Mobility Of Elements Research Articles

New data on mobility of transuranium elements in sediments of the Yenisei River

The inflow of transuranium elements to the Yenisei River was previously associated with the production of weapons-grade plutonium at the Mining-and-Chemical Combine (MCC, Zheleznogorsk, Russia), but the source of transuranium elements in the River today is fabrication of MOX fuel that started recently at the MCC. The current study presents results of sequential chemical extraction of radionuclides from sediment samples collected in 2014 and 2020 in two areas near the MCC discharge site and compares these results with the data obtained previously by sequential extraction of sediments collected during 1999–2007. Over the study period, the strength of binding of 137Cs and 60Co in the Yenisei River sediments was high (up to 100%) and remained so, while the percentages of 241Am and 152Eu in residual solids after sequential extraction increased considerably and the percentage of 239,240Pu in residual solids decreased in samples from all study areas. In samples collected at the position located close to the MCC discharge site, the percentages of the strongly bound 241Am and 152Eu as well as 239,240Pu were lower than in the samples from the other positions. The study demonstrated an enormous increase in 239,240Pu activity concentration in the top sediment layers collected at all positions in 2020 relative to 2014. In the same period, as literature data suggest, 239,240Pu activity concentrations also increased in aquatic organisms of the Yenisei River, which can be indicative of the growing potential bioavailability of plutonium in the aquatic ecosystem, which could be caused by the presence of the mobile form of plutonium in the routine discharges from the MCC.

Downregulation of transposable elements extends lifespan in Caenorhabditis elegans

Mobility of transposable elements (TEs) frequently leads to insertional mutations in functional DNA regions. In the potentially immortal germline, TEs are effectively suppressed by the Piwi-piRNA pathway. However, in the genomes of ageing somatic cells lacking the effects of the pathway, TEs become increasingly mobile during the adult lifespan, and their activity is associated with genomic instability. Whether the progressively increasing mobilization of TEs is a cause or a consequence of ageing remains a fundamental problem in biology. Here we show that in the nematode Caenorhabditis elegans, the downregulation of active TE families extends lifespan. Ectopic activation of Piwi proteins in the soma also promotes longevity. Furthermore, DNA N6-adenine methylation at TE stretches gradually rises with age, and this epigenetic modification elevates their transcription as the animal ages. These results indicate that TEs represent a novel genetic determinant of ageing, and that N6-adenine methylation plays a pivotal role in ageing control.

Impure CO2 storage reactions of sandstone, mudstone and carbonate cemented cores: Experimental CO2 SO2 NOX O2 reaction metal mobilisation and fate

CO2 geological storage can be part of the solution to reduce carbon emissions to the atmosphere. An understanding of the geochemical processes occurring during CO2 storage is needed to reduce risk. Drill cores from a low salinity reservoir site proposed for CO2 storage, and the overlying and underlying formations, were characterised for minerals by QEMSCAN, total metals and porosity. Elements including Li, Ba, Sr, K, Mg, V, Zn, REE, Fe, Pb, P, and S were relatively elevated in the Moolayember Formation underlying the reservoir. Synchrotron XFM showed the main host of Mn was siderite, with Rb in K-feldspar, Zn and Cu in sphalerite and chalcopyrite, and As in pyrite in coal pores associated with coal laminations. Drill cores are reacted at reservoir conditions with synthetic formation water and an impure CO2 stream composition of CO2-SOx-NOx-O2 expected to be injected at the site. Elements released were dependant on mineral content, with quartz rich reservoir, lower Precipice Sandstone core reactions resulting in dissolution of trace carbonates, alteration of sulphides and monazite, and variable elevated dissolved Pb, and U. Dissolved Co, Ni, Ca, Zn, Li, Rb, and U were released at relatively elevated concentrations from the mudstone. For carbonate cemented upper Precipice Sandstone or Moolayember Formation core strong dissolution of calcite and ankerite, with corrosion of siderite, Fe-rich chlorite, and sulphides or monazite were observed after reaction. Dissolved elements including Ca, Mg, Mn, Sr, and Ba increased in experiments from the reaction of calcite, siderite, and ankerite. Generally dissolved Fe, Pb, Cr, Cu, Co etc. increased from dissolution, and subsequently decreased in concentration with adsorption and precipitation processes. The fast mobilisation of elements including Fe and Pb are consistent with the release of metals from carbonate dissolution and desorption. The presence of O2 and NOX in the gas stream results in Fe-(oxyhydr)oxide precipitation especially where Fe has been rapidly mobilised from dissolution of siderite and Fe-chlorite. This acts as a sink for Fe and provides new adsorption sites for sequestering a proportion of the trace metals. These processes are applicable to other CO2 storage sites and potential leakage indicators in overlying drinking water aquifers. The findings are also more broadly applicable to subsurface energy storage such as compressed air renewable energy storage, CO2 enhanced recovery, geothermal, natural gas or hydrogen storage.

