Mono- and multimeric PSMA-targeting small molecule-thorium-227 conjugates for optimized efficacy and biodistribution in preclinical models.

PURPOSE: PSMA (prostate-specific membrane antigen) is highly expressed on prostate cancer (PrCa) cells and extensively used as a homing target for PrCa treatment. Most prominently, PSMA-targeting conjugate PSMA-617, carrying a DOTA chelator and labeled with therapeutic radionuclides like beta-emitting lutetium-177 or alpha-emitting actinium-225, has shown clinical activity in PrCa patients. We sought to develop PSMA-targeting small molecule (SMOL) conjugates that show high uptake in PSMA-expressing tumors and fast clearance, and can easily be labeled with the alpha emitter thorium-227 (half-life 18.7 days). METHODS: A novel linker motif with improved competition against 3H-PSMA-617 on PSMA-expressing LNCaP cells was identified. A 2,3-hydroxypyridinone chelator modified with carboxyl groups (carboxy-HOPO) with increased hydrophilicity and robust labeling with thorium-227 was developed and allowed the synthesis of mono-, di-, tri-, and tetrameric conjugates. The resulting monomeric and multimeric PSMA SMOL-TTCs (targeted thorium conjugate) were evaluated for cellular binding, internalization, and antiproliferative activity. The in vivo antitumor efficacy of the PSMA SMOL-TTCs was determined in ST1273 and KUCaP-1 PrCa models in mice, and their biodistribution was assessed in cynomolgus monkeys, minipigs, and mice. RESULTS: The monomeric and multimeric PSMA SMOL conjugates were readily labeled with thorium-227 at room temperature and possessed high stability and good binding, internalization, and antiproliferative activity in vitro. In vivo, the monomeric, dimeric, and trimeric PSMA SMOL-TTCs showed fast clearance, potent antitumor efficacy, and high uptake and retention in prostate tumors in mice. No major uptake or retention in other organs was observed beyond kidneys. Low uptake of free thorium-227 into bone confirmed high complex stability in vivo. Salivary gland uptake remained inconclusive as mini pigs were devalidated as a relevant model and imaging controls failed in cynomolgus monkeys. CONCLUSION: Monomeric and multimeric PSMA SMOL-TTCs show high tumor uptake and fast clearance in preclinical models and warrant further therapeutic exploration.

Thorium Alters Lung Surfactant Protein Expression in Alveolar Epithelial Cells: In Vitro and In Vivo Investigation.

Thorium-232 (Th), the most abundant naturally occurring nuclear fuel, has been identified as a sustainable source of energy. In view of its large-scale utilization and human evidence of lung disorders and carcinogenicity, it is imperative to understand the effect of Th exposure on lung cells. The present study investigated the effect of Th-dioxide (1-100 µg/mL, 24-48 h) on expression of surfactant proteins (SPs) (SP-A, SP-B, SP-C, and SP-D, which are essential to maintain lung's surface tension and host-defense) in human lung cells (WI26 and A549), representative of alveolar cell type-I and type-II, respectively. Results demonstrated the inhibitory effect of Th on transcriptional expression of SP-A, SP-B, and SP-C. However, Th promoted the mRNA expression of SP-D in A549 and reduced its expression in WI26. To a significant extent, the effect of Th on SPs was found to be in accordance with their protein levels. Moreover, Th exposure altered the extracellular release of SP-D/A from A549, which remained unaltered in WI26. Our results suggested the differential role of oxidative stress and ATM and HSP90 signaling in Th-induced alterations of SPs. These effects of Th were found to be consistent in lung tissues of mice exposed to Th aerosols, suggesting a potential role of SPs in Th-associated lung disorders.

Insights into ThB40: Stability, Electronic Structure, and Interaction.

