Tl Isotope Compositions Research Articles

Thallium concentration and thallium isotope composition of lateritic terrains

Continental weathering plays a key role in modifying the geochemical budget of terrestrial reservoirs. Laterites are the products of extreme sub-aerial continental weathering. This study presents the first investigation of thallium (Tl) abundances and stable isotopic compositions of lateritic terrains. Two laterite profiles from India of differing protolith and age are studied. Thallium concentrations range between 7 and 244 ng/g for a basalt-based lateritic profile and 37–652 ng/g within a greywacke lateritic profile. The average Tl stable isotope composition of the two profiles is similar to many typical igneous materials, however, the intense tropical weathering causes a small but resolvable fractionation of Tl stable isotopes towards heavy values in the residual soils. The profiles are dominated by significant positive isotope excursions (reported as ε205Tl relative to standard NBS997) of +3.5 ± 0.5 2sd and +6.2 ± 0.5 2sd at the inferred palaeowater tables within both laterite profiles. These signatures likely reflect combined changes in redox state and mineralogy. Extensive mineral dissolution under through-flowing fluids alongside the formation of new phases such as phyllosilicates and Mn- and Fe-oxides and hydroxides likely account for some of the Tl mobilisation, sorption and coprecipitation. In the case of laterites, the formation of the new phases and role of surface sorption likely contribute to stable Tl isotope fractionation. The identification of strong isotope excursions at inferred palaeowater tables encourages future research to determine specific mineral phases that may drive significant fractionation of Tl stable isotopes. This study showcases the magnitude of natural variation possible in terrestrial soils. Such information is key to the nascent application of Tl isotope compositions as tracers of anthropogenic pollution.

Variable Tl, Pb, and Cd concentrations and isotope compositions of enstatite and ordinary chondrites—Evidence for volatile element mobilization and decay of extinct 205Pb

AbstractNew Tl, Pb, and Cd concentration and Tl, Pb isotope data are presented for enstatite as well as L‐ and LL‐type ordinary chondrites, with additional Cd stable isotope results for the former. All three chondrite suites have Tl and Cd contents that vary by more than 1–2 orders of magnitude but Pb concentrations are more uniform, as a result of terrestrial Pb contamination. Model calculations based on Pb isotope compositions indicate that for more than half of the samples, more than 50% of the measured Pb contents are due to addition of modern terrestrial Pb. In part, this is responsible for the relatively young and imprecise Pb‐Pb ages determined for EH, L, and LL chondrites, which are hence only of limited chronological utility. In contrast, four particularly pristine EL chondrites define a precise Pb‐Pb cooling age of 4559 ± 6 Ma. The enstatite chondrites (ECs) have highly variable ε114/110Cd of between about +3 and +70 due to stable isotope fractionation from thermal and shock metamorphism. Furthermore, nearly all enstatite meteorites display ε205Tl values from −3.3 to +0.8, while a single anomalous sample is highly fractionated in both Tl and Cd isotopes. The majority of the ECs thereby define a correlation of ε205Tl with ε114/110Cd, which suggests that at least some of the Tl isotope variability reflects stable isotope fractionation rather than radiogenic ingrowth of 205Tl from 205Pb decay. Considering L chondrites, most ε205Tl values range between −4 and +1, while two outliers with ε205Tl ≤ −10 are indicative of stable isotope fractionation. Considering only those L chondrites which are least likely to feature Pb contamination or stable Tl isotope effects, the results are in accord with the former presence of live 205Pb on the parent body, with an initial 205Pb/204Pb = (1.5 ± 1.4) × 10−4, which suggests late equilibration of the Pb‐Tl system 26–113 Ma after carbonaceous chondrites (CCs). The LL chondrites display highly variable ε205Tl values from −12.5 to +14.9, also indicative of stable isotope effects. However, the data for three pristine LL3/LL4 chondrites display an excellent correlation between ε205Tl and 204Pb/203Tl. This defines an initial 205Pb/204Pb of (1.4 ± 0.3) × 10−4, equivalent to a 205Pb‐205Tl cooling age of 55 + 12/−24 Ma (31–67 Ma) after CCs.

Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial

Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ∼20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ∼million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates.This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl=−6.0±0.3 (±2 SD, n=41) while oxic waters from Cariaco and the Black Sea are −5.6 and −2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (−6) and continental material (−2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude less than each of the modern ocean outputs and imparts no isotopic fractionation. Thallium removal into pyrite appears to be associated with a small negative fractionation between −1 and −3 ε205Tl, which renders Tl-depleted waters below the chemocline enriched in isotopically-heavy Tl. Due to the quantitative removal of Tl from euxinic seawater, Tl isotope analyses of the authigenic fraction of underlying euxinic sediments from both the Black Sea and Cariaco Basin capture the Tl isotope value of the oxic portion of their respective water column with no net isotope fractionation. Since the Tl isotope composition of seawater is largely dictated by the relative fraction of Mn-oxide burial versus oceanic crust alteration, we contend that the Tl isotope composition of authigenic Tl in black shales, deposited under euxinic conditions but well-connected to the open ocean, can be utilized to reconstruct the Tl isotope composition of seawater, and thus to reconstruct the global history of Mn-oxide burial.

Thallium isotopes as tracers of recycled materials in subduction zones: Review and new data for lavas from Tonga-Kermadec and Central America

Sediment is actively being subducted in every convergent margin worldwide. Yet, geochemical data for arc lavas from several subduction zones, such as Northern Tonga and Costa Rica have revealed either attenuated or limited evidence for sediment in their mantle source regions. Here we use thallium (Tl) isotopes to trace slab components in lavas from the Tonga-Kermadec and Central American arcs. In general, both arcs display Tl isotope data that are most compatible with addition of sediment to the sub-arc mantle from the subducting slab. This evidence is particular strong in the Tonga-Kermadec arc where pelagic clays dominate the Tl budget along the entire arc. Contributions from altered oceanic crust as well as the Louisville Seamount chain that subducts underneath Northern Tonga are not visible in Tl isotopes, which is likely due to the very high Tl concentrations found in pelagic sediments outboard of the Tonga-Kermadec arc. Lavas from Central America reveal variable and systematic Tl isotope compositions along-strike. In particular, lavas from Nicaragua are dominated by contributions from sediments, whereas Costa Rican samples reveal a significant altered oceanic crust component with little influence from sediments on thallium isotope composition. The absence of a sediment signature in Costa Rica corresponds with the Cocos Ridge and the seamount province subduction, which results in a thinner sediment cover. Furthermore, the subducted sediment is dominated by carbonates with very low Tl concentrations and, therefore, small amounts of carbonate sediment added to the mantle wedge do not contribute significantly to the overall Tl budget.A review of Tl isotope and concentration data from the Aleutians, Marianas, Tonga-Kermadec and Central American arcs demonstrate that pelagic sediments are detectable in most arcs, whereas altered oceanic crust components only become appreciable when sediment Tl concentrations are very low (e.g. carbonate) or if sediments are no longer a significant component of the subducting slab (e.g. slab melting in Western Aleutians). As such, Tl isotopes are a promising tool to trace sediment subduction although this requires at least some pelagic sediment is present in the subducted sediment package.We suggest that thallium partitioning between the slab and mantle wedge is most likely controlled by retention in phengite or by partitioning into fluids. Residual phengite likely produces high Cs/Tl ratios because Tl should be more compatible in phengite than is Cs, however, this conclusion needs experimental verification. The stability of phengite is lower at higher fluid contents, which results in hyperbolic relationships between Cs/Tl and possible indicators of fluids such as Sr/Nd and Ba/Th. Thus, combined Tl isotopic and elemental systematics not only provide detailed information about the specific slab components that contribute to arc lavas, but also potentially shed light on the mineralogy and physical conditions of subducting slabs.