Response of Sm–Nd isotope systematics to complex thermal histories: A case study from 3.58 Ga gneisses of the Pilbara Craton

In felsic igneous rocks, the parent and daughter elements in the widely used Sm–Nd and Lu–Hf isotope tracer systems are mainly hosted in accessory phases. Recrystallisation and/or breakdown of these minerals during metamorphism, deformation and weathering potentially compromises the chemical and isotopic composition of the respective whole rocks, impeding the utility of such information for deducing the timing, rates and processes of crust-mantle differentiation in the early Earth. The different abilities of zircon and REE-rich minerals to withstand metamorphism have been suggested as a reason for the decoupling of the Lu–Hf and Sm–Nd isotope systems observed in a number of ancient gneiss terranes. The controls on element mobility and subsequent isotopic disturbance during recrystallisation and breakdown of LREE-rich accessory minerals are, however incompletely understood. Here, we use petrography, element mapping, and microanalysis of accessory minerals, in tandem with whole rock Sm–Nd data, to assess the reliability of the Sm–Nd system in the 3.59–3.58 Ga Mount Webber Gabbros, the oldest rocks in the Pilbara Craton (Western Australia). We show that despite multiple thermal events, which reset the mineral Sm–Nd systematics, and decomposition of the REE-rich mineral allanite, the Mount Webber rocks retained the Sm–Nd isotope signatures of their magmatic protoliths at the whole-rock scale. We show that the allanite breakdown occurred during modern, near-surface weathering processes at low temperature, such that the REE were sequestered into secondary minerals rather than escaping in higher temperature metamorphic fluids. The whole rock Sm–Nd, and zircon O–Hf signatures, together with new 142Nd isotope data, suggest derivation of the Mount Webber rocks from undifferentiated mantle sources that preserve no evidence for Hadean silicate Earth differentiation. This study highlights the benefits of a combined analytical approach using both in-situ and whole-rock isotope analyses to obtain a more complete record of the source and thermal evolution of ancient, highly metamorphosed igneous rocks.

Reference LINE-1 insertion polymorphisms correlate with Parkinson’s disease progression and differential transcript expression in the PPMI cohort

Long interspersed nuclear element-1 (LINE-1/L1) retrotransposons make up 17% of the human genome. They represent one class of transposable elements with the capacity to both mobilize autonomously and in trans via the mobilization of other elements, primarily Alu and SVA elements. Reference LINE-1 elements are, by definition, found in the reference genome, however, due to the polymorphic nature of these elements, variation for presence or absence is present within the population. We used a combination of clinical and transcriptomic data from the Parkinson’s Progression Markers Initiative (PPMI) and applied matrix expression quantitative trait loci analysis and linear mixed-effects models involving 114 clinical, biochemical and imaging data from the PPMI cohort to elucidate the role of reference LINE-1 insertion polymorphism on both gene expression genome-wide and progression of Parkinson’s disease (PD). We demonstrate that most LINE-1 insertion polymorphisms are capable of regulating gene expression, preferentially in trans, including previously identified PD risk loci. In addition, we show that 70 LINE-1 elements were associated with longitudinal changes of at least one PD progression marker, including ipsilateral count density ratio and UPDRS scores which are indicators of degeneration and severity. In conclusion, this study highlights the effect of the polymorphic nature of LINE-1 retrotransposons on gene regulation and progression of PD which underlines the importance of analyzing transposable elements within complex diseases.

