A systematic look at chromium isotopes in modern shells – implications for paleo-environmental reconstructions

The chromium isotope system (53Cr&thinsp;∕&thinsp;52Cr, expressed as δ53Cr relative to NIST SRM 979) in marine biogenic and non-biogenic carbonates is currently being evaluated as a proxy for the redox state of the ocean. Previous work has concentrated on using corals and foraminifera for this purpose, but investigations focusing on the behavior of Cr in bivalves as potential archives are lacking. Due to their often good preservation, fossil marine biogenic carbonates have the potential to serve as useful archives for the reconstruction of past ocean redox fluctuations and eventually link those to climatic changes throughout Earth's history. Here, we present an evaluation of the Cr isotope system in shells of some modern bivalves. Shell species from Lucidinadae, Cardiidae, Glycimerididae and Pectenidae, collected systematically from one Mediterranean location (Playa Poniente, Benidorm, Spain) over a 3-year period reveal δ53Cr values ranging from 0.15&thinsp;‰ to 0.65&thinsp;‰, values that are systematically below the local seawater δ53Cr value of 0.83±0.05&thinsp;‰. This attests to a significant reduction of dissolved seawater chromium in the process leading to calcification and thus for control of Cr isotope fractionation during biological routes. A similar, constant offset in δ53Cr values relative to surface seawater is observed in shells from Mytilius edulis from an arctic location (Godhavn, Disko Bay, Greenland). Chromium concentrations in the studied shells are significantly controlled by organic matter and typically range from 0.020 to 0.100&thinsp;ppm, with some higher concentrations of up to 0.163&thinsp;ppm recorded in Pectenidae. We also observe subtle, species-dependent differences in average Cr isotope signatures in the samples from Playa Poniente, particularly of Lucidinadae and Cardiidae, with considerably depressed and elevated δ53Cr values, respectively, relative to the other species investigated. Intra-species heterogeneities, both in Cr concentrations and δ53Cr values, are favorably seen to result from vital effects during shell calcification rather than from heterogeneous seawater composition. This is because we observe that the surface seawater composition in the particular Playa Poniente location remained constant during the month of July of the 3 years we collected bivalve samples. Intra-shell heterogeneities – associated with growth zones reflecting one to several years of growth, both in δ53Cr and Cr concentrations – are observed in a sample of Placuna placenta and Mimachlamys townsendi. We suspect that these variations are, at least partially, related to seasonal changes in δ53Cr of surface seawaters. Recognizing the importance of organic substances in the bivalve shells, we propose a model whereby reduction of Cr(VI) originally contained in the seawater as chromate ion and transported to the calcifying space, to Cr(III), is effectively adsorbed onto organic macromolecules which eventually get included in the growing shell carbonates. This study, with its definition of statistically sound offsets in δ53Cr values of certain bivalve species from ambient seawater, forms a base for future investigations aimed at using fossil shells as archives for the reconstruction of paleo-seawater redox fluctuations.</p

Heterogeneity and incorporation of chromium isotopes in recent marine molluscs (Mytilus)

The mollusc genus Mytilus is abundant in various modern marine environments and is an important substrate for palaeo-proxy work. The redox-sensitive chromium (Cr) isotope system is emerging as a proxy for changes in the oxidation state of the Earth's atmosphere and oceans. However, potential isotopic offsets between ambient sea water and modern biogenic carbonates have yet to be constrained. We measured Cr concentrations ([Cr]) and isotope variations (δ53 Cr) in recent mollusc shells (Mytilus) from open and restricted marine environments and compared these to ambient sea water δ53 Cr values. We found a large range in mollusc [Cr] (12-309 ppb) and δ53 Cr values (-0.30 to +1.25‰) and in the offset between δ53 Cr values of mollusc shells and ambient sea water ( Δ53CrseawaterbulkMytilus , -0.17 to -0.91‰). Step digestions of cultivated Mytilus edulis specimens indicate that Cr is mainly concentrated in organic components of the shell (periostracum: 407 ppb, n = 2), whereas the mollusc carbonate minerals contain ≤3 ppb Cr. Analyses of individual Cr-hosting phases (i.e., carbonate minerals and organic matrix) did not reveal significant differences in δ53 Cr values, and thus, we suggest that Cr isotope fractionation may likely take place prior to rather than during biomineralisation of Mytilus shells. Heterogeneity of δ53 Cr values in mollusc shells depends on sea water chemistry (e.g., salinity, food availability, faeces). The main control for δ53 Cr values incorporated into shells, however, is likely vital effects (in particular shell valve closure time) since Cr can be partially or quantitatively reduced in sea water trapped between closed shell valves. The δ53 Cr values recorded in Mytilus shells may thus be de-coupled from the redox conditions of ambient sea water, introducing additional heterogeneity that needs to be better constrained before using δ53 Cr values in mollusc shells for palaeo-reconstructions.Sylvie Bruggmann, Robert M. Klaebe, Cora Paulukat, Robert Fre

