Measurement of the Isotopic Composition of Molybdenum in Geological Samples by MC-ICP-MS using a Novel Chromatographic Extraction Technique

A novel preconcentration method is presented for the determination of Mo isotope ratios by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) in geological samples. The method is based on the separation of Mo by extraction chromatography using N-benzoyl-N-phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin (Amberlite CG-71). By optimising the procedure, Mo could be simply and effectively separated from virtually all matrix elements with a single pass through a small volume of BPHA resin (0.5 ml). This technique for separation and enrichment of Mo is characterised by high selectivity, column efficiency and recovery (~ 100%), and low total procedural blank (~ 0.18 ng). A 100Mo-97Mo double spike was mixed with samples before digestion and column separation, which enabled natural mass-dependent isotopic fractionation to be determined with a measurement reproducibility of < 0.09‰ (δ98/95Mo, 2s) by MC-ICP-MS. The mean δ98/95MoSRM 3134 (NIST SRM 3134 Mo reference material; Lot No. 891307) composition of the IAPSO seawater reference material measured in this study was 2.00 ± 0.03‰ (2s, n = 3), which is consistent with previously published values. The described procedure facilitated efficient and rapid Mo isotopic determination in various types of geological samples

Cadmium isotopic composition in the ocean

Author Posting. © Elsevier B.V., 2006. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 70 (2006): 5104-5118, doi:10.1016/j.gca.2006.07.036.The oceanic cycle of cadmium is still poorly understood, despite its importance for phytoplankton growth and paleoceanographic applications. As for other elements that are biologically recycled, variations in isotopic composition may bring unique insights. This article presents i) a protocol for the measurement of cadmium isotopic composition (Cd IC) in seawater and in phytoplankton cells; ii) the first Cd IC data in seawater, from two full depth stations, in the northwest Pacific and the northwest Mediterranean Sea; iii) the first Cd IC data in phytoplankton cells, cultured in vitro. The Cd IC variation range in seawater found at these stations is not greater than 1.5 eCd/amu units, only slightly larger than the mean uncertainty of measurement (0.8 eCd/amu). Nevertheless, systematic variations of the Cd IC and concentration in the upper 300m of the northwest Pacific suggest the occurrence of Cd isotopic fractionation by phytoplankton uptake, with a fractionation factor of 1.6±1.4 eCd/amu units. This result is supported by the culture experiment data suggesting that freshwater phytoplankton (Chlamydomonas reinhardtii and Chlorella sp.) preferentially take up light Cd isotopes, with a fractionation factor of 3.4±1.4 eCd/amu units. Systematic variations of the Cd IC and hydrographic data between 300 and 700m in the northwest Pacific have been tentatively attributed to the mixing of the mesothermal (temperature maximum) water (eCd/amu=-0.9±0.8) with the North Pacific Intermediate Water (eCd/amu=0.5±0.8). In contrast, no significant Cd IC variation is found in the northwest Mediterranean Sea. This observation was attributed to the small surface Cd depletion by phytoplankton uptake and the similar Cd IC of the different water masses found at this site. Overall, these data suggest that i) phytoplankton uptake fractionates Cd isotopic composition to a measurable degree (fractionation factors of 1.6 and 3.4 eCd/amu units, for the in situ and culture experiment data, respectively), ii) an open ocean profile of Cd IC shows upper water column variations consistent with preferential uptake and regeneration of light Cd isotopes, and iii) different water masses may have different Cd IC. This isotopic system could therefore provide information on phytoplankton Cd uptake and on water mass trajectories and mixing in some areas of the ocean. However, the very small Cd IC variations found in this study indicate that applications of Cd isotopic composition to reveal aspects of the present or past Cd oceanic cycle will be very challenging and may require further analytical improvements. Better precision could possibly be obtained with larger seawater samples, a better chemical separation of tin and a more accurate mass bias correction through the use of the double spiking technique

Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment

Paired dissolved and particulate phase Cu isotope distributions in the South Atlantic