Comparative assessment of bacterial diversity and composition in arsenic hyperaccumulator, Pteris vittata L. and non-accumulator, Pteris ensiformis Burm

The use of arsenic (As) for various industrial and agricultural applications has led to worldwide environmental contamination. Phytoremediation using hyperaccumulators is a sustainable soil As mitigation strategy. Microbial processes play an important role in the tolerance and uptake of trace elements such as in plants. The rhizospheric and endophytic microbial communities are responsible for accelerating the mobility of trace elements around the roots and the production of plant growth-promoting compounds and enzymes. Several studies have reported that the As hyperaccumulator, Pteris vittata L. (PV) influences the microbial community in its rhizosphere and roots. Deciphering the differences in the microbiomes of hyperaccumulators and non-accumulators is crucial in understanding the mechanism of hyperaccumulation. We hypothesized that there are significant differences in the microbiome of roots, rhizospheric soil, and bulk soil between the hyperaccumulator PV and a non-accumulator of the same genus, Pteris ensiformis Burm. (PE), and that the differential recruitment of bacterial communities provides PV with an advantage in As contaminated soil. We compared root endophytic, rhizospheric, and bulk soil microbial communities between PV and PE species grown in As-contaminated soil in a greenhouse setting. There was a significant difference (p < 0.001) in the microbiome of the three compartments between the ferns. Differential abundance analysis showed 328 Amplicon Sequence Variants (ASVs) enriched in PV compared to 172 in PE. The bulk and rhizospheric soil of both ferns were abundant in As-resistant genera. However, As-tolerant root endophytic genera were present in PV but absent in PE. Our findings show that there is a difference between the bacterial composition of an As hyperaccumulator and a non-accumulator species grown in As-contaminated soil. These differences need to be further explored to develop strategies for improving the efficiency of metal uptake in plants growing in As polluted soil.

Insights into mineralogical distribution mechanism and environmental significance from geochemical behavior of sediments in the Yellow River Basin, China

Mineralogical investigations on fluvial sedimentary sequences could provide historical environmental information on the effects of human activities and natural events. This study aims to identify the mineralogical distribution mechanism and environmental significance of sediments of the Yellow River Basin based on topographic analysis, statistics, weathering and recycling indices. In total, 107 samples were collected from sedimentary sequences in the source area, and the upper, middle, and lower reaches and analyzed for grain size, major elements, and mineral composition. The results showed that the climate conditions were cold and arid, where weak hydrolysis under continental weathering and strong erosion accelerated physical weathering. Clay minerals in the upper reaches primarily originated from the Tibetan Plateau, whereas the middle and lower reaches received input of aeolian deposits from Northern China. Quartz and feldspar in the middle and lower reaches may derive from the source area and upper reaches. Meanwhile, calcite and dolomite formed through diagenesis, with loess input from the Chinese Loess Plateau. Regarding heavy minerals, the dominant determinative factors of pyrite were post-depositional diagenesis and leaching. Hematite and amphibole primarily formed through magnetite conversion and contribution from regional sources, respectively. Moreover, the mineral distribution mechanism significantly affected the mobility and distribution of geochemical elements through diagenesis and alteration. The findings are instrumental in reconstructing the environmental evolution of large-scale watersheds across multiple climatic zones.

Geochemistry and mineralogy of a spodumene-pegmatite lithium ore at various mineral beneficiation stages

Spodumene is currently the main source of lithium (Li), and Li release in mine waters stands out as a common feature of the otherwise scarcely studied spodumene mine tailings. In order to study how mineral beneficiation affects the geochemical behavior of a pegmatitic spodumene ore and the quality of its drainage, materials from the Whabouchi mine project (Québec, Canada) were submitted to advanced mineralogical characterization and kinetic testing in columns and weathering cells. Materials were sampled at various pilot processing steps, from raw ore to concentrator feed and tailings from dense medium separation and spodumene flotation. Processing did not modify markedly the chemical composition of the minerals and the mineralogical assemblage, except the spodumene content. Besides the major quartz, feldspars, spodumene, and muscovite, many accessory minerals were identified including Nb-Ta oxides and U-bearing minerals. Kinetic testing results indicate that all the studied materials produce neutral to slightly alkaline leachates (pH 7–8). Generally, elemental concentrations decrease rapidly over the first few flushes, are higher in columns than in weathering cells, and are higher for finer-grained processed materials. Elemental mobility is not necessarily proportional to bulk-rock abundance and liquid-to-solid ratio, overall following the order Ca (10 s of mg/L) > Na, K (10 s of mg/L to sub-mg/L) > Li, U (mg to sub-mg/L) > Mn, Fe, Al (sub-mg/L). Uranium mobility seems linked to scattered Ca-uranyl-(Si or P)-bearing voids and fracture-filling soluble minerals rather than primary uraninite, and Ca-uranyl-carbonate complexation is suggested as a promoting factor. Thermodynamic equilibrium calculations only identify clay minerals and metal (hydr)oxides as possible secondary minerals; formation of Al and Fe colloids is experimentally evidenced. Specific surface area and rinsing volume-normalized release rates, however, highlight effects of both processing and the testing protocol on the reactivity of the studied materials. The most processed material studied, flotation tailings, consistently produced the lowest normalized release rates for all the elements surveyed, while the most aggressive testing protocol (weathering cells, with frequent flushes at a high liquid-to-solid ratio) always yielded the highest normalized release rates. This laboratory-scale study outlines how mineralogy (both major and trace), processing, and testing protocol, affect the geochemical behavior of pegmatitic spodumene ore and tailings.

