Cd Isotopic Compositions Research Articles

Precise determination of cadmium isotope fractionation in seawater by double spike MC-ICPMS

A new technique has been developed for the accurate and precise determination of the stable Cd isotope composition of seawater. The method utilizes a 110Cd– 111Cd double spike, and it involves separation of Cd from seawater by column chromatography and isotopic analyses by multiple collector inductively coupled plasma mass spectrometry. As a by-product, it also generates precise Cd concentration data. Repeated analyses of three pure Cd reference materials and three seawater samples yielded reproducibilities of about ±1.0 to ±1.6 ε 114/110Cd (2 SD), based on measurements that each consumed about ∼8 ng of natural Cd ( ε 114/110Cd is the deviation of the 114Cd/ 110Cd isotope ratio of a sample from the standard in parts per 10,000). This demonstrates that the new double spike technique is superior to published methods of Cd isotope analyses, with regard to the acquisition of precise data for samples of limited size. Additional experiments showed that as little as 1–5 ng of seawater Cd could be analyzed with a precision of about ±2 to ±6 ε 114/110Cd (2 SD). The accuracy of the seawater isotope data was ascertained by experiments in which a Cd-free seawater matrix was doped with small quantities of isotopically well-characterized Cd. Repeated mass scans that were carried out on purified Cd fractions of several samples furthermore demonstrated the absence of significant spectral interferences. The isotope data that were acquired for the three seawater samples reveal, for the first time, small but resolvable Cd isotope fractionations in the marine environment. Cadmium-rich intermediate water from the North Pacific was found to have an isotope composition of ε 114/110Cd = 3.2 ± 1.0. In contrast, Cd-depleted seawater from the upper water column of the Atlantic and Arctic Oceans displayed isotope compositions of ε 114/110Cd = 6.4 ± 1.1 and 6.6 ± 1.6, respectively. These observations are in accord with the interpretation that the isotope effects are due to the biological fractionation that occurs during the uptake of dissolved seawater Cd by phytoplankton.

Cadmium isotopic composition in the ocean

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 ε Cd/amu units, only slightly larger than the mean uncertainty of measurement (0.8 ε Cd/amu). Nevertheless, systematic variations of the Cd IC and concentration in the upper 300 m of the northwest Pacific suggest the occurrence of Cd isotopic fractionation by phytoplankton uptake, with a fractionation factor of 1.6 ± 1.4 ε Cd/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 ε Cd/amu units. Systematic variations of the Cd IC and hydrographic data between 300 and 700 m in the northwest Pacific have been tentatively attributed to the mixing of the mesothermal (temperature maximum) water ( ε Cd/amu = −0.9 ± 0.8) with the North Pacific Intermediate Water ( ε Cd/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 ε Cd/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.

Isotope fractionation of cadmium in lunar material

The double spike technique has been used to measure the isotope fractionation and elemental abundance of Cd in nine lunar samples, the Brownfield meteorite and the Columbia River Basalt BCR-1, by thermal ionisation mass spectrometry. Lunar soil samples give a tightly grouped set of positive isotope fractionation values of between + 0.42% and + 0.50% per mass unit. Positive isotope fractionation implies that the heavy isotopes are enhanced with respect to those of the Laboratory Standard. A vesicular mare basalt gave zero isotope fractionation, indicating that the Cd isotopic composition of the Moon is identical to that of the Earth. A sample of orange glass from the Taurus-Littrow region gave a negative isotope fractionation of − 0.23 ± 0.06% per mass unit, presumably as a result of redeposition of Cd from the Cd-rich vapour cloud associated with volcanism. Cadmium is by far the heaviest element to show isotope fractionation effects in lunar samples. The volatile nature of Cd is of importance in explaining these isotope fractionation results. Although a number of mechanisms have been postulated to be the cause of isotope fractionation of certain elements in lunar soils, we believe that the most likely mechanisms are ion and particle bombardment of the lunar surface.

Determination of the mass-dependence of cadmium isotope fractionation during evaporation

Mass fractionation laws relate the fractionation factor α A for one isotope ratio to the fractionation factor α B for a second isotope ratio of the same element, with a fractionation exponent β such that α A = α B β. The exponent β defines the mass-dependence of the mass fractionation law and thus determines the slope of a mass fractionation line in linearized three isotope space. The generalized power law (GPL) defines β as a function of a variable exponent n. The laws that aim to describe equilibrium and kinetic isotope fractionations are special cases of the GPL with n = −1 and n → 0, respectively. Large isotope fractionations (up to 10% for 106Cd/ 114Cd) were found to accompany the evaporation of molten Cd into vacuum at about 180°C. The slopes of the fractionation lines (β-values) were obtained by analyzing the Cd isotope compositions of the evaporation residues relative to the starting material with two different multiple collector-ICPMS instruments. For the most fractionated sample, the difference between the theoretical β-values, that describe kinetic and equilibrium isotope fractionation, is 10 to 20 times larger than the measurement uncertainty. A mass-dependence with n = −0.35 was determined for this sample. This result differs significantly from the value that would be expected for simple kinetic evaporation (n → 0), which is governed by the diffusion of monatomic Cd from the melt into vacuum. The observed “non-kinetic” mass-dependence probably results from partial recondensation (back reaction) of Cd vapor into the melt phase. This interpretation requires that equilibrium evaporation of Cd at about 180°C is associated with significant isotope fractionation. The present study demonstrates that the mechanism of isotope fractionation can be investigated by studying the associated mass-dependence, which can be determined by measuring the isotope ratios of a fractionated product relative to the starting material. The quantification of mass fractionation line slopes with the GPL should aid the interpretation of mass-dependent and small mass-independent isotope effects.