Investigation and Application of Thallium Isotope Fractionation

This contribution summarizes the current state of understanding and recent advances made in the field of stable thallium (Tl) isotope geochemistry. High precision measurements of Tl isotope compositions were developed in the late 1990s with the advent of multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS) and subsequent studies revealed that Tl, despite the small relative mass difference of the two isotopes, exhibits substantial stable isotope fractionation, especially in the marine environment. The most fractionated reservoirs identified are ferromanganese sediments with ɛ 205 Tl ≈ +15 and low temperature altered oceanic crust with ɛ 205 Tl ≈ −20. The total isotopic variability of more than 35 ɛ 205 Tl-units hence exceeds the current analytical reproducibility of the measurement technique by more than a factor of 70. This isotopic variation can be explained by invoking a combination of conventional mass dependent equilibrium isotope effects and nuclear field shift isotope fractionation, but the specific mechanisms are still largely unaccounted for. Thallium isotopes have been applied to investigate paleoceanographic processes in the Cenozoic and there is evidence to suggest that Tl isotopes may be utilized as a monitor of the marine manganese oxide burial flux over million year time scales. In addition, Tl isotopes can be used to calculate the magnitude of hydrothermal fluid circulation through ocean crust. It has also been shown that the subduction of marine ferromanganese sediments can be detected with Tl isotopes in lavas erupted in subduction zone settings as well as in ocean island basalts. Meteorite samples display Tl isotope variations that exceed the terrestrial range with a total variability of about 50 ɛ 205 Tl. The large isotopic diversity, however, is generated by both stable Tl isotope fractionations, which reflect the highly volatile and labile cosmochemical nature of the element, and radiogenic decay of extinct 205 Pb to 205 Tl with a half-life of about 15 Ma. The difficulty of deconvolving these two sources of isotopic variability restricts the utility of both the 205 Pb– 205 Tl chronometer and the Tl stable isotope system to inform on early solar system processes.

Thallium elemental behavior and stable isotope fractionation during magmatic processes

Stable thallium (Tl) isotopes are an extremely sensitive tracer for the addition of small amounts of sediments or materials altered at low temperatures to the source(s) of mantle-derived melts. The ability of Tl to trace such materials is due to the large concentration contrast between the mantle (Tl<2ng/g) and possible exotic inputs (Tl~100ng/g to >μg/g), which also often display fractionated Tl isotope compositions. However, the magnitude of Tl isotope fractionation induced by igneous processes alone has not been systematically assessed. Here, two suites of co-genetic magmas, spanning a large range of differentiation, from Hekla, Iceland, and Anatahan, in the Mariana arc, are used to assess the behavior of thallium and its stable isotope variations during magmatic processes. Thallium behaves as a near-perfectly incompatible lithophile element throughout magmatic evolution, mirroring elements such as Rb, Cs, and K. Lavas from Hekla have restricted Cs/Tl ratios and stable Tl isotope compositions, which overlap with mantle estimates. Lavas from subduction-related Anatahan volcano also have a restricted range in Tl isotope composition, which overlaps with Hekla and MORB, demonstrating that fractional crystallisation and partial melting does not fractionate stable Tl isotopes. Subduction environments display variable Cs/Tl, indicating that the subduction process commonly fractionates these two elements. The immunity of thallium stable isotopes to fractionation by magmatic processes coupled with its extreme sensitivity for tracing pelagic sediments, FeMn crusts and low temperature altered oceanic crust highlight its value in elucidating the nature of mantle sources of both oceanic basalts and arc lavas. Critically, meaningful interpretation of thallium isotope compositions need not be restricted to primitive lavas.

Isotopic Tracing of Thallium Contamination in Soils Affected by Emissions from Coal-Fired Power Plants.