Future food contaminants: An assessment of the plant uptake of Technology-critical elements versus traditional metal contaminants

Technology-critical elements (TCEs) include most rare earth elements (REEs), the platinum group elements (PGEs), and Ga, Ge, In, Nb, Ta, Te, and Tl. Despite increasing recognition of their prolific release into the environment, their soil to plant transfer remains largely unknown. This paper provides an approximation of the potential for plant uptake by calculating bioconcentration factors (BCFs), defined as the concentration in edible vegetable tissues relative to that in cultivation soil. Here data were obtained from an indoor cultivation experiment growing lettuce, chard, and carrot on 22 different European urban soils. Values of BCFs were determined from concentrations of TCEs in vegetable samples after digestion with concentrated HNO3, and from concentrations in soil determined after 1) Aqua Regia digestion and, 2) diluted (0.1 M) HNO3 leaching. For comparison, BCFs were also determined for 5 traditional metal contaminants (TMCs; As, Cd, Cu, Pb, and Zn). The main conclusions of the study were that: 1) BCF values for the REEs were consistently low in the studied vegetables; 2) the BCFs for Ga and Nb were low as well; 3) the BCFs for Tl were high relative to the other measured TCEs and the traditional metal contaminants; and 4) mean BCF values for the investigated TCEs were generally highest in chard and lowest in carrot. These findings provide initial evidence that there are likely to be real and present soil–plant transfer of TCEs, especially in the case of Tl. Improvements in analytical methods and detection limits will allow this to be further investigated in a wider variety of edible plants so that a risk profile may be developed

Urban vegetable contamination - The role of adhering particles and their significance for human exposure.

While urban-grown vegetables could help combat future food insecurity, the elevated levels of toxic metals in urban soils need to be met with measures that minimise transfer to crops. The study firstly examines soil/dust particle inclusion in leafy vegetables and its contribution to vegetable metals (As, Ba, Cd, Co, Cr, Cu, Ni, Pb, Sb, and Zn), using vegetable, soil and dust data from an open-field urban farm in southeastern Sweden. Titanium concentrations were used to assess soil/dust adherence. Results showed that vegetables contained 0.05-1.3 wt% of adhering particles (AP) even after washing. With 0.5 % AP, an adult with an average intake of vegetables could ingest approximately 100 mg of particles per day, highlighting leafy vegetables as a major route for soil/dust ingestion. The presence of adhering particles also significantly contributed to the vegetable concentrations of As (9-20 %), Co (17-20 %), Pb (25-29 %), and Cr (33-34 %). Secondly, data from an indoor experiment was used to characterise root metal uptake from 20 urban soils from Sweden, Denmark, Spain, the UK, and the Czech Republic. Combining particle adherence and root uptake data, vegetable metal concentrations were calculated for the 20 urban soils to represent hypothetical field scenarios for these. Subsequently, average daily doses were assessed for vegetable consumers (adults and 3-6 year old children), distinguishing between doses from adhering particles and root uptake. Risks were evaluated from hazard quotients (HQs; average daily doses/tolerable intakes). Lead was found to pose the greatest risk, where particle ingestion often resulted in HQs > 1 across all assessed scenarios. In summary, since washing was shown to remove only a portion of adhering metal-laden soil/dust particles from leafy vegetation, farmers and urban planners need to consider that measures to limit particle deposition are equally important as cultivating in uncontaminated soil. [Abstract copyright: Copyright © 2023. Published by Elsevier B.V.