Stable isotope compositions of cadmium in geological materials and meteorites determined by multiple-collector ICPMS

A new technique for the precise and accurate determination of Cd stable isotope compositions has been developed and applied to geological materials and meteorites. The Cd isotope analyses are performed by multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS) using external normalization to Ag for mass bias correction. The accuracy of the new procedure was ascertained by the comparison of data for meteorites with published results acquired by thermal ionization mass spectrometry and double spiking. Some results were also confirmed by measurements using external normalization to Sb on a different MC-ICPMS instrument. A long-term reproducibility of ± 1.1 εCd/amu (2 sd) was obtained for separate dissolutions and multiple analyses of several rock and meteorite samples (εCd/amu represents the deviation of a Cd isotope ratio of a sample relative to the JMC Cd standard in parts per 10 4, normalized to a mass difference of 1 amu). As little as 5–20 ng of Cd are sufficient for the acquisition of precise and accurate data. Terrestrial rock and mineral samples display little variations in Cd isotope compositions (εCd/amu between −1 and +1.2), except for a tektite sample that was found to be enriched in the heavy Cd isotopes by +7.6 εCd/amu. The carbonaceous chondrites Orgueil, Murchison and Allende have Cd isotope ratios that are unfractionated relative to the JMC Cd standard and terrestrial rocks. The ordinary chondrites analyzed in this study and a Rumuruti chondrite display Cd isotope fractionations, ranging from −19 to +36 εCd/amu. These results suggest that substantial (inorganic) natural Cd isotope fractionations are generated only by evaporation and/or condensation processes. The lack of resolvable Cd isotope variations between the different carbonaceous chondrites, despite large differences in Cd concentrations, implies that the primary depletion of Cd in the early solar system did not involve Rayleigh evaporation. The Cd isotope fractionation in ordinary and Rumuruti chondrites is probably due to the redistribution of Cd by evaporation and condensation processes during thermal metamorphism on the parent bodies. Models that explain the enrichments of highly volatile elements in unequilibrated ordinary chondrites by primary equilibrium condensation appear to be inconsistent with the Cd isotope data.

Certification of the Cu and Cd amount contents in artificial food digest using isotope dilution inductively coupled plasma mass spectrometry for Pilot Study 13 of the Comité Consultatif pour la Quantité de Matière

The Comité Consultatif pour la Quantité de Matière (CCQM) launched the Pilot Study 13, an interlaboratory comparison between the metrological organizations worldwide on the determination of Ca, Cu and Cd in artificial food digests. These samples (available in 7% HNO 3 and with a salinity evaluated around 370 mg kg −1, including approx. 30 mg Na kg −1) were prepared by gravimetrical mixing, and thus reference values traceable to the Kg for the three elements were available eventually. This paper describes the contribution of IRMM for the certification of the Cu and the Cd amount contents. The analytical protocol developed was based on isotope dilution associated to inductively coupled plasma mass spectrometry (ID-ICP-MS). The Cu measurements required 125-fold dilution of the initial sample solution. An interference of 23Na 40Ar + on 63Cu + was identified but, since the ratio between both species was over 1000, it was successfully overcome by the calculation of a correction factor for its effect on the Cu amount content directly. Dilution of the sample was not possible for Cd only present at the low ng g −1 level. Up to 1% difference was observed on Cd isotope ratio results between measurements performed directly or after matrix separation. This is rarely shown. As similar results could be obtained either way after the necessary corrections, the direct measurements approach associated to a correction for mass discrimination effects using the CCQM-P13 sample itself (and the IUPAC table values as reference for the natural Cd isotopic composition) was preferred as it was the easiest. SI traceable values were obtained for Cu and Cd with less than 1 and 1.5% combined uncertainty, respectively (6 995±55 ( k=2) nmol kg −1 and 45.53±0.64 ( k=2) nmol kg −1). The excellent agreement between these results and the reference values (less than 0.6 and 0.08% difference) further validated the analytical protocols developed.

Identification isotopique des apports métalliques dans un port par l'analyse de moules (Sète, Hérault)

The Cu, Zn, Cd, Pb concentrations and Pb isotopic compositions are determined in mussel flesh from Sete harbour (Herault) and the Thau lagoon. The mussels were sampled in specific places near industrial piers, boat workshops, a fertiliser factory and at the harbour extremities. The spatial variations in concentrations are linked to the industrial inputs. The interest of this study is that Pb isotopic compositions in the soft parts constrain the lead sources, by comparison with industrial products and natural endmember signatures, and identify water movements in the harbour.

Isotope composition of Cd, Ca and Mg in the Brownfield chondrite.

Isotope composition of Cd, Ca and Mg in the Brownfield chondrite.