Osmium Content Research Articles

Colorimetric probe for the determination of osmium through a novel optical sensor in environmental samples

A novel optical probe has been successfully developed for the selective detection of Os(VIII) ions. This osmium-sensing platform was intricately designed by incorporating 4-(thiazol-2-yldiazenyl)benzene-1,3-diol (TDBD) as the ionophore within a plasticized PVC membrane, and tributylphosphate (TBP) serving as the plasticizer. Upon exposure to Os(VIII) ions in a 0.5 M HClO4 acid milieu, the sensing membrane undergoes a distinctive chromatic transition, shifting from a yellow to a pink hue. The preparation of the sensor and the methodology for Os(VIII) determination were meticulously refined to achieve optimal performance. Under these carefully optimized experimental conditions, the proposed optode demonstrated an impressive linear detection range spanning from 2.5 × 10−9 to 2.5 × 10−5 M for Os(VIII), alongside remarkable detection and quantification limits of 7.24 × 10−10 and 2.4 × 10−9 M, respectively. The sensor consistently delivered highly reproducible results, as evidenced by relative standard deviation (RSD) values of 1.45% and 1.30% for Os(VIII) concentrations at 7.5 × 10−7 and 2.5 × 10−6 M, respectively, underscoring its precision and reliability. Furthermore, the sensor exhibited a swift response time of 3.0 min, further emphasizing its efficiency. The incorporation of PIMs into the sensor architecture led to a remarkable eight-fold enhancement in its response compared to counterparts lacking PIMs, signifying a significant performance improvement. In assessing potential interference, an investigation into the influence of other ions on Os(III) determination revealed that the prepared sensor displayed exceptional selectivity for Os(VIII) ions, with negligible responses observed in the presence of common ions. Collectively, these experimental findings underscore the sensor's efficacy as an invaluable tool for the precise analysis of osmium content in water samples, aligning it with the rigorous standards of international scientific research.

Sr, Nd, Pb, and Os Isotope Systematics and Derivation of Mesozoic Plume-Related Basalts of Antarctica: Karoo-Maud and Kerguelen Plume Realm

The study of Re–Os isotopic systematics of the Mesozoic magmas in East Antarctica and its comparison with Sr–Nd–Pb–Os published data allowed us to reveal the main features of Antarctic magmatism associated with the activity of the Karoo–Maud (Dronning Maud Land (DML), Karoo and Ferrar provinces) and the Kerguelen (Lambert rift area) plumes. It is shown that a melt source of the 180-Ma Karoo–Maud plume could be enriched lithospheric mantle. Variations of the 187Os/188Os ratio in the range of 0.1242–0.1426 characterize almost all types of melts in the Karoo and DML provinces, including both high- and low-Ti magmas as well as high-Mg ferropicrites produced by melting of mantle pyroxenite. This observation is consistent with previous assumption that magmas derived from pyroxenite mantle at the initial stage of plume impact represented melts of deep lithospheric fragments of ancient Gondwana paleocontinent that were entrapped by plume. Thereby, mantle heterogeneity recorded in the Nd–Pb–Sr isotopic compositions of the basalts is not expressed in the systematic variations of Re–Os isotope system. The magmatic source of the basalts of the Ferrar province differs from the source of Mesozoic magmatism in the Karoo and DML provinces by great variations in the 187Os/188Os ratio: from 0.1 to 0.31, and by the lower osmium contents, with limited variations of other isotopic systems, indicating an admixture of enriched EM-II source. This is consistent with inferred subduction reworking of the mantle of the western Antarctic margin (Sushchevskaya et al., 2022). Ultramafic picritic magmas from the Lambert Glacier area are characterized by a radiogenic osmium isotopic composition: 187Os/188Os 0.1582–0.2388. Source of these magmas could be ancient depleted mantle, which later experienced mantle metasomatism due to the multiple interactions with fluid-saturated melts. Picritic melts of the paleorift zone of the Lambert Glacier are close to a magma source of the Karoo and DML provinces in terms of Sr-Nd isotopic composition, but differ in more radiogenic lead.

Osmium isotope analysis as an innovative tool for provenancing ancient iron: A systematic approach.