IL-27 Regulates IL-18 Binding Protein in Skin Resident Cells

IL-18 is an important mediator involved in chronic inflammatory conditions such as cutaneous lupus erythematosus, psoriasis and chronic eczema. An imbalance between IL-18 and its endogenous antagonist IL-18 binding protein (BP) may account for increased IL-18 activity. IL-27 is a cytokine with dual function displaying pro- and anti-inflammatory properties. Here we provide evidence for a yet not described anti-inflammatory mode of action on skin resident cells. Human keratinocytes and surprisingly also fibroblasts (which do not produce any IL-18) show a robust, dose-dependent and highly inducible mRNA expression and secretion of IL-18BP upon IL-27 stimulation. Other IL-12 family members failed to induce IL-18BP. The production of IL-18BP peaked between 48–72 h after stimulation and was sustained for up to 96 h. Investigation of the signalling pathway showed that IL-27 activates STAT1 in human keratinocytes and that a proximal GAS site at the IL-18BP promoter is of importance for the functional activity of IL-27. The data are in support of a significant anti-inflammatory effect of IL-27 on skin resident cells. An important novel property of IL-27 in skin pathobiology may be to counter-regulate IL-18 activities by acting on keratinocytes and importantly also on dermal fibroblasts

Silicon and chromium stable isotopic systematics during basalt weathering and lateritisation: A comparison of variably weathered basalt profiles in the Deccan Traps, India

Global biomass production is fundamentally affected by the hydrological cycling of elements at the Earth's surface. Continental weathering processes are the major source for most bio-essential elements in marine environments and therefore affect primary productivity. In addition, critical zone biomass depends on energy and chemical exchange reactions in weathering profiles. The latter reservoirs are in turn influenced by different climatic conditions that control weathering and pore water parameters like pH and Eh, which regulate mineral break down rates and dictate the mobility and mass flux of elements. Two Deccan Traps basalt weathering profiles of contrasting age and alteration intensity provide a natural laboratory for investigating the effects of rock alteration on Si and Cr and their isotopic. systematics. The Quaternary Chhindwara profile has progressed to a moderate degree of alteration (saprolite), while the Paleogene Bidar example displays an extremely altered laterite. The Chhindwara saprolite profile shows a near uniform Cr and Si concentration and isotopic composition, whereas the Bidar laterite profile is characterised by an intense loss of Si, a large enrichment of Cr within the most altered uppermost levels, and a wide range of Cr stable isotope ratios (-0.85 to 0.36 parts per thousand delta Cr-53/52). A co-variation between Si and Cr isotopes, as well as their co-variation with iron content, provides empirical evidence that iron redistribution within the profile has a large effect on Cr mobility and Si isotopic fractionation. Therefore, it is concluded that iron oxides exert a primary control over the isotopic composition of both Cr and Si in pore waters of laterites. Since laterite formation is promoted by tropical climates, the results of this study provide new evidence to suggest that the hydrological Cr and Si fluxes originating from continental weathering have changed in accordance with large-scale, deep time climate variation and continental plate configuration. An increased flux of Si and greater magnitude of Cr mobility and isotopic fractionation are possibly amplified under CO2-rich, greenhouse episodes and/or when large landmasses were tectonically arranged at near equatorial latitudes

Chromium isotope fractionation between modern seawater and biogenic carbonates from the Great Barrier Reef, Australia: Implications for the paleo-seawater δ 53 Cr reconstruction