The interaction between nonmetal and metal atoms has attracted great interest in the development of organometallic compounds and their promising applications. In this study, we explored the interaction between boron and thorium atoms, based on the stable B40Th coordination compound, by employing density functional theory calculations. We elucidated the stability and geometries of the B40Th coordination compound and revealed the electron transfer from the metal atom Th to B40, which is evidenced by the natural bond orbital calculations. This electron transfer is attributed to the electron-withdrawing character of the boron atom and results in clear electrostatic interaction. Additionally, bond critical analysis and bond order calculations show obvious covalent characters between the metal and nonmetal atoms. The IR spectrum was simulated to give detailed information to identify this targeted compound in future experiments. This study is expected to enhance the understanding of metal-nonmetal interactions and provides useful information for constructing new organometallic compounds based on actinium metal atoms.

Natural radionuclides and radiological risk assessment in the stream and river sediments of a high background natural radiation area Kanyakumari, India.

The Kanyakumari coast is known to be a high background natural radiation area due to the placer deposits of heavy minerals such as ilmenite, monazite, and rutile. The Kanyakumari river sediments that could be the source of the elevated amounts of natural radionuclides in the coastal sands have been studied in this paper. The activity concentrations of primordial radionuclides 226Ra, 232Th, and 40K were determined using high-purity germanium (HPGe) gamma-ray spectrometry. The mean activity concentrations of 226Ra, 232Th, and 40K were found to be 75 Bq kg-1, 565 Bq kg-1, and 360 Bq kg-1, respectively. The mean absorbed dose rate was 395 nGy h-1. Radiological hazard parameters were studied and compared with the world average values. The contribution of 232Th to the total dose rate was found to be higher than that of the two other radionuclides. The high mean ratio of 232Th/226Ra suggested an enrichment of 232Th and the occurrence of 226Ra leaching due to an oxidizing environment. Principal component analysis (PCA) was carried out for the radionuclides in order to discriminate the source of the sediments. This study provides new insights into the distribution of natural radionuclides in sediments of rivers and streams.

Dissolution-Recrystallization: A Novel Mechanism for Fluorochromic Detection of Th4+ Using Color-Tunable Luminescent Metal-Organic Frameworks.

Thorium, a predominant actinide in the Earth's crust, presents significant environmental and health risks due to its radioactive nature. These risks are particularly pronounced during the mining and processing of monazite for rare earth elements (REEs), which contain substantial thorium concentrations. Current instrumental analysis methods for thorium, offer high accuracy but require laborious sample preparation and expensive instruments, making them unsuitable for on-site analysis. Herein, we present a class of color-tunable luminescent lanthanide-based metal-organic frameworks (Ln-MOFs) as fluorochromic sensors for Th4+ cations. Utilizing a heterobimetallic Eu3+/Tb3+ doping strategy, the luminescence colors of EuxTb1-x-BDC-OH can be finely tuned from red, to orange, and to green. More intriguingly, the higher Lewis acidity of Th4+ facilitates the transformation of EuxTb1-x-BDC-OH into a UiO-type Th-MOF via a dissolution-recrystallization mechanism. This process results in a gradual reduction of characteristic Ln3+ emissions and the emergence of blue color ligand-based fluorescence, thereby leading to selective fluorochromic responses with increasing Th4+ concentrations and enabling visible detection of Th4+ cations. Additionally, a custom-built portable optoelectronic device was fabricated, which directly converts luminescence colors into red-green-blue (RGB) values. This device enables easy quantification of Th4+ concentrations without the need for complex instrumentation.

Two-Electron Redox Reactivity of Thorium Supported by Redox-Active Tripodal Frameworks.