Here, for the first time, we report the thallium (Tl) isotope record in moderately contaminated soils with contrasting land management (forest and meadow soils), which have been affected by emissions from coal-fired power plants. Our findings clearly demonstrate that Tl of anthropogenic (high-temperature) origin with light isotope composition was deposited onto the studied soils, where heavier Tl (ε(205)Tl ∼ -1) naturally occurs. The results show a positive linear relationship (R(2) = 0.71) between 1/Tl and the isotope record, as determined for all the soils and bedrocks, also indicative of binary Tl mixing between two dominant reservoirs. We also identified significant Tl isotope variations within the products from coal combustion and thermo-desorption experiments with local Tl-rich coal pyrite. Bottom ash exhibited the heaviest Tl isotope composition (ε(205)Tl ∼ 0), followed by fly ash (ε(205)Tl between -2.5 and -2.8) and volatile Tl fractions (ε(205)Tl between -6.2 and -10.3), suggesting partial Tl isotope fractionations. Despite the evident role of soil processes in the isotope redistributions, we demonstrate that Tl contamination can be traced in soils and propose that the isotope data represent a possible tool to aid our understanding of postdepositional Tl dynamics in surface environments for the future.

Tracking along-arc sediment inputs to the Aleutian arc using thallium isotopes

Sediment transport from the subducted slab to the mantle wedge is an important process in understanding the chemical and physical conditions of arc magma generation. The Aleutian arc offers an excellent opportunity to study sediment transport processes because the subducted sediment flux varies systematically along strike (Kelemen et al., 2003) and many lavas exhibit unambiguous signatures of sediment addition to the sub-arc mantle (Morris et al., 1990). However, the exact sediment contribution to Aleutian lavas and how these sediments are transported from the slab to the surface are still debated. Thallium (Tl) isotope ratios have great potential to distinguish sediment fluxes in subduction zones because pelagic sediments and low-temperature altered oceanic crust are highly enriched in Tl and display heavy and light Tl isotope compositions, respectively, compared with the upper mantle and continental crust.Here, we investigate the Tl isotope composition of lavas covering almost the entire Aleutian arc a well as sediments outboard of both the eastern (DSDP Sites 178 and 183) and central (ODP Hole 886C) portions of the arc. Sediment Tl isotope compositions change systematically from lighter in the Eastern to heavier in the Central Aleutians reflecting a larger proportion of pelagic sediments when distal from the North American continent. Lavas in the Eastern and Central Aleutians mirror this systematic change to heavier Tl isotope compositions to the west, which shows that the subducted sediment composition is directly translated to the arc east of Kanaga Island. Moreover, quantitative mixing models of Tl and Pb, Sr and Nd isotopes reveal that bulk sediment transfer of ∼0.6–1.0% by weight in the Eastern Aleutians and ∼0.2–0.6% by weight in the Central Aleutians can account for all four isotope systems. Bulk mixing models, however, require that fractionation of trace element ratios like Ce/Pb, Cs/Tl, and Sr/Nd in the Central and Eastern Aleutians occurs after the sediment component was mixed with the mantle wedge. Models of Sr and Nd isotopes that involve sediment melting require either high degrees of sediment melting (>50%), in which case trace element ratios like Ce/Pb, Cs/Tl, and Sr/Nd of Aleutian lavas need to be produced after mixing with the mantle, or significant fluid additions from the underlying oceanic crust with Sr and Nd isotope compositions indistinguishable from the mantle wedge as well as high Sr/Nd ratios similar to that of low (<20%) degree sediment melts.Thallium isotope data from Western Aleutian lavas exhibit compositions slightly lighter than the upper mantle, which implies a negligible sediment flux at this location and probably involvement of low-temperature altered oceanic crust in the generation of these lavas. In general, the lightest Tl isotope compositions are observed for the highest Sr/Y ratios and most unradiogenic Sr and Pb isotope compositions, which is broadly consistent with derivation of these lavas via melting of eclogitized altered oceanic crust.