Rock glaciers in the Central Eastern Alps – How permafrost degradation can cause acid rock drainage, mobilization of toxic elements and formation of basaluminite

Rock glaciers in the Central Eastern Alps – How permafrost degradation can cause acid rock drainage, mobilization of toxic elements and formation of basaluminite

Transforming the untransformable with knockout minicircles: High-efficiency transformation and vector-free allelic exchange knockout in the fish pathogen Photobacterium damselae.

Gene inactivation studies are critical in pathogenic bacteria, where insights into species biology can guide the development of vaccines and treatments. Allelic exchange via homologous recombination is a generic method of targeted gene editing in bacteria. However, generally applicable protocols are lacking, and suboptimal approaches are often used for nonstandard but epidemiologically important species. Photobacterium damselae subsp. piscicida (Pdp) is a primary pathogen of fish in aquaculture and has been considered hard to transform since the mid-1990s. Consequently, conjugative transfer of RK2/RP4 suicide vectors from Escherichiacoli S17-1/SM10 donor strains, a system prone to off-target mutagenesis, was used to deliver the allelic exchange DNA in previous studies. Here we have achieved efficient electrotransformation in Pdp using a salt-free highly concentrated sucrose solution, which performs as a hypertonic wash buffer, cryoprotectant, and electroporation buffer. High-efficiency transformation has enabled vector-free mutagenesis for which we have employed circular minimalistic constructs (knockout minicircles) containing only allelic exchange essentials that were generated by Gibson assembly. Preparation of competent cells using sucrose and electroporation/integration of minicircles had virtually no detectable off-target promutagenic effect. In contrast, a downstream sacB selection apparently induced several large deletions via mobilization of transposable elements. Electroporation of minicircles into sucrose-treated cells is a versatile broadly applicable approach that may facilitate allelic exchange in a wide range of microbial species. The method permitted inactivation of a primary virulence factor unique to Pdp, apoptogenic toxin AIP56, demonstrating the efficacy of minicircles for difficult KO targets located on the high copy number of small plasmids.

New constraints on fluid chemistry and elemental mobility during hydrothermal alteration from thallium isotope systematics of the battle mountain district, North-central Nevada

The Battle Mountain area is a major porphyry style Au (–Cu) district in northern Nevada, forming one end of the Battle Mountain-Eureka mineral trend. This trend, along with several others in the north-central Nevada region, hosts some of the world's most prolific gold mineralization, which is oftentimes associated with a suite of trace elements including arsenic, antimony, tungsten, and thallium and can be related to or overprinted by hydrothermal alteration. However, determining the extent of control hydrothermal fluids exert on some of the deposits in the region has been difficult to ascertain. One of the associated trace metals in the region, thallium (Tl), is a highly incompatible element and, as such, dominantly resides in the continental crust, where it can be easily remobilized during hydrothermal alteration. While previous work has demonstrated the effects of hydrothermal alteration on Tl distribution and fractionation, the controls responsible for the observed Tl fractionation during hydrothermal alteration are still poorly characterized but may provide insight into fluid behavior. Here, we present new Tl isotope composition and concentration data for a suite of 54 mineral separates obtained from 43 samples from the Battle Mountain area, which range from unaltered intrusive igneous rocks through varying types and degrees of hydrothermally altered rocks.Measured Tl concentrations vary by more than an order of magnitude, from below detection limit (0.2 ppm in this study) to 2.0 ppm, while ε205Tl ranges between −5.0 and +2.2 (ε205Tl is the deviation of the 205Tl/203Tl isotope ratio of a sample from a standard in parts per 104). Thallium concentrations correlate positively with whole-rock potassium (K), thus show strong increases during K alteration, and demonstrate significantly lower ε205Tl values within K-altered samples. Conversely, during later, overprinting Na–Ca alteration, both K and Tl are removed, resulting in a noted decrease in Tl concentrations coupled with a shift to significantly higher ε205Tl values. It appears that during hydrothermal alteration, 203Tl is more easily (re)mobilized and (re)distributed, which reflects: 1) a first-order hydrothermal alteration control that relates to the transport of Tl during the formation of a new, metasomatic mineral assemblage (particularly the breakdown and/or formation of K-bearing minerals) and 2) a second-order mineralogical control, relating to inter-mineral equilibrium, which also results in a small fractionation effect.