The high stability of the + IVoxidation state limits thorium redox reactivity. Here we report the synthesis and the redox reactivity of two Th(IV) complexes supported by the arene-tethered tris(siloxide) tripodal ligands [(KOSiR2 Ar)3 -arene)]. The two-electron reduction of these Th(IV) complexes generates the doubly reduced [KTh((OSi(Ot Bu)2 Ar)3 -arene)(THF)2 ] (2OtBu ) and [K(2.2.2-cryptand)][Th((OSiPh2 Ar)3 -arene)(THF)2 ](2Ph -crypt) where the formal oxidation state of Th is +II. Structural and computational studies indicate that the reduction occurred at the arene anchor of the ligand. The robust tripodal frameworks store in the arene anchor two electrons that become available at the metal center for the two-electron reduction of a broad range of substrates (N2 O, COT, CHT, Ph2 N2 , Ph3 PS and O2 ) while retaining the ligand framework. This work shows that arene-tethered tris(siloxide) tripodal ligands allow implementation of two-electron redox chemistry at the thorium center while retaining the ligand framework unchanged.

Stepwise Crystallization of Millimeter Scale Thorium Cluster Single Crystals as a Bifunctional Platform for X-ray Detection and Shielding.

Monitoring and shielding of X-ray radiation are of paramount importance across diverse fields. However, they are frequently realized in separate protocols and a single material integrating both functions remained elusive. Herein, a hexanuclear cluster [Th6 (µ3 -OH)4 (µ3 -O)4 (H2 O)6 ](pba)6 (HCOO)6 (Th-pba-0D) incorporating high-Z thorium cations and 3-(pyridin-4-yl)benzoate ligands that can function as a brand-new dual-module platform for visible detection and efficient shielding of ionizing radiation is demonstrated. Th-pba-0D exhibits rather unique reversible radiochromism upon alternating X-ray and UV irradiation. Moreover, the millimeter scale crystal size of Th-pba-0D renders the penetration depth of X-ray visible to naked eye and leads to the unearthing of its high X-ray attenuation efficiency. Indeed, the shielding efficacy of Th-pba-0D is comparable to that of lead glass containing 40% PbO, and a Th-pba-0D pellet with a thickness of merely 1.2 mm can shield 99.73% X-ray (16 keV). These studies portend the possible utilization of thorium-bearing materials as a bifunctional platform for radiation detection and shielding.

The unremarkable alveolar epithelial glycocalyx: a thorium dioxide-based electron microscopic comparison after heparinase or pneumolysin treatment.

Recent investigations analyzed in depth the biochemical and biophysical properties of the endothelial glycocalyx. In comparison, this complex cell-covering structure is largely understudied in alveolar epithelial cells. To better characterize the alveolar glycocalyx ultrastructure, unaffected versus injured human lung tissue explants and mouse lungs were analyzed by transmission electron microscopy. Lung tissue was treated with either heparinase (HEP), known to shed glycocalyx components, or pneumolysin (PLY), the exotoxin of Streptococcus pneumoniae not investigated for structural glycocalyx effects so far. Cationic colloidal thorium dioxide (cThO2) particles were used for glycocalyx glycosaminoglycan visualization. The level of cThO2 particles orthogonal to apical cell membranes (≙ stained glycosaminoglycan height) of alveolar epithelial type I (AEI) and type II (AEII) cells was stereologically measured. In addition, cThO2 particle density was studied by dual-axis electron tomography (≙ stained glycosaminoglycan density in three dimensions). For untreated samples, the average cThO2 particle level was ≈ 18 nm for human AEI, ≈ 17 nm for mouse AEI, ≈ 44 nm for human AEII and ≈ 35 nm for mouse AEII. Both treatments, HEP and PLY, resulted in a significant reduction of cThO2 particle levels on human and mouse AEI and AEII. Moreover, a HEP- and PLY-associated reduction in cThO2 particle density was observed. The present study provides quantitative data on the differential glycocalyx distribution on AEI and AEII based on cThO2 and demonstrates alveolar glycocalyx shedding in response to HEP or PLY resulting in a structural reduction in both glycosaminoglycan height and density. Future studies should elucidate the underlying alveolar epithelial cell type-specific distribution of glycocalyx subcomponents for better functional understanding.

Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content.