The innovation of iron production is often considered one of the greatest technological advances in human history. A reliable provenancing method for iron is instrumental for the reconstruction of economic, social and geo-political aspects of iron production and use in antiquity. Although the potential of osmium isotopes analysis for this purpose has been previously suggested, here we present for the first time the results of osmium isotope analysis of ores, bloom and metal obtained from a set of systematic, bloomery iron-smelting experiments, utilizing selected ores from the Southern Levant. The results show that the 187Os/188Os ratio is preserved from ore to metal, with no isotopic fractionation. In addition, enrichment/depletion of osmium content was observed in the transition from ore to metal and from ore to slag. This observation has potential significance for our ability to differentiate between the various processes and sheds light on the suitability of various production remains for this method, which emerges as a robust and promising tool for the provenancing of archaeological ferrous metals.

Re Sulfides from Zhelos and Tokty-Oi Intrusions (East Sayan, Russia)

Re sulfides were discovered in Cu–Ni–platinum-group elements (PGE) ores of the Zhelos and Tokty-Oi intrusions. These intrusions can be considered as products of the mantle superplume responsible for Rodinia’s break-up. The mineral compositions were determined in situ in polished samples. Electron microprobe analyses were mostly consistent with a general formula of (Cu,Fe,Mo,Os,Re)5S8, (Cu,Fe,Mo,Os,Re)4S7, and (Cu,Fe,Mo,Re)S2. One of the major features of Re sulfide from the Zhelos intrusion is its high osmium content. The ΣMe/S ratio for a part of our data is consistent with that of the tarkianite. Re sulfides from the Tokty-Oi have a ΣMe/S ratio similar to those in rheniite or dzeskazganite, but differ from them by the presence of Fe and Cu and the metal-to-metal ratio. The localization of the Re sulfide within the chalcopyrite suggests its crystallization from the residual Cu-rich liquid.

Refinement of the Micro‐Distillation Technique for Isotopic Analysis of Geological Samples with pg‐Level Osmium Contents

In recent years, the 187Re–187Os isotope system has been increasingly used to study samples containing very small quantities of Os. For such samples, optimisation of measurement procedures is essential to minimise the loss of Os before mass spectrometric measurements. Micro‐distillation is a necessary purification step that is applied after the main Os chemical separation procedure, prior to Os isotope ratio measurements by negative‐thermal ionisation mass spectrometry (N‐TIMS). However, unlike the other separation steps, this procedure has not yet been optimised for small samples. In this study, we present a refined micro‐distillation method that achieved higher yields and allowed high‐precision R(187Os/188Os) expressed as 187Os/188Os measurements for small‐sized geological samples that contain only a few pg Os. The Os recovery in the micro‐distillation step was tested by changing the operating conditions including heating time and temperature, and amounts of oxidant and reductant. Recoveries were measured by the isotope dilution ICP‐MS method after the addition of 190Os‐enriched spike solution. We found that the most critical factor controlling the chemical yield of Os during micro‐distillation is the extent of dilution of the reductant (HBr) by H2O evaporated from the oxidant. A refined micro‐distillation method, in which the amount of oxidant solution is reduced from the conventional method, achieved an improved chemical yield of Os (~ 90%). This refined method was applied to the measurement of 187Os/188Os by N‐TIMS of varying test portions of the geological reference material BIR‐1a. The resulting 187Os/188Os ratios of BIR‐1a matched the literature data, with propagated uncertainties of 0.2, 1.1 and 11% digested sample quantities containing 150, 10 and 1 pg of Os, respectively.