Assessment of environmental parameters effect on potentially toxic elements mobility in foreshore sediments to support marine-coastal contamination prediction

Potentially toxic elements (PTEs) presence in marine sediments can significantly affect the environmental quality and negatively influence economy and recreational activities in related areas. Accordingly, contamination monitoring and control in the marine environment is a fundamental task. In this work, four PTEs behavior (i.e. As, Hg, Pb, and Zn) in sandy foreshore sediments (SFSs) was thoroughly investigated at different pH, redox potential and temperature conditions of the marine water. For all the tests, the released As was 2.7–6 times higher than its initial concentration in water. Nonetheless, final mass balances showed that preferential release in the liquid phase occurred for Pb and Hg (up to 10 % and 9.1 %, respectively). Moreover, final Zn and Hg content increase in SFSs labile fractions indicated their higher bioavailability after the tests. The obtained results outline an approach useful to predict the contaminants behavior in marine matrices and support environmental monitoring and preservation strategies.

The role of root carboxylate release on rare earth element (hyper)accumulation in plants – a biogeochemical perspective on rhizosphere chemistry

AbstractThe paper of van der Ent et al. (Plant Soil 485:247–257, 2023), published in the previous issue, reports the hyperaccumulation of rare earth elements (REE) in plant species from the Proteaceae for the first time. Indeed, the high REE accumulation in Proteaceae is not completely unexpected, given that the plants release large amounts of carboxylates to acquire phosphorus and micronutrients. However, it is somewhat questionable that the efficiency of element mobilization alone sufficiently explains the large variability in REE accumulation among different taxa of Proteaceae or other P-efficient species that typically show low concentrations of REE. Given that REE3+ share chemical similarities to Ca2+ but form stable complexes with ligands similar to Al3+, it is reasonable that uptake and accumulation of REE depend not solely on element mobility but also on the dynamics of element speciation governed by the formation, stability, and fate of carboxylate-REE-complexes in the rhizosheaths. The rationale behind this contention is that for elements with low mobility in soil, changes in chemical speciation may increase the availability only if the complex stabilities that depend on rhizosphere pH allow a breakdown during uptake. In this commentary, we explore the idea that REE accumulation depends on rhizosphere processes related to nutrient acquisition and element exclusion that overlap in time, space, and function depending on the composition of metal-chelating ligands released by plant roots in concert with rhizosphere pH. Based on data from greenhouse and field experiments, we propose a model where plants with a P-mining strategy (hyper)accumulate REE when rhizosphere pH is below a critical value shifting the REE speciation to available forms.

A novel method for in situ imaging of root exudates and labile elements reveals phosphorus deficiency-induced mobilization of rare earth elements in the rhizosphere of Phytolacca americana

A novel method for in situ imaging of root exudates and labile elements reveals phosphorus deficiency-induced mobilization of rare earth elements in the rhizosphere of Phytolacca americana

Online data resource for exploring transposon insertion polymorphisms in public soybean germplasm accessions.