Thorium oxide has many important applications in industry. In this article, theoretical calculations have been carried out to explore the hydrolysis reactions of the ThOn (n=1-3) clusters. The reaction mechanisms of the O-deficient ThO and the O-rich ThO3 are compared with the stoichiometric ThO2 . The theoretical results show good agreement with the prior experiments. It is shown that the hydrolysis mainly occurred on the singlet potential surface. The overall reactions consist of two hydrolysis steps which are all favourable in energy. The effects of oxygen content on the hydrolysis are elucidated. Interestingly, among them, the peroxo group O2 2- in ThO3 is converted to the HOO- ligand, behaving like the terminal O2- in the hydrolysis which is transformed into the HO- groups. In addition, natural bond orbital (NBO) analyses were employed to further understand the bonding of the pertinent species and to interpret the differences in hydrolysis.

Actinide-Actinide Bonding: Electron Delocalisation and σ-Aromaticity in the Tri-Thorium Cluster [{Th(η8 -C8 H8 )(µ-Cl)2 }3 K2 ].

The tri-thorium cluster [{Th(η8 -C8 H8 )(µ3 -Cl)2 }3 {K(THF)2 }2 ]∞ (Nature 2021, 598, 72-75) was reported to feature intriguing σ-aromatic bonding between the thorium atoms, a mode of metal-metal bonding unique in the actinide series. However, the presence of this bonding motif has since been challenged by others. Here, we computationally explore electron delocalisation in a molecular cluster fragment of [{Th(η8 -C8 H8 )(µ3 -Cl)2 }3 {K(THF)2 }2 ]∞ and examine its responses to an applied magnetic field using a variety of methods. We also discuss the importance of the choice of basis set for the Th atoms and issues regarding locating QTAIM bond critical points. When taken together, the computed data consistently suggest the presence of delocalised Th-Th bonding and Th3 σ-aromaticity.

Age-Dating of Foliage and Soil Organic Matter: Aligning 228Th:228Ra and 7Be:210Pb Radionuclide Chronometers over Annual to Decadal Time Scales.

The 228Th:228Ra ratios of foliage and organic soil horizons evolve with time following a predictable radioactive decay law and thus provide a new chronometer for absolute age-dating of plant and soil organic matter. Preferential uptake of 228Th (t0.5 = 1.9 years) and 228Ra (t0.5 = 5.9 years) by canopy tree species, ferns, and mosses, drives disequilibrium in the 232Th-228Ra-228Th radioactive decay series within forest vegetation and organic soils. With examples from northeastern USA, we verify a new 228Th:228Ra age model by demonstrating its concordance with the fallout radionuclide chronometer 7Be:210Pb in the 0 to 5-year time frame [R2 = 0.87, RMSE = 0.5 years]. At our locality, canopy tree species assimilate 228Th with a typical initial ratio (228Th:228Ra)0 ∼ 0.3, but in several instances, both deciduous and coniferous tree species show a preference for Th over Ra with (228Th:228Ra)0 exceeding 5. While the 228Th:228Ra system is restricted to organic soil horizons, concordance of 228Th:228Ra with established 7Be:210Pb and 241Am bomb-pulse chronometers establishes a coherent age-dating system of soil organic matter based on three independent chronometers and five particle reactive metals, and spanning 0-200 years in time scale that encompasses both organic and mineral soils to depths of up to 30 cm. Concordance indicates that these metals all follow common processes of organometallic colloid formation and migration and, in conjunction with 14C, may open new opportunities to understand soil pedogenic processes that regulate the storage of carbon and atmospheric metals such as Pb and Hg.

A comparison of the chemo- and radiotoxicity of thorium and uranium at different enrichment grades.