Re-Os Geochronological Evidence for Multiple Paleoproterozoic Gold Events at the Scale of the West African Craton

The Archean-Proterozoic craton of West Africa hosts numerous gold deposits, which are spatially and temporally related to the Eburnean orogeny that took place between 2250 and 1980 Ma, and included multiple deformation events. The majority of these gold deposits are located along shear zones. The structural history is relatively well established for most gold deposits, but absolute timing of the mineralization is commonly lacking. Five deposits hosted in the Baoule-Mossi domain, located in the southwestern part of the West African craton, were studied to better constrain timing of gold events: Nassara and Kiaka in Burkina Faso and Wassa, Damang, and Obuasi in southern Ghana. Gold mineralization was structurally characterized at each deposit, and dated by the Re-Os method on pyrite, arsenopyrite, and pyrrhotite grains that were coeval with the gold deposition. Combined structural and Re-Os geochronological constraints allow two groups of gold deposits to be distinguished. Early orogenic gold formed during the Eoeburnean orogeny, i.e., between 2190 and 2125 Ma, as represented by Kiaka1 at 2157 ± 24 Ma, and Wassa1 at 2164 ± 14 Ma. These early gold occurrences are expressed as early disseminated gold enrichment (1–3 g/t Au) at Kiaka, and gold hosted in folded and boudinaged quartz veins that are transposed along the primary S₁ foliation at Wassa. These Re-Os ages on the early sulfides at Wassa and Kiaka are significant because they definitively provide the first direct age constraints on gold-only Eoeburnean mineralization in the Birimian of West Africa. Late orogenic gold, hosted by brittle structures and with higher gold grades (up to 60g/t at Kiaka), formed during late Eburnean deformation (D₃–D₅ events) between 2120 and 2000 Ma, as represented by the Re-Os dating of these ores at Wassa at 2055 ± 18 Ma and Obuasi at 2045 ± 40 Ma. Similar-style ores dated at Nassara at 2131 ± 99 Ma and Damang at 2080 ± 135 Ma, but both with large uncertainties, and an undated younger event at Kiaka, are also suggested to be part of this later mineralizing episode. The high uncertainties on the Nassara and Damang ages may be directly linked to the low rhenium and osmium contents of the studied samples. These results highlight the polyphase character of the widespread gold mineralization in the West African craton. Although the late stages of the Eburnean orogeny constitute a prolific period for the formation of high-grade gold mineralization, identification of less well-studied early-stage gold deposits, which can also contain large quantities of gold, is critical for mineral exploration in the West African craton.

Estimating the Compressibility of Osmium from Recent Measurements of Ir-Os Alloys under High Pressure.

Several fcc- and hcp-structured Ir-Os alloys have been recently studied up to 30 GPa at room temperature by means of synchrotron-based X-ray powder diffraction in diamond anvil cells. Using their bulk moduli, which increase with increasing osmium content, showing a deviation from linearity, and after employing a thermodynamical model, it was concluded that the bulk modulus for osmium is slightly smaller than that for diamond. Here, a similar conclusion is obtained upon employing an alternative model, thus strengthening the conclusion that osmium is the densest but not the most incompressible element. This is particularly interesting for Earth Sciences because it may be of key importance toward clarifying the anomalous elastic properties of the Earth's core.

Compressibility of Ir–Os alloys under high pressure

Several fcc- and hcp-structured Ir–Os alloys were prepared from single-source precursors in hydrogen atmosphere at 873K. Their atomic volumes measured at ambient conditions using powder X-ray diffraction follow nearly linear dependence as a function of composition. Alloys have been studied up to 30GPa at room temperature by means of synchrotron-based X-ray powder diffraction in diamond anvil cells. Their bulk moduli increase with increasing osmium content and show a deviation from linearity. Bulk modulus of hcp-Ir0.20Os0.80 is identical to that of pure Os (411GPa) within experimental errors. Peculiarities on fcc-Ir0.80Os0.20 compressibility curve indicate possible changes of its electronic properties at ∼20GPa.

Pharmacopeial requirements for elemental impurities: a novel approach to the trace determination of osmium by oxidative pressure vessel sample digestion and measurement using inductively coupled plasma mass spectrometry (ICP-MS) after complexation and stabilisation