Soybean (Glycine max L. Merrill) is one of the most important economical crops. A large number of whole-genome resequencing datasets have been generated and are increasingly expanded for exploring genetic diversity and mining important quantitative trait loci. Most genome-wide association studies have focused on single-nucleotide polymorphisms, short insertions, and deletions. Nevertheless, structure variants mainly caused by transposon element mobilization are not fully considered. To fill this gap, we uniformly processed the publicly available whole-genome resequencing data from 5,521 soybean germplasm accessions and built an online soybean transposon insertion polymorphisms database named Soybean Transposon Insertion Polymorphisms Database (SoyTIPdb) (https://biotec.njau.edu.cn/soytipdb). The collected germplasm accessions derived from more than 45 countries and 160 regions representing the most comprehensive genetic diversity of soybean. SoyTIPdb implements easy-to-use query, analysis, and browse functions to help understand and find meaningful structural variations from TE insertions. In conclusion, SoyTIPdb is a valuable data resource and will help soybean breeders/researchers take advantage of the whole-genome sequencing datasets available in the public depositories.

Modified open-system hydrous pyrolysis

As an alternative to classic batch hydrous pyrolysis experiments, this proof-of-concept study presents a version of open-system hydrous pyrolysis (OSHP) in which the design of the apparatus allows for a small, continuous flow of only liquid-phase water to pass through the reactor during artificial maturation. This allows volatile, liquid, and soluble materials to migrate freely through and out of the system, whereas insoluble mineral matter and kerogen remain within the reactor. This apparatus differs from previous OSHP designs in the ability to maintain true open-system conditions, thus minimizing any cracking or back reaction of the products with the residual kerogen.Using the OSHP apparatus, immature Anna Shale (Pennsylvanian age, Illinois Basin) containing Type II marine kerogen was matured artificially at experimental temperatures ranging from 300 to 360 °C for up to 72 h. Petrographically, the immature Anna Shale is dominated by a micrinitic groundmass, and contains lesser amounts of vitrinite (both collotelinite and collodetrinite), inertodetrinite, bituminite, solid bitumen, and alginite. Under run conditions, mean random reflectance increased from 0.46 to 1.81% for vitrinite and from 0.66% to 1.50% for solid bitumen. Alginite fluorescence changed from a bright yellow to dull red-orange and decreased in intensity until all fluorescence was lost in shales pyrolyzed at temperatures ≥350 °C. Rock-Eval Tmax increased from 425° to 520 °C, TOC decreased (e.g., from 12.5% to ∼9% at a run temperature of 360 °C), S1 decreased from 0.71 to ∼ < 0.1 mg HC/g shale, S2 decreased from ∼40 to <1.0 mg HC/g shale, and HI decreased from ∼300 to <10 mg HC/g TOC. These changes are consistent with the maturation of the immature shale through the oil window and into the gas window. With increased maturity, the shale showed a loss in mass: shorter runs (≤ 24 h) typically lost <10%, whereas longer runs (72 h) lost 12–20%. These losses were likely due to the loss of moisture, liberation of hydrocarbons and other gases, and depletion in total sulfur from 2.03 to ∼0.1 wt% (much of which was pyritic sulfur); higher mass losses may have included retention of material in the reactor, tubing, or frits. Petrographic observations revealed that pyrite framboids, which were abundant in the immature shale, decreased in samples pyrolyzed at temperatures >330 °C and showed evidence of alteration to hematite.The OSHP design was intended to mimic normal burial maturation. However, based on the significant depletion in sulfur (i.e., pyrite), the current design and run parameters may more closely replicate conditions associated with hydrothermal alteration, possibly those associated with intrusion of organic-rich rocks. It is also possible that the OSHP approach could lead to a better understanding of organic-mineral interactions and mobility of elements, especially trace elements, during maturation.

Mobility of the Major and Trace Elements in the Coal Mining Wastes

Domestic and foreign static tests are considered to assess the impact of mineral waste from coal mining and processing on water objects when waste is placed in dumps or used for reclamation purposes. The results of static tests according to GOST R 58914–2020 for three samples of mineral waste taken from hard and brown coal deposits are presented. The wastes differ significantly in mineral and chemical composition, including sulfur content. It is shown that the high content of sulfur in the waste, including it in a water-soluble form, determines the low pH value of the aqueous extract. This, in turn, leads to an increase in the yield of water-soluble substances and to an increase in the mobility of major and trace elements.