Thallium as a tracer of fluid–rock interaction in the shallow Mariana forearc

Fluids driven off the subducting Pacific plate infiltrate the shallow Mariana forearc and lead to extensive serpentinization of mantle peridotite. However, the sources, pathways, and chemical modifications of ascending, slab-derived fluids remain poorly constrained and controversial. In this study, we use thallium (Tl) concentrations and isotopic ratios of serpentinized peridotite and rodingitized diabase from the South Chamorro and Conical Seamounts to discriminate between potential fluid sources with distinct Tl isotope compositions. Serpentinite samples from the Mariana forearc all display ε205Tl>−0.5 (where ε205Tl=10,000×(Tl205/Tlsample203−Tl205/TlSRM997203)/(Tl205/TlSRM997203)), which is significantly enriched in 205Tl compared to the normal mantle (ε205Tl=−2). Given that high temperature hydrothermal processes do not impart significant Tl isotope fractionation, the isotope compositions of the serpentinites must reflect that of the serpentinizing fluid. Pelagic sediments are the only known slab component that consistently displays ε205Tl>−0.5 and, therefore, we interpret the heavy Tl isotope signatures as signifying that the serpentinizing fluids were derived from subducting pelagic sediments. A rodingitized diabase from Conical Seamount was found to have an ε205Tl of 0.8, suggesting that sediment-sourced serpentinization fluids could also affect diabase and other mafic lithologies in the shallow Mariana forearc. Forearc rodingitization of diabase led to a strong depletion in Tl content and a virtually complete loss of K, Na and Rb. The chemical composition of hybrid fluids resulting from serpentinization of harzburgite with concomitant rodingitization of diabase can be highly alkaline, depleted in Si, yet enriched in Ca, Na, K, and Rb, which is consistent with the composition of fluids emanating from mud volcanoes in the Mariana forearc. Our study suggests that fluid–rock interactions between sedimentary, mafic, and ultramafic lithologies are strongly interconnected even in the shallowest parts of subduction zones. We conclude that transfer of fluids and dissolved elements at temperatures and pressures below 400 °C and 1 GPa, respectively, must be taken into account when elemental budgets and mass transfer between the subducting plate, the forearc, the deep mantle and the ocean are evaluated.

Tracing anthropogenic thallium in soil using stable isotope compositions.

Thallium stable isotope data are used in this study, for the first time, to apportion Tl contamination in soils. In the late 1970s, a cement plant near Lengerich, Germany, emitted cement kiln dust (CKD) with high Tl contents, due to cocombustion of Tl-enriched pyrite roasting waste. Locally contaminated soil profiles were obtained down to 1 m depth and the samples are in accord with a binary mixing relationship in a diagram of Tl isotope compositions (expressed as ε(205)Tl, the deviation of the (205)Tl/(203)Tl ratio of a sample from the NIST SRM 997 Tl isotope standard in parts per 10(4)) versus 1/[Tl]. The inferred mixing endmembers are the geogenic background, as defined by isotopically light soils at depth (ε(205)Tl ≈ -4), and the Tl emissions, which produce Tl-enriched topsoils with ε(205)Tl as high as ±0. The latter interpretation is supported by analyses of the CKD, which is also characterized by ε(205)Tl ≈ ± 0, and the same ε(205)Tl value was found for a pyrite from the deposit that produced the cocombusted pyrite roasting waste. Additional measurements for samples from a locality in China, with outcrops of Tl sulfide mineralization and associated high natural Tl backgrounds, reveal significant isotope fractionation between soils (ε(205)Tl ≈ +0.4) and locally grown green cabbage (ε(205)Tl between -2.5 and -5.4). This demonstrates that biological isotope fractionation cannot explain the isotopically heavy Tl in the Lengerich topsoils and the latter are therefore clearly due to anthropogenic Tl emissions from cement processing. Our results thus establish that isotopic data can reinforce receptor modeling for the toxic trace metal Tl.

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.

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.

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.