A novel approach for post-digestion stabilisation of osmium was developed and evaluated as a proof of concept during this study. Regulatory requirements for the testing of Os contents in pharmaceutical products are now included in the new general USP chapters 〈232〉 and 〈233〉, as well as in EP chapters 5.20 and 2.4.20. A new ICH guideline for elemental impurities Q3D is in preparation. Therefore, trace elemental analysis of Os will be required for release testing of pharmaceutical substances and final products in the near future. In this study Os determination was performed by inductively coupled plasma mass spectrometry (ICP-MS) after nitric acid pressure vessel digestion. Since osmium in an oxidising and acidic environment readily forms volatile species, there is a need for osmium stabilization to prevent the loss of these fractions or to prevent overestimation due to vapour enrichment in spray chambers used on ICP instruments. Pressure vessel digestion with nitric acid is a universal mineralisation method for organic compounds in order to determine trace elemental concentrations and will be required to meet the new pharmacopeial regulations. Therefore, it is in principle possible to cover the whole list of required elements in USP 〈232〉 to be tested in one digestion run, now including osmium, since an aliquot of the digestion solution is stabilised using the presented stabilisation solution whereas the rest of the digestion solution can be used for the determination of the other required trace element contents. In this study we demonstrated the suitability of thiourea as a complexing agent for osmium. Already millimolar quantities of thiourea in combination with ascorbic acid in acidic media allowed the stabilization of μg L−1 quantities of osmium in solution following high-pressure digestion. To meet method validation requirements, a spike recovery experiment with real world samples, the pharmaceutical excipient Avicel, was performed to evaluate this type of stabilization in combination with high-pressure digestion with concentrated nitric acid. First proof of concept experiments showed average recoveries of 81% for samples spiked with 1.0 μg g−1 osmium and a precision of 7% for six-fold preparation and measurement. Additional experiments showed that matrix-matched calibrations may be mandatory for reliable determination of osmium contents.

Masking is the Effective Alternative to the Separation during Osmium Determination by Means of Azo Dyes in Complex Samples

The selectivity of the spectrophotometric methods for determination of microgram quantities of osmium (IV) with acidic monoazo dyes Tropaeolin O (TpO) and Tropaeolin OOO-I (TpOOOI) in the presence of concomitant metals, particularly platinum group, heavy and rare earths (RE) has been studied. The tolerance ratios of interfering elements have been established. The selectivity of the interaction of TpOOOI with osmium (IV) relatively to platinum group elements (PGEs) is much better than TpO. It has been established that the influence of interfering ions can be easily eliminated by means of masking agents viz. EDTA, tartrate, citrate, pyrophosphate and fluoride, and thereby the selectivity of the methods of osmium determination with TpO and TpOOOI has been sufficiently improved. The methods have been approved during the analyses of various model solutions containing ruthenium, platinum, palladium, rhodium and iridium and the masking reagents. Also osmium content has been determined in the intermetallic alloy Nd20Os15Sі65. The standard deviations did not exceed typical values for spectrophotometric methods (RSDs < 5 %). Thus the elaborated methods with various masking agents may be used for direct determination of osmium in complex samples without any preliminary separation of osmium in the form of OsO4 as well as without the extraction of matrices elements.

A new method for analysis of osmium isotopes and concentrations in surface and subsurface water samples

We describe a new method for the determination of osmium (Os) content and 187Os/ 188Os isotopic ratio in water samples, particularly adapted to analysis of reducing waters such as groundwaters. The critical feature of the method is the improved oxidation step. We use a high pressure asher (HPA-S) to achieve oxidation of all Os species at high pressure (~ 130 bars) and high temperature (250 °C). A series of tests was performed on two groundwater samples in order to study the general behavior of Os during oxidation and to optimize the various parameters of the method. At high temperature (≥ 250 °C), using hydrogen peroxide as an oxidant, complete spike-sample equilibration and oxidation of Os species to the highest oxidation state (OsO 4) are obtained in less than 10 h. A strong contrast in oxidation behavior was observed between tests performed at high (250 °C) and low temperature (100 °C). The results for both samples indicate a difference in the oxidation kinetics between spike and sample. They also demonstrate that a non-negligible proportion of each sample is easily oxidized at low temperature whereas high temperatures are required to oxidize the rest of the sample. This last observation could provide evidence for the existence of several species of osmium in groundwater samples. Our results underscore the need for high temperatures to assure spike-sample equilibration and complete oxidation of all Os species potentially present in water. The method presented here, which is adapted to various matrices, opens the possibility of analyzing Os concentrations and isotopic compositions in groundwater and thus to better constrain the potential sources of osmium delivered to the ocean.