Uranium and thorium are heavy metals, and all of their isotopes are radioactive, so it is impossible to study chemical effects entirely independent of the radiation effects. In the present study, we tried to compare the chemo- and radiotoxicity of both metals, taking into account deterministic radiation damages reflected by acute radiation sickness and stochastic radiation damages leading to long-term health impairments (e.g., tumor induction). We made at first a literature search on acute median lethal doses that may be expected to be caused by chemical effects, as even acute radiation sickness as a manifestation of acute radiotoxicity occurs with latency. By simulations based on the biokinetic models of the International Commission on Radiological Protection and using the Integrated Modules for Bioassay Analysis software, we determined the amounts of uranium at different enrichment grades and thorium-232 leading to a short-term red bone marrow equivalent dose of 3.5 Sv considered to cause 50% lethality in humans. Different intake pathways for incorporation were considered, and values were compared to the mean lethal doses by chemotoxicity. To assess stochastic radiotoxicity, we calculated the uranium and thorium amounts leading to a committed effective dose of 200 mSv that is often considered critical. Mean lethal values for uranium and thorium are in the same order of magnitude so that the data do not give evidence for substantial differences in acute chemical toxicity. When comparing radiotoxicity, the reference units (activity in Bq or weight in g) must always be taken into account. The mean lethal equivalent dose to the red bone marrow of 3.5 Sv is reached by lower activities of thorium compared to uranium in soluble compounds. However, for uranium as well as thorium-232, acute radiation sickness is expected only after incorporation of amounts exceeding the mean lethal doses by chemotoxicity. Thus, acute radiation sickness is not a relevant clinical issue for either metal. Concerning stochastic radiation damages, thorium-232 is more radiotoxic than uranium if incorporating the same activities. Using weight units for comparison show that for soluble compounds, thorium-232 is more radiotoxic than low-enriched uranium in the case of ingestion but even more toxic than high-enriched uranium after inhalation or intravenous administration. For insoluble compounds, the situation differs as the stochastic radiotoxicity of thorium-232 ranges between depleted and natural uranium. For acute effects, the chemotoxicity of uranium, even at high enrichment grades, as well as thorium-232 exceeds deterministic radiotoxicity. Simulations show that thorium-232 is more radiotoxic than uranium expressed in activity units. If the comparison is based on weight units, the rankings depend on the uranium enrichment grades and the route of intake.

Rapid Elution of 226Th from a Two-Column 230U/226Th Generator with Diluted and Buffer Solutions.

A radionuclide generator of the short-lived alpha emitter 226Th was proposed. An original scheme consisting of two in-series chromatographic columns was developed for rapidly producing a neutral citric-buffered eluate of high purity 226Th. The first column filled with TEVA resin retained the parent 230U, while 226Th was eluted with 7 M HCl solution to be immediately adsorbed on the second column containing DGA resin or UTEVA resin. Having substituted the strongly acidic medium of second column with neutral salt solution, 226Th was desorbed with diluted citric buffer solution. One cycle of generator milking took 5-7 min and produced >90% of 226Th in 1.5 mL of eluate (pH 4.5-5.0) appropriate for direct use in radiopharmaceutical synthesis. The 230U impurity in 226Th eluate was less than 0.01%. The proposed two-column 230U/226Th generator was tested over 2 months including a second loading of 230U additionally accumulated from 230Pa.

Tackling Issues Observed during the Development of a Liquid Chromatography Method for Small Molecule Quantification in Antibody-Chelator Conjugate.

In the context of targeted radionuclide therapy, antibody-chelator conjugates (ACCs) are an evolving class of antibody-related drugs with promising applications as tumor-targeted pharmaceuticals. Generally, a typical ACC consists of a recombinant monoclonal antibody (mAb) coupled to radionuclide via a chelating agent. Characterizing the ACC structure represents an analytical challenge since various impurities must be constantly monitored in the presence of formulation components during the quality control (QC) process. In this contribution, a reliable method devoted to the monitoring of an ACC sample, and its small molecule-related synthesis impurities, has been developed via liquid chromatography (LC). A problem-solving approach of common analytical issues was used to highlight some major issues encountered during method development. This included separation of poorly retained impurities (issue #1); interferences from the formulation components (issue #2); analysis of impurities in presence of ACC at high concentration (issue #3); and recovery of impurities during the whole analytical procedure (issue #4). To the best of our knowledge, this is the first time that a chromatographic method for the analysis of ACC synthesis impurities is presented. In addition, the developed approach has the potential to be more widely applied to the characterization of similar ACCs and other antibody-related drugs.

