Tl Isotopes Research Articles

β-decay and β-delayed Neutron Emission Measurements at GSI-FRS Beyond [formula omitted], for r-process Nucleosynthesis

New measurements of very exotic nuclei in the neutron-rich region beyond N=126 have been performed at the GSI facility with the fragment separator (FRS). The aim of the experiment is to determine half-lives and β-delayed neutron emission branching ratios of isotopes of Hg, Tl and Pb in this region. This contribution summarizes final counting statistics for identification and for implantation, as well as the present status of the data analysis of the half-lives. In summary, isotopes of Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn and Fr were clearly identified and several of them (208-211Hg, 211-215Tl, 214-218Pb) were implanted with enough statistics to determine their half-lives. About half of them are expected to be neutron emitters, in such cases it will become possible to obtain the neutron emission probabilities, Pn.

Thallium geochemistry in the metamorphic Lengenbach sulfide deposit, Switzerland: Thallium-isotope fractionation in a sulfide melt

The Lengenbach (Switzerland) Pb-As-Tl-Zn deposit was formed from a sulfide melt at about 500 °C during Alpine metamorphism, but details on its formation and especially the source of the metals are still under debate. In this study we present two sample sets to address these questions: 1. MC-ICP-MS analyses of thallium isotopes in sulfides, sulfosalts, and melt inclusions from the Alpine metamorphic Lengenbach deposit in the Binn Valley of Switzerland, the non-metamorphic Wiesloch Mississippi Valley-type deposit in Southern Germany, and the Cu- and As-rich mineralization at Pizzo Cervandone about 2 km SW of the Lengenbach deposit, which has been discussed as potential source of the Lengenbach metals. 2. LA-ICP-MS analyses of micas from the Lengenbach deposit and surrounding country rocks between the deposit and the Pizzo Cervandone to trace potential metal-bearing fluid pathways. We found that Tl isotope compositions expressed as ɛ205Tl values in all investigated samples range from −4.1 ± 0.5 to +1.9 ± 0.5. The whole variation can be seen in the Lengenbach deposit alone, which hence records considerable fractionation even during high-temperature processes involving a sulfide melt. This large range of ɛ205Tl is thought to be caused by nuclear volume-dependent fractionation. Interestingly, the common fahlores at Lengenbach behave differently from all other investigated sulfosalts: based on their heavy isotopic composition together with a low As/S-ratio, they do not seem to be crystallized from the sulfide melt, but are interpreted to have formed from hydrothermal fluids enriched in the heavy Tl isotopes. Although As mobilization in the gneisses and dolomites surrounding the Lengenbach deposit is evident based on secondary arsenites, no traces of such a country rock fluid could be found in fissure micas at Lengenbach. Hence, considerations involving K/Rb, Rb/Tl, As/S, and Pb/Tl ratios in the sulfides and micas imply that the element enrichment in the Lengenbach deposit is either pre-Alpine or related to peak metamorphism, but occurred definitely before mica growth at Lengenbach.

The geochemistry of Tl and its isotopes during magmatic and hydrothermal processes: The peralkaline Ilimaussaq complex, southwest Greenland

We use thallium (Tl) concentrations, K/Rb, K/Tl and Rb/Tl ratios and Tl isotopes in minerals from the alkaline to peralkaline Ilimaussaq complex (South Greenland) to trace magmatic differentiation, crustal assimilation, magmatic degassing, ore precipitation and hydrothermal metasomatism. Closed-system magmatic differentiation is marked by a coherent decrease of K/Tl- and K/Rb-ratios, whereas crustal assimilation results in a strong Tl-enrichment, causing low K/Tl-ratios compared to K/Rb-ratios. Thallium isotopes show only slight changes during orthomagmatic differentiation and the assimilation of crustal material cannot be traced, since the isotopic composition of the average crust is within the range of the mantle and mantle-derived rocks. Magmatic degassing, however, increases Rb/Tl-ratios and changes the isotopic composition of Tl. The released fluids are enriched in Tl, characterized by high 205Tl/203Tl ratios and can precipitate Tl-rich sulfide and silicate minerals as indicated by some late-magmatic hydrothermal veins, which contain a conspicuous assemblage of Tl–Fe–Cu-sulfides (thalcusite, djerfisherite, chalcothallite). The oxidative alteration of these assemblages at high pH results in small-scale redistribution of Tl. Thallium released by this process is entrained into late-stage Tl-enriched astrophyllite.