Cretaceous oceanic anoxic event 2 triggered by a massive magmatic episode

Oceanic anoxic events (OAEs) were episodes of widespread marine anoxia during which large amounts of organic carbon were buried on the ocean floor under oxygen-deficient bottom waters. OAE2, occurring at the Cenomanian/Turonian boundary (about 93.5 Myr ago), is the most widespread and best defined OAE of the mid-Cretaceous. Although the enhanced burial of organic matter can be explained either through increased primary productivity or enhanced preservation scenarios, the actual trigger mechanism, corresponding closely to the onset of these episodes of increased carbon sequestration, has not been clearly identified. It has been postulated that large-scale magmatic activity initially triggered OAE2 (refs 4, 5), but a direct proxy of magmatism preserved in the sedimentary record coinciding closely with the onset of OAE2 has not yet been found. Here we report seawater osmium isotope ratios in organic-rich sediments from two distant sites. We find that at both study sites the marine osmium isotope record changes abruptly just at or before the onset of OAE2. Using a simple two-component mixing equation, we calculate that over 97 per cent of the total osmium content in contemporaneous seawater at both sites is magmatic in origin, a approximately 30-50-fold increase relative to pre-OAE conditions. Furthermore, the magmatic osmium isotope signal appears slightly before the OAE2-as indicated by carbon isotope ratios-suggesting a time-lag of up to approximately 23 kyr between magmatism and the onset of significant organic carbon burial, which may reflect the reaction time of the global ocean system. Our marine osmium isotope data are indicative of a widespread magmatic pulse at the onset of OAE2, which may have triggered the subsequent deposition of large amounts of organic matter.

Osmium isotope distribution within the Palaeozoic Alexandrinka seafloor hydrothermal system in the Southern Urals, Russia

The Re–Os distribution and isotopic composition have been studied within different ore facies, host-rocks and sediments from the Alexandrinka volcanogenic hydrothermal massive sulphide deposit, Southern Urals, Russia. The osmium contents increase and the initial 187Os/ 188Os isotopic compositions decrease in the ore facial range: sulphide chimneys–stockwork zone–seafloor massive and clastic sulphides–metalliferous sediments. This range reflects variable degrees of reduced hydrothermal fluid–oxidized seawater mixing during the hydrothermal ore-forming process. The Os isotopic composition of the hydrothermal sulphide chimney ( 187Os/ 188Os = 1.3) is estimated to be a minimum value of the Devonian hydrothermal fluid, which is an intermediate between initial Os isotopic compositions of island-arc volcanics and interlayered sediments. The initial Os isotopic composition of metalliferous sediments ( 187Os/ 188Os ∼ 0.17–0.2) possibly reflects that of the Devonian seawater. The low rhenium concentrations in metalliferous sediments (about 1–2 ppb) could indicate oxic formation conditions. The Re–Os isotope data define a best-fit line corresponding to a Late Devonian age of 355 ± 15 Ma (2σ) with initial 187Os/ 188Os of 0.12 ± 0.19. This age could indicate a late Os isotope reequilibration due to ongoing hydrothermal fluid flow from the Givetian (stratigraphic age ∼ 375 Ma) until the closure of the Ural paleoocean in the Late Devonian. The Os contents are higher and Re/Os ratio is lower within Palaeozoic island-arc hosted Urals VHMS deposits compared with TAG deposit in MOR setting.

Trace Analysis of Scorodite Mineral for its Osmium and Other Metals Content

Trace Analysis of Scorodite Mineral for its Osmium and Other Metals Content

Re–Os and Pb isotope systematics in reduced fjord sediments from Saanich Inlet (Western Canada)