Ab Initio Calculations on the Ground and Excited Electronic States of Thorium-Ammonia, Thorium-Aza-Crown, and Thorium-Crown Ether Complexes.

Positively charged metal-ammonia complexes are known to host peripheral, diffuse electrons around their molecular skeleton. The resulting neutral species form materials known as expanded or liquid metals. Alkali, alkaline earth, and transition metals have been investigated previously in experimental and theoretical studies of both the gas and condensed phase. This work is the first ab initio exploration of an f-block metal-ammonia complex. The ground and excited states are calculated for Th0-3+ complexes with ammonia, crown ethers, and aza-crown ethers. For Th3+ complexes, the one valence electron Th populates the metal's 6d or 7f orbitals. For Th0-2+, the additional electrons prefer occupation of the outer s- and p-type orbitals of the complex, except Th(NH3)10, which uniquely places all four electrons in outer orbitals of the complex. Although thorium coordinates up to ten ammonia ligands, octa-coordinated complexes are more stable. Crown ether complexes have a similar electronic spectrum to ammonia complexes, but excitations of electrons in the outer orbitals of the complex are higher in energy. Aza-crown ethers disfavor the orbitals perpendicular to the crowns, attributed to the N-H bonds pointing along the plane of the crowns.

Evaluation of radioactive and heavy metal pollution in agricultural soil surrounding the lignite-fired thermal power plant using pollution indices.

Soil pollution caused by heavy metals negatively affects the environment and human health. However, the assessment of the environmental and ecological risks caused by heavy metals in agricultural soils in developing countries is limited. This study was carried out to determine heavy metal pollution and its possible sources in the agricultural lands surrounding the lignite-fired Afsin-Elbistan thermal power plant (TPP). A total of 52 soil samples were collected from the agricultural soils surrounding the TPP, and seven different heavy metal (U, Th, Ni, Fe, Cu, Cr and Zn) analyzes were performed on these samples. Soil samples were taken according to the prevailing wind direction. Nickel had a higher geoaccumulation index (1.40) and enrichment factor (5.09) values than the other metals. In addition, U posed a "moderate potential ecological risk" in the study area. Pearson correlation and principal component analyses showed that U, Ni, and Cr were controlled by anthropogenic sources.

Alpha spectrometry isotopic ratios indications in the Paleozoic sedimentary rock of El Gor area, Southwestern Sinai, Egypt: insights on uranium mobility age.

The study area is located between longitude 33° 18' 00" - 33° 21' 00" E and latitude 28° 59' - 29° 01' N and covers approximately 700 km2. Uranium and thorium isotopes were determined by alpha spectrometry. The activity concentrations of 238U, 234U and 235U were ranged between 245.5 ± 8.3-465.2 ± 15.2 Bq.kg-1 with an average 345.5 ± 10.4-452.5 ± 9.3 Bq.kg-1 and 890.5 ± 21.3 Bq.kg-1 with an average 632.3 ± 14.9-11.40 ± 0.5 Bq.kg-1 and 21.50 ± 1.4 Bq.kg-1, respectively. The activity concentration of 232Th, 230Th and 228Th were ranged between 153.1 ± 0.3-318.1 ± 2.9 Bq.kg-1, 149.5 ± 0.7-280.8 ± 2.2 Bq.kg-1 and 36.9 ± 0.1-60.5 ± 0.9 Bq.kg-1. The 230Th/232Th activity ratios in all samples were lower than 20, indicating that these samples have been contaminated by detrital 230Th. Th/U ratio varied between 1.3 and 2.1 with an average 1.8; all values were lower than 3.5, indicated enrichment of uranium. 234U/238U activity ratios that higher than unity indicates that an isotope of uranium has migrated within the rock. From the isotopes of uranium and thorium and their activity ratios, the isochron age for the collected samples was about 58.96 ka.

