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1.
Nature ; 592(7853): 248-252, 2021 04.
Article in English | MEDLINE | ID: mdl-33790469

ABSTRACT

The archaeological record of Africa provides the earliest evidence for the emergence of the complex symbolic and technological behaviours that characterize Homo sapiens1-7. The coastal setting of many archaeological sites of the Late Pleistocene epoch, and the abundant shellfish remains recovered from them, has led to a dominant narrative in which modern human origins in southern Africa are intrinsically tied to the coast and marine resources8-12, and behavioural innovations in the interior lag behind. However, stratified Late Pleistocene sites with good preservation and robust chronologies are rare in the interior of southern Africa, and the coastal hypothesis therefore remains untested. Here we show that early human innovations that are similar to those dated to around 105 thousand years ago (ka) in coastal southern Africa existed at around the same time among humans who lived over 600 km inland. We report evidence for the intentional collection of non-utilitarian objects (calcite crystals) and ostrich eggshell from excavations of a stratified rockshelter deposit in the southern Kalahari Basin, which we date by optically stimulated luminescence to around 105 ka. Uranium-thorium dating of relict tufa deposits indicates sporadic periods of substantial volumes of fresh, flowing water; the oldest of these episodes is dated to between 110 and 100 ka and is coeval with the archaeological deposit. Our results suggest that behavioural innovations among humans in the interior of southern Africa did not lag behind those of populations near the coast, and that these innovations may have developed within a wet savannah environment. Models that tie the emergence of behavioural innovations to the exploitation of coastal resources by our species may therefore require revision.


Subject(s)
Archaeology , Calcium Carbonate/analysis , Egg Shell , Grassland , Inventions/history , Rain , Struthioniformes , Africa, Southern , Animals , Calcium Carbonate/chemistry , Caves , History, Ancient , Humans , Magnesium , Thorium , Uranium
2.
Nature ; 590(7844): 97-102, 2021 02.
Article in English | MEDLINE | ID: mdl-33536651

ABSTRACT

Following early hypotheses about the possible existence of Arctic ice shelves in the past1-3, the observation of specific erosional features as deep as 1,000 metres below the current sea level confirmed the presence of a thick layer of ice on the Lomonosov Ridge in the central Arctic Ocean and elsewhere4-6. Recent modelling studies have addressed how an ice shelf may have built up in glacial periods, covering most of the Arctic Ocean7,8. So far, however, there is no irrefutable marine-sediment characterization of such an extensive ice shelf in the Arctic, raising doubt about the impact of glacial conditions on the Arctic Ocean. Here we provide evidence for at least two episodes during which the Arctic Ocean and the adjacent Nordic seas were not only covered by an extensive ice shelf, but also filled entirely with fresh water, causing a widespread absence of thorium-230 in marine sediments. We propose that these Arctic freshwater intervals occurred 70,000-62,000 years before present and approximately 150,000-131,000 years before present, corresponding to portions of marine isotope stages 4 and 6. Alternative interpretations of the first occurrence of the calcareous nannofossil Emiliania huxleyi in Arctic sedimentary records would suggest younger ages for the older interval. Our approach explains the unexpected minima in Arctic thorium-230 records9 that have led to divergent interpretations of sedimentation rates10,11 and hampered their use for dating purposes. About nine million cubic kilometres of fresh water is required to explain our isotopic interpretation, a calculation that we support with estimates of hydrological fluxes and altered boundary conditions. A freshwater mass of this size-stored in oceans, rather than land-suggests that a revision of sea-level reconstructions based on freshwater-sensitive stable oxygen isotopes may be required, and that large masses of fresh water could be delivered to the north Atlantic Ocean on very short timescales.


Subject(s)
Fresh Water/analysis , Ice Cover/chemistry , Oceans and Seas , Arctic Regions , Foraminifera/isolation & purification , Fossils , Geologic Sediments/chemistry , History, Ancient , Isotopes/analysis , Plankton/isolation & purification , Protactinium/analysis , Thorium/analysis , Time Factors
3.
Eur J Nucl Med Mol Imaging ; 51(3): 669-680, 2024 Feb.
Article in English | MEDLINE | ID: mdl-37882848

ABSTRACT

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.