Thallium isotope variations in an ore-bearing continental igneous setting: Collahuasi Formation, northern Chile

Thallium is a highly incompatible element and a large fraction of the bulk silicate Earth Tl budget is, therefore, expected to reside in the continental crust. Nonetheless, the Tl isotope systematics of continental rocks are essentially unexplored at present. Here, we present new Tl isotope composition and concentration data for a suite of 36 intrusive and extrusive igneous rocks from the vicinity of porphyry Cu deposits in the Collahuasi Formation of the Central Andes in northern Chile. The igneous lithologies of the rocks are variably affected by the hydrothermal alteration that accompanied the formation of the Cu deposits. The samples display Tl concentrations that vary by more than an order of magnitude, from 0.1 to 3.2 μg/g, whilst ε 205Tl ranges between −5.1 and +0.1 (ε 205Tl is the deviation of the 205Tl/ 203Tl isotope ratio of a sample from a standard in parts per 10 4). These variations are primarily thought to be a consequence of hydrothermal alteration processes, including metasomatic transport of Tl, and formation/breakdown of Tl-bearing minerals, which are associated with small but significant Tl isotope effects. The Tl abundances show excellent correlations with both K and Rb concentrations but no co-variation with Cu. This demonstrates that Tl displays only limited chalcophile affinity in the continental crust of the Collahuasi Formation, but behaves as a lithophile element with a distribution that is primarily governed by partitioning of Tl + into K +-bearing phases. Collahuasi samples with propylitic alteration features, which are derived from the marginal parts of the hydrothermal systems, have, on average, slightly lighter Tl isotope compositions than rocks from the more central sericitic and argillic alteration zones. This small but statistically significant difference most likely reflects preferential retention of isotopically heavy Tl in alteration phases, such as white micas and clays, which formed during sericitic and argillic alteration.

The thallium isotope composition of carbonaceous chondrites — New evidence for live 205Pb in the early solar system

The extinct radionuclide 205Pb, which decays to 205Tl with a half-life of 15 Ma, is of considerable cosmochemical interest, as it is the only short-lived isotope that is produced exclusively by s-process nucleosynthesis. Evidence for the existence of 205Pb in the early solar system has only recently been obtained from analyses of IAB iron meteorites, but significant uncertainties remain about the initial 205Pb abundance and Tl isotope composition of the solar system. In an attempt to better constrain these values, a comprehensive 205Pb– 205Tl isochron study was carried out on ten carbonaceous chondrites of groups CI, CM, CV, CO and CR. The Pb and Cd isotope compositions of the meteorites were also determined, to correct for terrestrial Pb contamination and eliminate samples that exhibit fractionated Tl isotope compositions from thermal processing. The analyses revealed only limited variation in ε 205Tl, with values of between − 4.0 and + 1.2, but nonetheless the Tl isotope compositions correlate with Pb/Tl ratios. This correlation is unlikely to be due to stable isotope fractionation from terrestrial weathering or early solar system processes, and is most readily explained by in situ decay of 205Pb to 205Tl. Previous 53Mn– 53Cr and 107Pd– 107Ag studies of bulk carbonaceous chondrites provide evidence that the Pb–Tl isochron records volatile fractionation in the solar nebula at close to 4567 Ma. The isochron thus yields the initial 205Pb abundance and Tl isotope composition of the solar system, with values of 205Pb/ 204Pb SS,0 = (1.0 ± 0.4) × 10 − 3 and ε 205Tl SS,0 = − 7.6 ± 2.1, respectively. These results confirm the previous Pb–Tl data for IAB iron meteorites, which provided the first clear evidence for the existence of live 205Pb in the early solar system. The initial 205Pb SS,0 abundance inferred from carbonaceous chondrites demonstrates that the 205Pb– 205Tl decay system is well suited for chronological studies of early solar system processes that produce fractionations in Pb/Tl ratios, including core crystallization and the mobilization of volatiles during thermal processing. The 205Pb SS,0 abundance is close to the upper limit of nucleosynthetic production estimates for AGB stars and thus in accord with contributions of such stars to the early solar system budget of freshly synthesized radioisotopes.

