Anthropogenic Forcing of the Baltic Sea Thallium Cycle.

Anthropogenic activities have fundamentally changed the chemistry of the Baltic Sea. According to results reported in this study, not even the thallium (Tl) isotope cycle is immune to these activities. In the anoxic and sulfidic ("euxinic") East Gotland Basin today, Tl and its two stable isotopes are cycled between waters and sediments as predicted based on studies of other redox-stratified basins (e.g., the Black Sea and Cariaco Trench). The Baltic seawater Tl isotope composition (ε205Tl) is, however, higher than predicted based on the results of conservative mixing calculations. Data from a short sediment core from East Gotland Basin demonstrates that this high seawater ε205Tl value originated sometime between about 1940 and 1947 CE, around the same time other prominent anthropogenic signatures begin to appear in the same core. This juxtaposition is unlikely to be coincidental and suggests that human activities in the surrounding area have altered the seawater Tl isotope mass-balance of the Baltic Sea.

Protracted oxygenation across the Cambrian-Ordovician transition: A key initiator of the Great Ordovician Biodiversification Event?

Fluctuations in marine oxygen concentrations have been invoked as a primary driver for changes in biodiversity throughout Earth history. Expansions in reducing marine conditions are commonly invoked as key causal mechanisms for mass extinctions, while increases in marine oxygenation are becoming an increasingly common causal mechanism invoked for biodiversification events. Here we utilize a multiproxy approach to constrain local and global marine paleoredox conditions throughout the late Cambrian-Early Ordovician from two drill core successions in Baltoscandia. Local paleoredox proxies such as manganese concentrations and iron speciation reveal that both sites in the Baltic paleobasin had persistently anoxic and predominantly euxinic (anoxic and sulfidic) bottom water conditions throughout the study interval. Corresponding trace metal datasets indicate nuanced contraction and expansion of global anoxic and euxinic conditions along continental margins during the late Cambrian-Early Ordovician. Lastly, thallium isotope data from these locally reducing sections suggest a global expansion of oxygenated shelf and deeper marine environments from the late Cambrian into the Early Ordovician. This evidence for increasingly oxic marine environments coincides with increases in burrowing depth and tiering in marine animals, as well as diversification of body fossils throughout this ~8-million-year interval. The collective geochemical datasets provide some of the first direct paleoredox evidence for an increase in marine oxygen concentrations as a key mechanism for the Ordovician radiation of marine life.

Thallium isotopic compositions as tracers in environmental studies: A review.

Thallium is a highly poisonous heavy metal. Since Tl pollution control has been neglected worldwide until the present, countless Tl pollutants have been discharged into the environment, endangering the safety of drinking water, farmland soil, and food chain, and eventually posing a great threat to human health. However, the source, occurrence, pathway and fate of Tl in the environment remains understudied. As Tl in non-contaminated systems and from anthropogenic origin exhibits generally different isotopic signatures, which can provide fingerprint information and a novel way for tracing the anthropogenic Tl sources and understanding the environmental processes. This review summarizes: (i) the state-of-the-art development in highly-precise determination analytical method of Tl isotopic compositions, (ii) Tl isotopic fractionation induced by the low-temperature surface biogeochemical process, (iii) Tl isotopic signature of pollutants derived from anthropogenic activities and isotopic fractionation mechanism of Tl related to the high-temperature industrial activities, and (iv) application of Tl isotopic composition as a new tracer emerging tracer for source apportionment of Tl pollution. Finally, the limitations and possible future research about Tl isotopic application in environmental contamination is also proposed: (1) Tl fractionation mechanism in different environmental geochemistry processes and industrial activities should be further probed comprehensively; (2) Tl isotopes for source apportionment should be further applied in other different high Tl-contaminated scenarios (e.g., agricultural systems, water/sediment, and atmosphere).

Constraining oceanic oxygenation during the Shuram excursion in South China using thallium isotopes.

Ediacaran sediments record an unusual global carbon cycle perturbation that has been linked to widespread oceanic oxygenation, the Shuram negative C isotope excursion (NCIE). However, proxy-based estimates of global ocean redox conditions during this event have been limited largely due to proxy specificity (e.g., euxinic sediments for Mo and U isotopes). Modern global seawater documents a homogenous Tl isotope composition (ε205 Tl = -6.0) due to significant manganese oxide burial, which is recorded in modern euxinic sediments. Here, we provide new data documenting that sediments deposited beneath reducing but a non-sulfidic water column from the Santa Barbara Basin (ε205 Tl = -5.6 ± 0.1) also faithfully capture global seawater Tl isotope values. Thus, the proxy utilization of Tl isotopes can extend beyond strictly euxinic settings. Second, to better constrain the global redox conditions during the Shuram NCIE, we measured Tl isotopes of locally euxinic and ferruginous shales of the upper Doushantuo Formation, South China. The ε205 Tl values of these shales exhibit a decreasing trend from ≈-3 to ≈-8, broadly coinciding with the onset of Shuram NCIE. There are ε205 Tl values (-5.1 to -7.8) during the main Shuram NCIE interval that approach values more negative than modern global seawater. These results suggest that manganese oxide burial was near or even greater than modern burial fluxes, which is likely linked to an expansion of oxic conditions. This ocean oxygenation may have been an important trigger for the Shuram NCIE and evolution of Ediacaran-type biota. Subsequently, Tl isotopes show an increasing trend from the modern ocean value to values near the modern global inputs or even heavier (ε205 Tl ≈ -2.5 ~ 0.4), occurring prior to recovery from the NCIE. These records may suggest that there was a decrease in the extent of oxygenated conditions in the global oceans during the late stage of the Shuram NCIE.

Thallium isotopes reveal protracted anoxia during the Toarcian (Early Jurassic) associated with volcanism, carbon burial, and mass extinction.

For this study, we generated thallium (Tl) isotope records from two anoxic basins to track the earliest changes in global bottom water oxygen contents over the Toarcian Oceanic Anoxic Event (T-OAE; ∼183 Ma) of the Early Jurassic. The T-OAE, like other Mesozoic OAEs, has been interpreted as an expansion of marine oxygen depletion based on indirect methods such as organic-rich facies, carbon isotope excursions, and biological turnover. Our Tl isotope data, however, reveal explicit evidence for earlier global marine deoxygenation of ocean water, some 600 ka before the classically defined T-OAE. This antecedent deoxygenation occurs at the Pliensbachian/Toarcian boundary and is coeval with the onset of initial large igneous province (LIP) volcanism and the initiation of a marine mass extinction. Thallium isotopes are also perturbed during the T-OAE interval, as defined by carbon isotopes, reflecting a second deoxygenation event that coincides with the acme of elevated marine mass extinctions and the main phase of LIP volcanism. This suggests that the duration of widespread anoxic bottom waters was at least 1 million years in duration and spanned early to middle Toarcian time. Thus, the Tl data reveal a more nuanced record of marine oxygen depletion and its links to biological change during a period of climatic warming in Earth's past and highlight the role of oxygen depletion on past biological evolution.