Mass spectrometry and decay spectroscopy of isomers across theZ=82shell closure

Recent results from a measurement campaign studying the isomerism in neutron-deficient Tl isotopes are presented. The measurements make use of a nuclear spectroscopy setup coupled to the high-resolution Penning-trap mass spectrometer ISOLTRAP at CERN's radioactive ion-beam facility ISOLDE. The mass values of ${}^{190,194}$Tl are improved and a mass-spin-state assignment is carried out. An additional mass measurement of the grandparent nuclide ${}^{198}$At allows the deduction of the spin-state ordering in ${}^{190}$Tl. As a result, the excitation energies of the isomers in both Tl isotopes are determined for the first time to ${E}_{\mathrm{ex}}{(}^{194}\text{Tl})=260(15)$ keV and ${E}_{\mathrm{ex}}{(}^{190}\text{Tl})=89(12)$ keV. Furthermore, this allows anchoring of the ground-state and isomer masses of ${}^{194}$Bi, ${}^{202}$Fr, and ${}^{206}$Ac, which are linked by two independent $\ensuremath{\alpha}$-decay chains.

High spin spectroscopy of201Tl

The high spin structure of ${}^{201}$Tl has been studied by $\ensuremath{\gamma}$-ray spectroscopic method using the ${}^{198}$Pt(${}^{7}$Li,4$n$)${}^{201}$Tl reaction at 45 MeV beam energy. The level scheme of ${}^{201}$Tl has been considerably extended through the observation of 31 new transitions. Several new band structures have been established. The 9/2${}^{\ensuremath{-}}$ oblate band has been significantly extended beyond the particle alignment frequencies. The band structures and the other excited states have been compared with the neighboring odd-$A$ Tl isotopes and with the even-even core nucleus ${}^{200}$Hg. The total Routhian surface calculations have been performed to study the deformation and shape changes as a function of spin in this nucleus.

Changes in the mean-square charge radii and magnetic moments of neutron-deficient Tl isotopes

In-source laser spectroscopy experiments for neutron-deficient thallium isotopes at the 276.9-nm atomic transition have been carried out at the Investigation of Radioactive Isotopes on Synchrocyclotron facility of Petersburg Nuclear Physics Institute. New data on isotope shifts and the hyperfine structure for ${}^{183\ensuremath{-}207}$Tl isotopes and isomers are presented. The changes in the mean-square charge radii and magnetic-moment values are deduced. It is shown that nuclear properties of Tl isotopes and isomers smoothly change at the neutron midshell and beyond without development of strong deformation in contrast to the adjacent Hg nuclei. A rather great isomer shift between $I$ $=$ 1/2 and $I$ $=$ 9/2 states for odd Tl isotopes is preserved for both sides of the previously investigated mass range. For the first time, a similar isomer shift is found for the odd-odd isotope ${}^{186}$Tl. The close resemblance of the charge radii isotopic behavior for the Tl and Pb ground states is demonstrated.

Towards an understanding of thallium isotope fractionation during adsorption to manganese oxides

We have conducted the first study of Tl isotope fractionation during sorption of aqueous Tl(I) onto the manganese oxide hexagonal birnessite. The experiments had different initial Tl concentrations, amounts of birnessite, experimental durations, and temperatures, but all of them exhibit heavy Tl isotope compositions for the sorbed Tl compared with the solution, which is consistent with the direction of isotope fractionation observed between seawater and natural ferromanganese sediments. However, the magnitude of fractionation in all experiments (α≈1.0002–1.0015, where α=205Tl/203Tlsolid/205Tl/203Tlliq is smaller than observed between seawater and natural sediments (α≈1.0019–1.0021; Rehkämper et al., 2002, Earth. Planet. Sci. Lett. 197, 65–81). The experimental results display a strong correlation between the concentration of Tl in the resulting Tl-sorbed birnessite and the magnitude of fractionation. This correlation is best explained by sorption of Tl to two sites on birnessite, one with large isotope fractionation and one with little or no isotope fractionation. Previous work (Peacock and Moon, 2012, Geochim. Cosmochim. Acta 84, 297–313) indicates that Tl in natural ferromanganese sediments is oxidized to Tl(III) and adsorbed over Mn vacancy sites in the phyllomanganate sheets of birnessite, and we hypothesize that this site is strongly fractionated from Tl in solution due to the change in oxidation state from aqueous Tl(I). In most experiments, which have orders of magnitude more Tl associated with the solid than in nature, these vacancy sites are probably fully saturated, so various amounts of additional Tl are likely sorbed to either edge sites on the birnessite or triclinic birnessite formed through oxidative ripening of the hexagonal starting material, with unknown oxidation state and little or no isotopic fractionation. Thus each experiment displays isotopic fractionation governed by the proportions of Tl in the fractionated and slightly fractionated sites, and those proportions are controlled by how much total Tl is sorbed per unit of birnessite. In the experiments with the lowest initial Tl concentrations in solution (∼0.15–0.4μg/g) and the lowest concentrations of Tl in the resulting Tl-sorbed birnessite (⩽17μgTl/mg birnessite), we observed the largest isotopic fractionations, and fractionation is inversely proportional to the initial aqueous Tl concentration. Again, this correlation can be explained by the simultaneous occupation of two different sorption sites; vacancy sites that carry isotopically fractionated Tl and a second site carrying slightly fractionated Tl. The fractionation factors observed in nature exceed those in the experiments likely because the Tl concentrations in seawater and in ferromanganese sediments are three to four orders of magnitude lower than in our experiments, and therefore the second slightly fractionated sorption site is not significantly utilized. Temperature (6–40°C) and experimental duration (3min–72h) appear to have little or no effects on isotope behaviour in this system.