Re–Os and Pb–Pb isotopic analysis of reduced varved sediments cored in the deeper basin of Saanich Inlet (B.C.) are presented. From core top to 61 cm down-core, spanning approximately the last 100 yrs of sedimentation, 187Os/ 188Os ratio and Os concentration respectively increase from ∼ 0.8 to ∼ 0.9 and from 55 to 60 ppt, whereas Re concentration decreases from 3600 to 2600 ppt. Re correlates with C org ( R 2 = 0.6) throughout the entire section, whereas Os follows Re and C org trends deeper down-core, suggesting a decoupling of a Re- and Os-geochemistry during burial and/or very early diagenesis. No systematic compositional differences are observed between seasonal laminae. 204Pb-normalized lead isotope ratios increase from sediment surface down to 7 cm down-core, then decrease steadily to pre-industrial levels at ∼ 50 cm down-core. This pattern illustrates the contamination from leaded gasoline until the recent past. The measured Pb isotopic ratios point primarily toward gasoline related atmospheric lead from the USA. The osmium isotopic values measured are significantly lower than those of modern seawater-Os. In comparison with other anoxic environments, the osmium content of Saanich Inlet sediments is low, and its Os isotopic composition suggests significant inputs from unradiogenic sources (detrital and/or dissolved). Ultramafic lithologies in the watershed of the Fraser River are suspected to contribute to sedimentary inputs as well as to the input of dissolved unradiogenic osmium in the water of Saanich Inlet. The presence of some unradiogenic Os from anthropogenic contamination cannot be discounted near the core top, but since deeper, pre-anthropogenic levels also yielded unradiogenic Os results, one is led to conclude that the overall low 187Os/ 188Os ratios result from natural geochemical processes. Thus, the bulk sediment of Saanich Inlet does not appear to record 187Os/ 188Os composition of the marine end-member of the only slightly below normal salinity, fjord water. The low seawater-derived Os content of the sediment, coupled with unradiogenic Os inputs from local sources, explains the overall low isotopic values observed. As a consequence, such near-shore anoxic sediments are unlikely to record changes in the past ocean Os isotopic composition.

Osmium catalyzed asymmetric dihydroxylation of methyl trans-cinnamate in ionic liquids, followed by supercritical CO 2 product recovery

In this work, osmium-catalyzed asymmetric dihydroxylation (AD) of methyl trans-cinnamate was studied. Osmium and chiral ligand catalysts were immobilized in ionic liquid only, without any other reaction solvents, while the recovery of the product was performed by extraction with supercritical CO 2, and compared with results obtained by extractions with organic solvents such as hexane and diethyl ether. In supercritical CO 2 extraction experiments, optimal extraction pressure was found and ionic liquid chosen, so that the highest reaction yields coupled with lowest osmium content in the crude product can be achieved. Finally, recycle experiments of the same (ionic liquid + catalytic system) mixture were successfully conducted. Application of ionic liquids and supercritical CO 2 in osmium catalyzed AD allows for the isolation of the diol basically without contamination with osmium, in high yield and enantiomeric excess, and it makes possible the efficient reuse of ionic liquid solvent and the catalytic system.

Ionic liquids as a convenient new medium for the catalytic asymmetric dihydroxylation of olefins using a recoverable and reusable osmium/ligand.

The use of room-temperature ionic liquids (RTILs) in the Sharpless catalytic asymmetric dihydroxylation (AD) as a cosolvent or replacement of the tert-butanol was studied in detail by screening 11 different RTILs. The AD reaction is faster in 1-n-butyl-3-methylimidazolium hexafluorophosphate [C(4)mim][PF(6)] as a cosolvent than in the conventional system of tert-butanol/H(2)O. For the range of six substrates tested, comparable or even higher yields and enantiomeric excess (ee) were found using [C(4)mim][PF(6)] or 1-n-octyl-3-methylimidazolium hexafluorophosphate [C(8)mim][PF(6)] compared to the conventional solvent system. Due to high affinity of the catalytic osmium/quiral ligand system to the ionic liquid, the use of ionic liquid/water (biphasic) or ionic liquid/water/tert-butanol (monophasic) solvent systems provides a recoverable, reusable, robust, efficient, and simple system for the AD reaction. Using 1-hexene and [C(4)mim][PF(6)] as RTIL it was possible to reuse the catalytic system for 9 cycles with only a 5% of yield reduction from the first cycle, allowing an overall yield of 87%, TON = 1566, and with similar ee. Additionally, for each cycle, after extraction of the reaction mixture with diethyl ether, the osmium content in the organic phase (containing the AD product) and in the aqueous phase was in the range of the detection limit (<or=3%, <or=7 ppb) and 3-6% of initial amount, respectively. In contrast, the ionic liquid phase retained more than 90% of the osmium content of the previous cycle.