Thallium isotopes as a potential tracer for the origin of cratonic eclogites

Cratonic eclogites are inferred to originate either from subducted ocean crust or mantle melts accreted onto the roots of continents. These models have different implications for the growth of continents, but it is currently difficult to determine the origin of individual eclogite suites. Upper ocean crust altered at low temperatures and marine sediments both display high thallium (Tl) concentrations and strongly fractionated Tl isotope signatures relative to the ambient upper mantle. In this study we carry out the first examination of the suitability of Tl isotopes as a tracer for an ocean-crust origin of cratonic eclogites. We have analysed the Tl isotope composition of clinopyroxene and garnet in six eclogites from the Kaalvallei and Bellsbank kimberlite pipes in South Africa. Minerals were pre-cleaned with an HCl leaching technique and the leachates display variably light Tl isotope ratios. These most likely reflect low-temperature hydrothermal alteration occurring after eruption of the kimberlite that carried the eclogites to the surface. The leached mineral pairs all display identical Tl isotope ratios, strongly suggesting that the source of the analysed Tl is identical for each mineral pair. It is, however, not possible to exclude the possibility that the analysed Tl originates from kimberlitic material that was not removed by the cleaning procedure. Only one of the six samples exhibits a Tl isotope composition different from ambient mantle. Assuming that the Tl isotope signatures indeed represent the eclogite minerals and not any form of contamination, the Tl isotope composition in this sample is consistent with containing a minor component (<3%) of ocean crust altered at low temperatures. Thallium isotopes may become one of the most sensitive indicators for the presence of low-T altered ocean crust because of the stark contrast in Tl concentration and isotopic composition between the mantle and altered ocean crust. In fact, no other chemical or isotopic tracer could have provided an indication that any of the samples studied here had a subduction origin. However, much work is still required before it becomes clear if Tl isotope measurements are a viable means to establish the origin of cratonic eclogites.

Investigation of thallium fluxes from subaerial volcanism—Implications for the present and past mass balance of thallium in the oceans

A suite of 34 volcanic gas condensates and particulates from Kilauea (Hawaii), Mt. Etna and Vulcano (Italy), Mt. Merapi (Indonesia), White Island and Mt. Nguaruhoe (New Zealand) were analysed for both Tl isotope compositions and Tl/Pb ratios. When considered together with published Tl–Pb abundance data, the measurements provide globally representative best estimates of Tl/Pb = 0.46 ± 0.25 and ε 205Tl = −1.7 ± 2.0 for the emissions of subaerial volcanism to the atmosphere and oceans (ε 205Tl is the deviation of the 205Tl/ 203Tl isotope ratio from NIST SRM 997 isotope standard in parts per 10,000). Compared to igneous rocks of the crust and mantle, volcanic gases were found to have (i) Tl/Pb ratios that are typically about an order of magnitude higher, and (ii) significantly more variable Tl isotope compositions but a mean ε 205Tl value that is indistinguishable from estimates for the Earth’s mantle and continental crust. The first observation can be explained by the more volatile nature of Tl compared to Pb during the production of volcanic gases, whilst the second reflects the contrasting and approximately balanced isotope fractionation effects that are generated by partial evaporation of Tl during magma degassing and partial Tl condensation as a result of the cooling and differentiation of volcanic gases. Mass balance calculations, based on results from this and other recent Tl isotope studies, were carried out to investigate whether temporal changes in the volcanic Tl fluxes could be responsible for the dramatic shift in the ε 205Tl value of the oceans at ∼55 Ma, which has been inferred from Tl isotope time series data for ferromanganese crusts. The calculations demonstrate that even large changes in the marine Tl input fluxes from volcanism and other sources are unable to significantly alter the Tl isotope composition of the oceans. Based on modelling, it is shown that the large inferred change in the ε 205Tl value of seawater is best explained if the oceans of the early Cenozoic featured significantly larger Tl output fluxes to oxic pelagic sediments, whilst the sink fluxes to altered ocean crust remained approximately constant.