This study investigates chromium isotope variations (δ53Cr) and REE patterns in present-day biogenic carbonates and ocean waters from Lady Elliot Island (LEI) located in the southern Great Barrier Reef (GBR), Australia, which is one of the world's largest carbonate-producing shelf ecosystems. Our results from thoroughly cleaned biogenic carbonates collected at LEI, with no detectable evidence for lithogenic Cr and/or Mn–Fe oxide coating contamination, revealed a systematic and statistically significant correlation (r2=0.83, p<0.05) between δ53Cr and cerium anomaly (Ce/Ce*) data in molluscan shells (i.e., gastropods). This in turn implies a redox-controlled incorporation of Cr from seawater into a shell during mineralization mediated by the organism. In particular, shells with higher δ53Cr values, which approach the Cr isotope composition of local seawater, tend to be associated with more negative Ce/Ce*. Importantly, the intercept of the above δ53Cr vs. Ce/Ce* correlation points to the Cr isotope composition of local ocean water, which has an average δ53Cr of +0.82±0.13‰ (2σ relative to SRM 979). These findings thus indicate that the above multi-proxy approach could be used to reconstruct the δ53Cr signature of local paleo-seawater based on Ce/Ce* and δ53Cr data in a set of well-preserved fossil skeletal carbonates (i.e., molluscan shells) collected at a specific site. Interestingly, the only calcifying organism from LEI that yielded identical δ53Cr vs. Ce/Ce* values as those in ambient ocean water was a microbial calcitic carbonate produced by red coralline algae (Lithothamnion sp.). This organism thus seems to incorporate Cr isotopes and REE from seawater without additional biological discrimination and/or isotope fractionation effects. Considering that calcite is a more stable CaCO3 polymorph during post-depositional alternation and diagenetic stabilization of marine carbonates (compared to aragonite), the fossil counterparts of these algal-microbial carbonates (microbialites) might thus represent ideal natural archives of the paleo-seawater δ53Cr and Ce/Ce* variations over geological time. Finally, our compilation of δ53Cr data from recent marine biogenic carbonates originating from the main oceanic provinces (South/North Pacific, South/North Atlantic, Caribbean, Mediterranean Sea) confirms that marine carbonates tend to be systematically enriched in light Cr isotopes relative to local ocean waters. Trace element constraints, however, indicate that some of these shifts to lower δ53Cr values (i.e., approaching −0.1 per mil) are related to a presence of lithogenic Cr in the shells, causing a diagenetic overprint of the primary marine δ53Cr signal

Immune escape pathways from the HBV core_18-27 CD8 T cell response are driven by individual HLA class I alleles.

Background and aims: There is growing interest in T cell-based immune therapies for a functional cure of chronic HBV infection including check-point inhibition, T cell-targeted vaccines or TCR-grafted effector cells. All these approaches depend on recognition of HLA class I-presented viral peptides. The HBV core region 18-27 is an immunodominant target of CD8+ T cells and represents the prime target for T cell-based therapies. Here, a high-resolution analysis of the core18-27 specific CD8+ T cell and the selected escape pathways was performed. Methods: HLA class I typing and viral sequence analyses were performed for 464 patients with chronic HBV infection. HBV-specific CD8+ T-cell responses against the prototype and epitope variants were characterized by flow cytometry. Results: Consistent with promiscuous presentation of the core18-27 epitope, antigen-specific T cells were detected in patients carrying HLA-A*02:01, HLA-B*35:01, HLA-B*35:03 or HLA-B*51:01. Sequence analysis confirmed reproducible selection pressure on the core18-27 epitope in the context of these alleles. Interestingly, the selected immune escape pathways depend on the presenting HLA-class I-molecule. Although cross-reactive T cells were observed, some epitope variants achieved functional escape by impaired TCR-interaction or disturbed antigen processing. Of note, selection of epitope variants was exclusively observed in HBeAg negative HBV infection and here, detection of variants associated with significantly greater magnitude of the CD8 T cell response compared to absence of variants. Conclusion: The core18-27 epitope is highly variable and under heavy selection pressure in the context of different HLA class I-molecules. Some epitope variants showed evidence for impaired antigen processing and reduced presentation. Viruses carrying such escape substitutions will be less susceptible to CD8+ T cell responses and should be considered for T cell-based therapy strategies