Kalkkop Crater, Cape Province, South Africa: Confirmation of impact origin using osmium isotope systematics

The Kalkkop structure, a circular depression with a diameter of 640 m, is situated in the Eastern Cape Province, South Africa. In 1992, a bore hole was drilled in the center of the crater to a depth of 151.8 m. To assess a possible impact origin of this structure, the abundances and isotopic ratios of osmium and rhenium were measured in breccias and in sandstones and shales derived from the basement. The basement rocks show rhenium and osmium abundances and isotopic compositions of osmium and neodymium ( 187Os 188Os = 0.61 to 0.92 and ϵ Nd = −6 to−7) that are typical for continental crust. One of the breccia samples shows a significantly elevated osmium content and a much lower ( 187Os 188Os ratio of about 0.215 (( 187Os 188Os ratio = 1.79 ). This ratio is much closer to meteoritic compositions than to crust, indicating the presence of about 0.05% of an extraterrestrial component in the breccia. This is the first time that osmium isotope systematics have been used to confirm the impact origin of a crater structure, and demonstrates their sensitivity for impact studies.

Glucose electrodes based on cross-linked [Os(bpy)2Cl]+/2+ complexed poly(1-vinylimidazole) films.

Enzyme electrodes based on a redox hydrogel formed upon complexing water-soluble poly(1-vinylimidazole) (PVI) with [Os(bpy)2Cl]+ and cross-linked with water-soluble poly(ethylene glycol) diglycidyl ether (molecular weight 400, peg 400) are described. The properties of the electrodes depended on their polymers' osmium content, the extent of cross-linking, the pH, and the ionic strength in which they were used. The redox hydrogels' electron diffusion coefficients (De) increased with osmium content of their polymers. The De values were 1.5 x 10(-8), 1.3 x 10(-8), and 4.3 x 10(-9) cm2/s for PVI3-Os, PVI5-Os, and PVI10-Os, respectively, the subscripts indicating the number of monomer units per osmium redox center. De decreased with increasing ionic strength and increased upon protonation of the polymer. In glucose electrodes, made by incorporating into their films glucose oxidase (GOX) through covalent bonding in the cross-linking step, glucose was electrooxidized at > 150 mV (SCE). The characteristics of these electrodes depended on the GOX concentration, film thickness, O2 concentration, pH, NaCl concentration, and electrode potential. The steady-state glucose electrooxidation currents were independent of the polymers' osmium content in the studied (3-10 monomer units per osmium center) range. Electrodes containing 39% GOX reached steady-state glucose electrooxidation current densities of 400 microA/cm2 and, when made with thick gel films, were selective for glucose in the presence of physiological concentrations of ascorbate and acetaminophen.

Thermodynamics and kinetics of heterogeneous electron transfer at glassy carbon/osmium-containing metallopolymer interfaces

The standard rate constant (k0) and transfer coefficient (α), characterising the heterogeneous electron-transfer reaction, have been evaluated for glassy carbon electrodes modified with [Os(bipy)2(PVP)nCl]Cl (bipy = 2,2′-bipyridine, PVP = poly(4-vinylpyridine), 25 n 5) using sampled current voltammetry. The effect of variations in osmium content within the film, electrolyte concentration and temperature on these parameters is examined in hydrochloric and perchloric acid. The relevant enthalpies (ΔH0#)real, (ΔH0#)ideal and entropies (ΔS0#)real, (ΔS0#)ideal, as well as, the reaction entropy of activation (ΔS0rc) for the heterogeneous electron-transfer reactions at the electrode/metallopolymer interface have been evaluated. The influence of the immobilised film on doublelayer formation and heterogeneous kinetics is discussed and the results correlated with homogeneous charge-transport data. The results obtained suggest that the changes in the supporting electrolyte and redox site loading influence the physico-chemical properties of the polymer phase rather than the local microenvironment of the redox centre.