Thallium isotope evidence for a permanent increase in marine organic carbon export in the early Eocene

The first high resolution thallium (Tl) isotope records in two ferromanganese crusts (Fe–Mn crusts), CD29 and D11 from the Pacific Ocean are presented. The crusts record pronounced but systematic changes in 205Tl/ 203Tl that are unlikely to reflect diagenetic overprinting or changes in isotope fractionation between seawater and Fe–Mn crusts. It appears more likely that the Fe–Mn crusts track the Tl isotope composition of seawater over time. The present-day oceanic residence time of Tl is estimated to be about 20,000 yr, such that the isotopic composition should reflect ocean-wide events. New and published Os isotope data are used to construct age models for these crusts that are consistent with each other and significantly different from previous age models. Application of these age models reveals that the Tl isotope composition of seawater changed systematically between ~ 55 Ma and ~ 45 Ma. Using a simple box model it is shown that the present day Tl isotope composition of seawater depends almost exclusively on the ratio between the two principal output fluxes of marine Tl. These fluxes are the rate of removal of Tl from seawater via scavenging by authigenic Fe–Mn oxyhydroxide precipitation and the uptake rate of Tl during low temperature alteration of oceanic crust. It is highly unlikely that the latter has changed greatly. Therefore, assuming that the marine Tl budget has also not changed significantly during the Cenozoic, the low 205Tl/ 203Tl during the Paleocene is best explained by a more than four-fold higher sequestration of Tl by Fe–Mn oxyhydroxides compared with at the present day. The calculated Cenozoic Tl isotopic seawater curve displays a striking similarity to that of S, providing evidence that both systems may have responded to the same change in the marine environment. A plausible explanation is a marked and permanent increase in organic carbon export from ~ 55 Ma to ~ 45 Ma, which led to higher pyrite burial rates and a significantly reduced flux of Fe–Mn oxide removal as a result of increased biological uptake of Fe and Mn.

Lead Isotope Homogeneity of NIST SRM 610 and 612 Glass Reference Materials: Constraints from Laser Ablation Multicollector ICP‐MS (LA‐MC‐ICP‐MS) Analysis

This contribution presents data for laser ablation multicollector ICP‐MS (LA‐MC‐ICP‐MS) analyses of NIST SRM 610 and 612 glasses with the express purpose of examining the Pb isotope homogeneity of these glasses at the ∼ 100 μm spatial scale, relevant to in situ analysis. Investigation of homogeneity at these scales is important as these glasses are widely used as calibrators for in situ measurements of Pb isotope composition. Results showed that at the levels of analytical uncertainty obtained, there was no discernable heterogeneity in Pb isotope composition of NIST SRM 610 and also most probably for NIST SRM 612. Traverses across the ∼ 1.5 mm glass wafers supplied by NIST, consisting of between 75 and 133 individual measurements, showed no compositional outliers at the two standard deviation level beyond those expected from population statistics. Overall, the measured Pb isotope ratios from individual traverses across NIST SRM 610 and 612 wafers closely approximate single normally‐distributed populations, with standard deviations similar to the average internal uncertainty for individual measurement blocks. Further, Pb isotope ratios do not correlate with Tl/Pb ratios measured during the analysis, suggesting that regions of volatile element depletion (marked by low Tl/Pb) in these glasses are not associated with changes in Pb isotope composition. For NIST SRM 610 there also appeared to be no variation in Pb isotope composition related to incomplete mixing of glass base and trace element spike during manufacture. For NIST SRM 612 there was some dispersion of measured ratios, including some in a direction parallel to the expected mixing line for base‐spike mixing. However, there was no significant correlation parallel to the mixing line. At this time this cannot be unequivocally demonstrated to result from glass heterogeneity, but it is suggested that NIST SRM 610 be preferred for standardising in situ Pb isotope measurements. Data from this study also showed significantly better accuracy and somewhat better precision for ratios corrected for mass bias by external normalisation to Pb isotope ratios measured in bracketing calibrators compared to mass bias corrected via internal normalisation to measured 205Tl/203Tl, although the Tl isotopic composition of both glasses appears to be homogeneous.