Bonding and Reactivity in Terminal versus Bridging Arenide Complexes of Thorium Acting as ThII Synthons.

Thorium redox chemistry is extremely scarce due to the high stability of ThIV . Here we report two unique examples of thorium arenide complexes prepared by reduction of a ThIV -siloxide complex in presence of naphthalene, the mononuclear arenide complex [K(OSi(Ot Bu)3 )3 Th(η6 -C10 H8 )] (1) and the inverse-sandwich complex [K(OSi(Ot Bu)3 )3 Th]2 (µ-η6 ,η6 -C10 H8 )] (2). The electrons stored in these complexes allow the reduction of a broad range of substrates (N2 O, AdN3 , CO2 , HBBN). Higher reactivity was found for the complex 1 which reacts with the diazoolefin IDipp=CN2 to yield the unexpected ThIV amidoalkynyl complex 5 via a terminal N-heterocyclic vinylidene intermediate. This work showed that arenides can act as convenient redox-active ligands for implementing thorium-ligand cooperative multielectron transfer and that the reactivity can be tuned by the arenide binding mode.

Shallow particulate organic carbon regeneration in the South Pacific Ocean.

Particulate organic carbon (POC) produced in the surface ocean sinks through the water column and is respired at depth, acting as a primary vector sequestering carbon in the abyssal ocean. Atmospheric carbon dioxide levels are sensitive to the length (depth) scale over which respiration converts POC back to inorganic carbon, because shallower waters exchange with the atmosphere more rapidly than deeper ones. However, estimates of this carbon regeneration length scale and its spatiotemporal variability are limited, hindering the ability to characterize its sensitivity to environmental conditions. Here, we present a zonal section of POC fluxes at high vertical and spatial resolution from the GEOTRACES GP16 transect in the eastern tropical South Pacific, based on normalization to the radiogenic thorium isotope 230Th. We find shallower carbon regeneration length scales than previous estimates for the oligotrophic South Pacific gyre, indicating less efficient carbon transfer to the deep ocean. Carbon regeneration is strongly inhibited within suboxic waters near the Peru coast. Canonical Martin curve power laws inadequately capture POC flux profiles at suboxic stations. We instead fit these profiles using an exponential function with flux preserved at depth, finding shallow regeneration but high POC sequestration below 1,000 m. Both regeneration length scales and POC flux at depth closely track the depths at which oxygen concentrations approach zero. Our findings imply that climate warming will result in reduced ocean carbon storage due to expanding oligotrophic gyres, but opposing effects on ocean carbon storage from expanding suboxic waters will require modeling and future work to disentangle.

The enrichment of rare earth from magnesium salt leaching solution of ion-adsorbed type deposit: A waste-free process for removing impurities.

Due to the complex composition of ion-adsorbed type rare earth ore leaching solution, there are challenges in the process of rare earth (RE) separation, such as large RE loss rate, low product purity, radioactive residue and so on. In this article, 8-hydroxyquinoline modified silica gel (HQ-SiO2) and 2,2'-(1,4-phenylenebis(oxy)) dioctanoic acid (PPBOA) were used to form an efficient process for impurities removal and RE enrichment. Solid phase extraction successfully intercepted 96.7% of the radioactive element thorium. The concentration of aluminium was reduced to 2.14 ppm by frank chromatography. Rare earth elements were enriched from 336.35 mg/L to 237.75 g/L by extraction-precipitation, that is, the enrichment multiple reached more than 700 and the proportion of RE was increased from 21.85% to 96.62%. The loss rate of RE was controlled below 1.59%. Moreover, the magnesium salt leaching solution could be recycled for the leaching of RE ores. Although some liquid waste need to be treated in the processes of HQ-SiO2 production and regeneration, the integrated process helps to decrease volatile organic solvent, acid-base consumption, wastewater and waste residue. It is an environment-friendly RE enrichment and impurity removal process, which shows application potential in the production field of ion-adsorbed type rare earth mineral products.