Assessing the utility of thallium and thallium isotopes for tracing subduction zone inputs to the Mariana arc

We provide the first exploration of thallium (Tl) abundances and stable isotope compositions as potential tracers during arc lava genesis. We present a case study of lavas from the Central Island Province (CIP) of the Mariana arc, supplemented by representative sedimentary and altered oceanic crust (AOC) inputs from ODP Leg 129 Hole 801 outboard of the Mariana trench. Given the large Tl concentration contrast between the mantle and subduction inputs coupled with previously published distinctive Tl isotope signatures of sediment and AOC, the Tl isotope system has great potential to distinguish different inputs to arc lavas. Furthermore, CIP lavas have well-established inter island variability, providing excellent context for the examination of Tl as a new stable isotope tracer.In contrast to previous work (Nielsen et al., 2006b), we do not observe Tl enrichment or light ε205Tl (where ε205Tl is the deviation in parts per 10,000 of a sample 205Tl/203Tl ratio compared to NIST SRM 997 Tl standard) in the Jurassic-aged altered mafic ocean crust subducting outboard of the Marianas (ε205Tl=−4.4 to 0). The lack of a distinctive ε205Tl signature may be related to secular changes in ocean chemistry. Sediments representative of the major lithologies from ODP Hole Leg 129 801 have 1–2 orders of magnitude of Tl enrichment compared to the CIP lavas, but do not record heavy signatures (ε205Tl=−3.0 to +0.4), as previously found in similar sediment types (ε205Tl>+2.5; Rehkämper et al., 2004).We find a restricted range of ε205Tl=−1.8 to −0.4 in CIP lavas, which overlaps with MORB. One lava from Guguan falls outside this range with ε205Tl=+1.2. Coupled Cs, Tl and Pb systematics of Guguan lavas suggests that this heavy Tl isotope composition may be due to preferential degassing of isotopically light Tl. In general, the low Tl concentrations and limited isotopic range in the CIP lavas is likely due to the unexpectedly narrow range of ε205Tl found in Mariana subduction inputs, coupled with volcaniclastic, rather than pelagic sediment as the dominant source of Tl.Much work remains to better understand the controls on Tl processing through a subduction zone. For example, Tl could be retained in residual phengite, offering the potential exploration of Cs/Tl ratios as a slab thermometer. However, data for Tl partitioning in phengite (and other micas) is required before developing this application further. Establishing a database of Tl concentrations and stable isotopes in subduction zone lavas with different thermal parameters and sedimentary inputs is required for the future use of Tl as a subduction zone tracer.

