively. The reagent blanks of the procedures were 0.42–0.60 pg Ir. It was found that Ir in the Bering Sea and in the Arctic Ocean displayed different types of vertical profiles.

Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril’sk, Russia

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril’sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into pentlandite.

Anomalous iridium enrichment at the Triassic–Jurassic boundary, Blomidon Formation, Fundy basin, Canada

We present new analyses that confirm Ir enrichment (up to 0.31 ng/g) in close proximity to the palynological Triassic-Jurassic boundary in strata near the top of the Blomidon Formation at Partridge Island, Nova Scotia. High Ir concentrations have been found in at least two samples within the uppermost 70 cm of the formation. Ratios of other PGEs and Au to Ir are generally higher by an order of magnitude than in ordinary chondrites. No impact-related materials have been identified at #is horizon in the Blomidon Formation, therefore we cannot confirm an extraterrestrial source for the anomalous Ir levels. We consider, however, the possibility that regional basaltic volcanism is a potential source for the Ir in these sediments. The elevated Ir concentrations are found in reduced, grey colored mudstones, so redox concentration is a possible explanation for the distribution of Ir in these strata.

Application of Metalfix Chelamine prior to the determination of noble metals by the inductively coupled plasma atomic emission spectrometry

Metalfix Chelamine chelating resins of two different bead sizes (150–300 and 40–80 μm) were examined and compared regarding their application for sorption of Au, Ir, Pd, Pt, Rh and Ru ions from medium of HCl, HNO 3 and mixtures of HCl and HNO 3. The quantitative enrichment of Au, Ir, Pd and Pt was established for the resin of 150–300 μm particle size and for solutions acidified with HCl and HNO 3 (3:1) up to the concentration of 0.50 mol l −1. In the case of Rh and Ru, the uptake of these metals by the resin was lower than 50%. For the elution, solutions of different reagents, i.e. HCl, HNO 3, KCN, KI, KSCN and (NH 2) 2CS, were studied with respect to the complete release of the analytes retained by the resin. In addition, influence of various base metals, i.e. Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, on the retention of the noble metals was investigated. Under the selected conditions for the retention and elution of Au, Ir, Pd and Pt, the analytical performance of the proposed pre-concentration procedure was evaluated and it was applied to the determination of these noble metals in anodic sludge sample.

Ag, Ta, Ru, and Ir enrichment in surface soil: Evidence for land pollution of heavy metal from atmospheric deposition

No observation has so far been reported that heavy metal elements from atmospheric deposition were accumulated widely in the surface soil layers. In this research, 28 soil profiles from different climate zones and agro‐ecosystems in China were studied, and obvious enrichment of Ag, Ta, Ru, and Ir in the surface soils was discovered. It indicates that pollution of heavy metals emitted into the atmosphere from industrial activities is no longer limited to soils in the vicinity of power, metallurgic, metalworking, and machine‐making industries, and they may settle down extensively on land besides cities and industrial regions.

The K–T boundary in Oman: identified using magnetic susceptibility field measurements with geochemical confirmation

Recognizing distal ejecta marker horizons and correlating these among widely separated sections is typically difficult in the absence of visually distinctive marker beds. Here we propose a magnetic susceptibility (MS) field method to locate such horizons, and explore the K–T boundary interval at Abat, Oman, as a test of the method. A distinctive pattern of high MS values was used to approximately locate the K–T boundary interval in a sequence of platform carbonates, which were then sampled in detail. Whole-rock geochemical enrichments in Ir, V, As, Ni, Co, Zn and Zr and a large negative carbon isotope anomaly confirmed the inferred boundary location. Common microspherules whose chemistry reflects the whole-rock geochemistry are associated with the boundary interval. The association suggests that the microspherules formed during or as a result of the impact. The geochemical record at the Abat locality shows two levels where Ir is high (>1 ppb) suggesting input from two impacts, separated in the section by 1.35 m. The upper level is chosen as the boundary interval based on the high Ir (1.19 ppb), δ 13C negative excursion (∼7‰), and distinctive MS pattern.