Subject(s)
Prostatic Neoplasms , Thorium , Male , Humans , Animals , Mice , Swine , Tissue Distribution , Macaca fascicularis/metabolism , Swine, Miniature/metabolism , Glutamate Carboxypeptidase II/metabolism , Antigens, Surface/metabolism , Prostatic Neoplasms/diagnostic imaging , Prostatic Neoplasms/metabolism , Radiopharmaceuticals , Chelating Agents/chemistry , Cell Line, Tumor
4.
Environ Sci Technol ; 58(28): 12330-12342, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38772857

ABSTRACT

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.


Subject(s)
Alveolar Epithelial Cells , Thorium , Humans , Alveolar Epithelial Cells/metabolism , Alveolar Epithelial Cells/drug effects , Mice , Animals , A549 Cells , Pulmonary Surfactant-Associated Proteins/metabolism
5.
Radiat Environ Biophys ; 63(1): 97-107, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38197922

ABSTRACT

Uranium mining can cause environmental impacts on non-human biota around mine sites. Because of this, the reduction in non-human biota exposure becomes an important issue. Environmental radioprotection results from the evolution of human radioprotection; it is based on dose rate to non-human biota and uses, as a biological target, and has harmful effects on populations. In the present study, a flooded impoundment created following dam construction in a uranium mine plant undergoing decommissioning was investigated. Internal dose rates due to activity concentration of natural uranium (Unat) and 232Th in omnivorous, phytophagous, and carnivorous fish species were estimated. Radionuclide activity concentrations were obtained by spectrophotometry with arsenazo III in the visible range. The dose rate contribution of 232Th was lower than that of Unat. There were no differences between the internal dose rates to studied fish species due to 232Th, but there were differences for Unat. A dose rate of 2.30·10-2 µGy∙d-1 was found due to the two studied radionuclides. Although this value falls below the benchmark for harmful effects, it is important to acknowledge that the assessment did not account for other critical radionuclides from uranium mining, which also contribute to the internal dose. Moreover, the study did not assess external doses. As a result, the possibility cannot be excluded that dose rates at the study area overcome the established benchmarks for harmful effects.


Subject(s)
Radiation Monitoring , Uranium , Water Pollutants, Radioactive , Animals , Thorium/analysis , Uranium/analysis , Brazil , Radioisotopes , Water Pollutants, Radioactive/analysis
6.
Proc Natl Acad Sci U S A ; 118(16)2021 04 20.
Article in English | MEDLINE | ID: mdl-33846250

ABSTRACT

Modern human behavioral innovations from the Middle Stone Age (MSA) include the earliest indicators of full coastal adaptation evidenced by shell middens, yet many MSA middens remain poorly dated. We apply 230Th/U burial dating to ostrich eggshells (OES) from Ysterfontein 1 (YFT1, Western Cape, South Africa), a stratified MSA shell midden. 230Th/U burial ages of YFT1 OES are relatively precise (median ± 2.7%), consistent with other age constraints, and preserve stratigraphic principles. Bayesian age-depth modeling indicates YFT1 was deposited between 119.9 to 113.1 thousand years ago (ka) (95% CI of model ages), and the entire 3.8 m thick midden may have accumulated within ∼2,300 y. Stable carbon, nitrogen, and oxygen isotopes of OES indicate that during occupation the local environment was dominated by C3 vegetation and was initially significantly wetter than at present but became drier and cooler with time. Integrating archaeological evidence with OES 230Th/U ages and stable isotopes shows the following: 1) YFT1 is the oldest shell midden known, providing minimum constraints on full coastal adaptation by ∼120 ka; 2) despite rapid sea-level drop and other climatic changes during occupation, relative shellfish proportions and sizes remain similar, suggesting adaptive foraging along a changing coastline; 3) the YFT1 lithic technocomplex is similar to other west coast assemblages but distinct from potentially synchronous industries along the southern African coast, suggesting human populations were fragmented between seasonal rainfall zones; and 4) accumulation rates (up to 1.8 m/ka) are much higher than previously observed for dated, stratified MSA middens, implying more intense site occupation akin to Later Stone Age middens.