Non-linear signal response functions and their effects on the statistical and noise cancellation properties of isotope ratio measurements by multi-collector plasma mass spectrometry

A nebulizer-centric response function model of the analytical inductively coupled argon plasma ion source was used to investigate the statistical frequency distributions and noise reduction factors of simultaneously measured flicker noise limited isotope ion signals and their ratios. The response function model was extended by assuming i) a single gaussian distributed random noise source (nebulizer gas pressure fluctuations) and ii) the isotope ion signal response is a parabolic function of the nebulizer gas pressure.Model calculations of ion signal and signal ratio histograms were obtained by applying the statistical method of translation to the non-linear response function model of the plasma. Histograms of Ni, Cu, Pr, Tl and Pb isotope ion signals measured using a multi-collector plasma mass spectrometer were, without exception, negative skew. Histograms of the corresponding isotope ratios of Ni, Cu, Tl and Pb were either positive or negative skew. There was a complete agreement between the measured and model calculated histogram skew properties.The nebulizer-centric response function model was also used to investigate the effect of non-linear response functions on the effectiveness of noise cancellation by signal division. An alternative noise correction procedure suitable for parabolic signal response functions was derived and applied to measurements of isotope ratios of Cu, Ni, Pb and Tl. The largest noise reduction factors were always obtained when the non-linearity of the response functions was taken into account by the isotope ratio calculation.Possible applications of the nebulizer-centric response function model to other types of analytical instrumentation, large amplitude signal noise sources (e.g., lasers, pumped nebulizers) and analytical error in isotope ratio measurements by multi-collector plasma mass spectrometry are discussed.

Trace elements and Pb isotope records in Dome C (East Antarctica) ice over the past 800,000 years

Trace elements (V, Cr, Mn, Fe, Co, Cu, Zn, As, Rb, Sr, Mo, Cd, Sb, Ba, Tl, Pb, Bi, Th and U) and Pb isotopic compositions from the EPICA (European Project for Ice Coring in Antarctica) Dome C ice core have been determined using inductively coupled plasma sector field mass spectrometry (ICP-SFMS) and thermal ionization mass spectrometry (TIMS), covering the period from ~533 kyr BP to ~800 kyr BP, respectively. Our data have enabled us to extend the previous EDC records of trace elements and Pb isotopes from the Holocene back to the Marine Isotopic Stage 20.2, ~800 kyr BP. We here discuss the EDC records of Ba, Rb, Mo, Sb, Cd, Tl, Bi and Pb isotopes. Crustal elements such as Ba and Rb show well defined variations in concentrations in relation to climatic conditions with lower values during the interglacial periods and much higher values during the coldest periods of the last eight climatic cycles. Volcanogenic Cd, Tl and Bi show a less pronounced relationship between concentrations and climatic conditions. The isotopic signatures of Pb suggest that changes in the provenance of dust reaching the East Antarctic Plateau from Potential Source Areas occurred during the interglacial periods before the MBE. Our data suggest that the main factors affecting deposition fluxes and sources of natural trace elements over Antarctica are most likely linked to a progressive coupling of the climates of Antarctica and lower latitudes over the past 800 kyr.

Spectroscopy of Neutron-Deficient Nuclei Near the Z=82 Closed Shell via Symmetric Fusion Reactions

In-beam and decay-spectroscopy studies of neutron-deficient nuclei near the Z=82 shell closure were carried out using the Fragment Mass Analyzer (FMA) and the Gammasphere array, in conjunction with symmetric fusion reactions and the Recoil Decay Tagging (RDT) technique. The primary motivation was to study properties of 179 Tl and 180 Tl, and their daughter, and grand-daughter isotopes. For the first time, in-beam structures associated with 179 Tl and 180 Tl were observed, as well as γ rays associated with the 180 Tl α decay. No long-lived isomer was identified in 180 Tl, in contrast with the known systematics for the heavier odd-odd Tl isotopes.

New laser setup at the IRIS facility. Magnetic moments and mean squared charge radii of neutron deficient Tl isotopes

A new laser installation for the resonance ionization spectroscopy in a laser ion source and for rare isotope production has been put into operation at the IRIS mass-separator, working on-line with the 1 GeV proton beam of the Petersburg Nuclear Physics Institute synchrocyclotron. Isotope shift and hyperfine splitting of 276.9 nm atomic transition in the long chain of Tl isotopes and isomers have been measured. New data on the magnetic moments and changes in mean squared charge radius for 183,184,185,185m,186m2,195m,197mTl have been obtained.