© 2018 The Authors Copper (Cu) is both an essential micronutrient and toxic to photosynthesizing microorganisms at low concentrations. Its dissolved vertical distribution in the oceans is unusual, being neither a nutrient-type nor scavenged-type element. This distribution is attributed to biological uptake in the surface ocean with remineralisation at depth, combined with strong organic complexation by dissolved ligands, scavenging onto particles, and benthic sedimentary input. We present coupled dissolved and particulate phase Cu isotope data along the UK-GEOTRACES South Atlantic section, alongside higher resolution dissolved and particulate phase Cu concentration measurements. Our dissolved phase isotope data contribute to an emerging picture of homogeneous deep ocean δ65Cu, at about +0.65‰ (relative to NIST SRM 976). We identify two pools of Cu in the particulate phase: a refractory, lithogenic pool, at about 0‰, and a labile pool accessed via a weak acidic leach, at about +0.4‰. These two pools are comparable to those previously observed in sediments. We observe deviations towards lighter δ65Cu values in the dissolved phase associated with local enrichments in particulate Cu concentrations along the continental slopes, and in the surface ocean. Copper isotopes are thus a sensitive indicator of localised particle-associated benthic or estuarine Cu inputs. The measurement of Cu isotopes in seawater is analytically challenging, and we call for an intercalibration exercise to better evaluate the potential impacts of UV-irradiation, storage time, and different analytical procedures

Anoxic development of sapropel S1 in the Nile Fan inferred from redox sensitive proxies, Fe speciation, Fe and Mo isotopes

Redox conditions and the mechanisms of redox development are a critical aspect of Eastern Mediterranean sapropels, whose formation in oxygen-depleted waters is closely related to water column stratification at times of global sea level rise and insolation maxima. Sapropels in the Nile Fan formed at relatively shallow water depths under the influence of the monsoon-driven freshwater output from the River Nile. This work evaluates the redox evolution of Holocene sapropel S1 in VALPAMED cruise core MD9509, recovered at 880 mbsl in the NE Nile Fan, using a combination of geochemical element proxies, Fe speciation, Fe and Mo isotopes studies. The productivity and redox proxies (Ba/Al, Mo/Al, U/Al, V/Al, Sb/Al) show well-defined enrichments in the sapropel, but with a marked minimum at ca 8.2 ka indicative of reventilation corresponding to a well known global cooling event. Peak productivity and reducing signals occur close to the initiation of sapropel formation. The proxy signals in sapropel 9509 are stronger and of longer duration than those of a second sapropel S1, recovered at the same depth, but 380 km to the north (MD9501), supporting the notion (suggested in previous studies) of more reduced conditions in the Nile Fan. The MoEF vs. UEF enrichment factor variations in core 9509 infer a transition from open marine suboxic conditions in the enclosing non-sapropel sediments to anoxic non-sulphidic water column conditions in the sapropel. Correspondingly, the highly reactive Fe pool (FeHR) measured in Fe speciation studies is dominated by Fe(oxyhydr) oxide minerals in the background sediments, whereas pyrite (Fepy) becomes the dominant component of the FeHR pool in the sapropel. Maximum Fepy values in the sapropel coincide with peak productivity and reducing conditions, implying a clear link between trace element uptake, diagenetic bacterial sulphate reduction in anoxic porewater and Fe mobilization in the sapropel. Iron isotope compositions (δ56Fe) in the sapropel do not show any departure from primary (marine and detrital) source sediment values, and the absence of an Fe/Al vs. δ56Fe trend strongly argues against an Fe shuttle. Molybdenum isotopes, however, show marked non-conservative fractionation patterns. Background sediment δ98/95Mo values (0.2 to 0.7‰) are compatible with fractionation upon absorptive uptake by Fe (oxyhydr)oxides and pyrite. In contrast, minimum δ98/95Mo values exhibited at peak sapropel (reducing and pyrite producing) conditions are most closely modeled by Mo isotope fractionation during kinetically controlled conversion of aqueous molybdate to thiomolybdate species. The conservative Fe isotope behavior/Mo isotope fractionation minima in the sapropel may be a characteristic of organic-rich sediment diagenesis below an anoxic non-sulphidic water body, without the operation of a benthic Fe shuttle

Hedging lookback and partial lookback options using Malliavin calculus

The paper considers a Black and Scholes economy with constant coefficients. A contingent claim is said to be simple if the payoff at maturity is a function of the value of the underlying security at maturity. To replicate a simple contingent claim one uses so called delta-hedging, and the well-known strategy is derived from Itô calculus and the theory of partial differentiable equations. However, hedging path-dependent options require other tools since the price processes, in general, no longer have smooth stochastic differentials. It is shown how Malliavin calculus can be used to derive the hedging strategy for any kind of path-dependent options, and in particular for lookback and partial lookback options