Early diagenetic mobilization of rare earth elements and implications for the Ce anomaly as a redox proxy

The Rare Earth Elements (REE) archived in carbonate rocks retain a wealth of information on paleo-seawater chemistry and local-regional redox conditions. However, interpretations are often ambiguous due to the potential for REE remobilization in marine environments. In this regard, many carbonate rocks that retain primary seawater isotopic signatures exhibit non-seawater-like REE patterns, implying either unusual REE behaviour in seawater or diagenetic overprinting of otherwise well-preserved rock samples. Here, we apply sequential leaching to constrain the possible effects of different REE-bearing phases on measured carbonate REE patterns in order to address this quandary. Our results show that the exchangeable phase contains negligible REE, but could be an important host phase for other elements such as Sr, Ba and K. The acidified hydroxylamine hydrochloride leach is shown here not only to dissolve Fe–Mn oxides but also phosphate minerals, which induces middle REE enrichment in corresponding leachates of dolostone samples in our study. The demonstrable Fe–Mn oxide phase in limestone samples is characterized by middle and/or light REE enrichment and positive Eu anomalies, which are attributed to hydrothermal processes and continuing exchange with marine fluids after initial precipitation. The non-seawater-like REE patterns observed in the carbonate phase of otherwise well-preserved limestones resemble those of the co-existing Fe–Mn oxide fraction, and are interpreted to reflect the dissolution of REE carrier phases during early diagenesis. This view is supported by fluid-rock interaction modelling, which shows how REE can be mobilized at relatively low fluid/rock ratios in shallow porewaters. Non-seawater-like REE patterns may therefore be caused by the incorporation of REE from shallow porewaters before final lithification due to an elevated flux of particulate REE carrier phases, e.g. Fe–Mn oxides and organic matter, to the seafloor. In spite of the sensitivity of carbonate REE patterns to early diagenetic exchange, the co-occurrence of non-seawater-like patterns with primary strontium and carbon isotope values suggests that REE should not be viewed as a general indicator for the preservation of other geochemical proxies. Importantly, Ce anomalies of the carbonate phase will also be affected by porewaters, masking primary seawater values. Our results favour a reevaluation of redox interpretations by taking into account REE patterns as a whole.

Fluid mobilization of rare earth elements, Th, and U during the terrestrial alteration of H chondrites

AbstractThe chemical effects of terrestrial alteration, with a particular focus on lithophile trace elements, were studied for a set of H chondrites displaying various degrees of weathering from fresh falls to altered finds collected from hot deserts. According to their trace element distributions, a considerable fraction of rare earth elements (REEs), Th, and U resides within cracks observed in weathered meteorite specimens. These cracks appear to accumulate unbound REEs locally accompanied by Th and U relative to the major element abundances, especially P and Si. The deposition of Ce is observed in cracks in the case of most of the weathered samples. Trace element maps visually confirm the accumulation of these elements in such cracks, as previously inferred based on chemical leaching experiments. Because the positive Ce anomalies and unbound REE depositions in cracks occur in all weathered samples studied here while none of such features are observed in less altered samples including falls (except for altered fall sample Nuevo Mercurio), these features are interpreted to have been caused by terrestrial weathering following chemical leaching. However, the overall effects on the bulk chemical composition remain limited as the data for all Antarctic meteorites studied in this work (except for heavily weathered sample A 09516, H6) are in good agreement with published data for unaltered meteorites.

Element dissolution from Zn-bearing rocks treated with chemical and biotic agents: A prospective circular economy strategy for metal recovery from secondary resources

Calamine susceptibility to dissolution requires a detailed experimental evaluation to uncover an alternative management option for these materials. This study aimed to investigate the (bio)leaching behaviours of Zn/Pb-bearing calamines to quantify their potential as a Zn resource. Chemical treatments, including the application of mineral (H2SO4, HCl and HNO3) and organic acids (citric and oxalic acids), along with biotic treatments involving the bacteria Acidithiobacillus thiooxidans and Pseudomonas fluorescens, were used to analyse the mobilisation mechanisms, namely acidification and complexation. The results showed that HCl and HNO3 were the most efficient chemical agents, with an extraction efficiency as high as 39 % (Zn). A. thiooxidans extracted the largest amount of Zn (40 %), which proves that the efficiency of the biotic process can be nearly the same as that of the chemical process. However, the main mechanism governing element mobility was the pH factor. This study shows the potential of calamines as prospective materials for the recovery of Zn and other elements (Ge, Tl), even in those treatment conditions that require further optimisation.