Nuclear field shift effect in isotope fractionation of thallium

Environmental transport of Tl is affected by redox reaction between Tl(I) and Tl(III) and ligand exchange reactions of them. In order to deepen the knowledge of Tl chemistry, we investigated fractionation of Tl stable isotopes (203Tl and 205Tl) in a chemical exchange system. Tl isotopes were fractionated in a liquid–liquid extraction system, in which aqueous and organic phases are hydrochloric acid solution and dichloroethane including a crown ether, respectively. After purification by ion-exchange chemistry, the isotope ratio of 205Tl/203Tl in equilibrated aqueous phase was measured precisely by multiple-collector–inductively-coupled-plasma–mass-spectrometry. A large isotope fractionation >1 ‰ was found. Electronic structures of possible Tl species (hydrated Tl+, Tl3+, and Tl chlorides) were calculated by ab initio methods, and the isotope fractionation factor was theoretically obtained. The isotope fractionation via intramolecular vibrations was calculated to be much smaller than the experimental result. The isotope fractionation via isotopic change in nuclear volume, named the nuclear field shift effect, was calculated to be >1 ‰ in Tl(I)–Tl(III) redox systems and/or ligand exchange systems of Tl(III). The nuclear field shift effect was found to be the major origin of Tl isotope fractionation.

First measurement of beta decay half-lives in neutron-rich Tl and Bi isotopes

Neutron-rich isotopes around lead, beyond N=126, have been studied exploiting the fragmentation of an uranium primary beam at the FRS-RISING setup at GSI. For the first time β-decay half-lives of Bi219 and Tl211,212,213 isotopes have been derived. The half-lives have been extracted using a numerical simulation developed for experiments in high-background conditions. Comparison with state of the art models used in r-process calculations is given, showing a systematic underestimation of the experimental values, at variance from close-lying nuclei.

Hyperfine structure anomaly and magnetic moments of neutron deficient Tl isomers withI=9/2

The hyperfine structure of 276.9-nm atomic transition has been studied by the resonant ionization spectroscopy method at mass-separator IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron), Petersburg Nuclear Physics Institute (PNPI) for the odd Tl isomers with $I$ = 9/2 and $A$ = 187--197. A differential hyperfine structure anomaly for $6p{}^{\phantom{\rule{0.16em}{0ex}}2\phantom{\rule{-0.16em}{0ex}}}{P}_{1/2}$ and $7s{}^{\phantom{\rule{0.16em}{0ex}}2\phantom{\rule{-0.16em}{0ex}}}{S}_{1/2}$atomic states in Tl isomers with $I$ = 9/2 has been determined. It is described by the recently developed theoretical approach fairly well. This enables one to recalculate the magnetic moments of ${}^{187\ensuremath{-}193}$Tl${}^{m}$ ($I$ = 9/2) from previously measured hyperfine splittings for $7s{}^{\phantom{\rule{0.16em}{0ex}}2\phantom{\rule{-0.16em}{0ex}}}{S}_{1/2}$ states and to determine for the first time the magnetic moments for ${}^{197}$Tl${}^{m}$ and ${}^{195}$Tl${}^{m}$ ($I$ = 9/2) from hyperfine splittings for $6p{}^{\phantom{\rule{0.16em}{0ex}}2\phantom{\rule{-0.16em}{0ex}}}{P}_{1/2}$ states with properly taking into account the rather great hyperfine structure anomaly. Similar measurements with greater accuracy have been proposed for the other nuclear states in odd-odd Tl isotopes. These measurements could shed light on the nuclear magnetization distribution in these isotopes.

High spin band structures in doubly odd194Tl

The high-spin states in odd-odd $^{194}$Tl nucleus have been studied by populating them using the $^{185,187}$Re($^{13}$C, xn) reactions at 75 MeV of beam energy. $\gamma-\gamma$ coincidence measurement has been performed using the INGA array with a digital data acquisition system to record the time stamped data. Definite spin-parity assignment of the levels was made from the DCO ratio and the IPDCO ratio measurements. The level scheme of $^{194}$Tl has been extended up to 4.1 MeV in excitation energy including 19 new gamma ray transitions. The $\pi h_{9/2} \otimes \nu i_{13/2}$ band, in the neighboring odd-odd Tl isotopes show very similar properties in both experimental observables and calculated shapes. Two new band structures, with 6-quasiparticle configuration, have been observed for the first time in $^{194}$Tl. One of these bands has the characteristics of a magnetic rotational band. The cranked shell model calculations, using a deformed Woods-Saxon potential, have been performed to obtain the total Routhian surfaces in order to study the shapes of the bands and the band crossing in $^{194}$Tl. The semiclassical formalism has been used to describe the magnetic rotational band.

Oxidative scavenging of thallium by birnessite: Explanation for thallium enrichment and stable isotope fractionation in marine ferromanganese precipitates

Tl stable isotopes recorded in marine ferromanganese crusts show great promise as a tracer of past marine and climatic conditions. Key to interpreting recent Tl stable isotope time-series data is a detailed, molecular-level understanding of Tl scavenging by ferromanganese crust minerals and Tl stable isotope fractionation occurring during uptake. To this end, we determine the mechanism of Tl sorption to the primary ferromanganese minerals in crusts, namely hexagonal birnessite, todorokite and ferrihydrite, using XAS. We compliment our data with micro-focus XAS of a Tl-enriched hydrogenetic ferromanganese crust. We show that Tl(I) is oxidised to Tl(III) during sorption to hexagonal birnessite, but not during sorption to todorokite, triclinic birnessite and ferrihydrite. Tl(III) forms an inner-sphere complex at the hexagonal birnessite surface, located at vacant octahedral sites in the phyllomanganate sheets. We show that oxidation of Tl(I) to Tl(III) during reductive dissolution of birnessite is thermodynamically unfavourable; and propose that oxidation of Tl(I) is driven by the formation of the Tl(III) surface complex. Recent theoretical calculations predict a large equilibrium stable isotope fractionation between Tl(I) and Tl(III), leading to Tl(III) species that are enriched in the heavy 205Tl isotope. In light of this work, we propose a molecular sorption–oxidation–fractionation mechanism that provides a unifying explanation for the recently observed geochemical behaviour of Tl in marine ferromanganese-rich sediments. In this mechanism, the proportion of hexagonal birnessite dictates the extent of Tl oxidation, which controls the extent of Tl enrichment and isotope fractionation. This work is among the first to provide a molecular explanation for reported trends in trace element enrichments and stable isotope compositions in geologic deposits. Our molecular sorption–oxidation–fractionation mechanism will ultimately help interpret Tl signals in marine sedimentary archives to provide new constraints on past oceanic and climatic change. In addition, our mechanism should also help explain compositional relationships of other redox-sensitive elements in ferromanganese-rich marine sediments that might also be used as paleoceanographic and paleoclimate proxies.

New laser setup for the selective isotope production and investigation in a laser ion source at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility

New laser installation for the resonance ionization spectroscopy in a laser ion source and for rare isotope production has been recently put into operation at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility (Petersburg Nuclear Physics Institute, Gatchina). This is a significant improvement of a previous target-laser ion source device of the IRIS mass-separator, working on-line with 1 GeV proton beam of PNPI (Petersburg Nuclear Physics Institute) synchrocyclotron. It makes possible for us to get the isobarically clean radioactive isotope beams of a great number of chemical elements. New laser setup provides the two- or three-resonance step ionization in the range of wavelength of 265-850 nm. The first results obtained at the laser setup for Tl isotopes are presented.

An isotopic perspective on mass bias and matrix effects in multi-collector inductively-coupled-plasma mass spectrometry

Lead and Tl isotope intensities and ratios were measured in radial and axial plasma profiles using multi-collector inductively-coupled-plasma mass spectrometry (MC-ICP-MS). Signal profiles for 204Pb, 206Pb, 207Pb and 208Pb display mass dependent radial and axial distributions in the plasma. In radial profiles lighter isotopes exhibit greater dispersal from the plasma axis than heavier isotopes, in agreement with ICP-MS elemental observations. However, signal maxima (Imax) for heavier Pb isotopes occur closer to the load coil than Imax for lighter Pb isotopes, the reverse of ICP-MS elemental observations. These mass dependent distributions predict that the radial dispersion and axial Imax locations for 203Tl and 205Tl isotopes should occur interspersed with the values for simultaneously measured Pb isotopes. Instead however, their values are appropriate for masses greater that 208Pb, indicating that the observed profiles are not the product of a single stage mass dependent process and that other element properties also effect the distributions. Isotope ratio (and thus mass bias) variation with sampling depth reflects both the mass dependent separation of the numerator and denominator isotope Imax along the axis of the plasma and the distance along the axis of the plasma over which the isotope signals are distributed. Addition of matrix to the plasma significantly reduces the variability of these two characteristics suggesting that more accurate correction of instrumental mass bias and more accurate normalization of sample ratios to standard values could be achieved by addition of a common matrix to samples and standards.

Thallium isotopes in early diagenetic pyrite – A paleoredox proxy?

This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ∼183Ma) are compared with data from Late Neogene (<10Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment–water interface due to the sulfidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment–water interface.The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate.The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.