Subject(s)
Archaeology/methods , Geologic Sediments/analysis , Radiometric Dating/methods , Adaptation, Physiological/physiology , Animals , Egg Shell/chemistry , Fossils , History, Ancient , Hominidae , Humans , South Africa , Struthioniformes/physiology , Thorium/analysis , Thorium/chemistry , Uranium/analysis , Uranium/chemistry
7.
J Environ Manage ; 365: 121616, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38941854

ABSTRACT

Volcanic eruption is associated with the release of large volumes of pollutants in the environment, which can pose a risk to humans and other living organisms. The elemental and radioisotope composition of ash released during the Shiveluch Volcano eruption in 2023 was analyzed using ICP-MS and low-background gamma spectrometry. The ash consisted of 59% SiO2, 16.7% Al2O3, 5.3% CaO, 4.6 % Na2O, 4.5% Fe2O3, 1.4% K2O, 0.48% TiO2, 0.17% P2O5, 0.15% S, 0.078% MnO and 44 trace elements. Hazard Quotient and Hazard Index were calculated in order to evaluate the potential health risks to children and adults due to exposure to contaminants via inhalation, ingestion, and dermal contact. All values were below the unit, indicating a low probability of non-carcinogenic and cancerogenic risk occurrence in target groups. The average activity concentrations of the natural radionuclides were 350, 12.4 and 4.84 Bq/kg for 40K, 226Ra and 232Th. Radiological indices, including external and internal risk assessment, radium equivalent activity, annual effective dose, gamma index, and excess lifetime cancer risk were calculated to estimate the radiological hazard for the population. The values of all indices were below the recommended safety limits, indicating a low level of hazard for the exposed population.


Subject(s)
Metals , Radioisotopes , Volcanic Eruptions , Humans , Metals/analysis , Radioisotopes/analysis , Radium/analysis , Risk Assessment , Thorium/analysis
8.
Int J Environ Health Res ; 34(1): 273-294, 2024 Jan.
Article in English | MEDLINE | ID: mdl-36587371

ABSTRACT

Chemical contamination of seafood has become a global health concern. Carp fish is one of the most widely consumed globally, and several studies have been conducted on the contamination of carp fish with radioisotopes. In the current study, a meta-analysis and probabilistic exposure assessment regarding the Potassium-40 (40K), Polonium-210 (210Po), Radium-226 (226Ra), and Thorium-230 (230Th) in the fillet tissue of carp fish were performed. In this regard, Scopus and PubMed were screened to retrieve the associated citations with on the concentration of radioisotopes in the fillet tissue of carp fish until October 2021. The rank order of radioisotopes in fillet tissue carp fish was 40K (103.49 Bq kg-1) > 210Po (9.39 Bq kg-1) > 226Ra (0.62 Bq kg-1) > 230Th (0.39 Bq kg-1). The highest effective dose due to 210Po ingestion was observed in Spain (male; 4.44E-05 Sv y-1, female; 2.67E-06 Sv y-1); 40K (female, 5.07E-07 Sv y-1); 226Ra (male, 9.93E-09 Sv y-1). The mean of effective dose (ED) in the male and females in India due to ingestion of 230Th as result of carp fish consumption was (1.70E-06 Sv y-1) and (7.01E-08 Sv y-1), respectively. The probabilistic exposure assessment by the Monte Carlo simulation method revealed that consumers of fillet tissue carp fish content of radioisotopes are at a safe range (0.001 Sv y-1).


Subject(s)
Carps , Radioisotopes , Seafood , Animals , Female , Male , Fishes , Polonium , Potassium Radioisotopes , Radioisotopes/analysis , Radium , Seafood/analysis , Thorium
9.
Environ Geochem Health ; 46(2): 66, 2024 Feb 08.
Article in English | MEDLINE | ID: mdl-38329628

ABSTRACT

The radiation arising from naturally occurring radioactive materials (NORMs) is the foremost contributor to the collective dose received by the global population. The present study aims to measure the natural background radiation level and the associated gamma radiation dose in air in the Beldih apatite mine region of Purulia district, India. This study is primarily focused on the determination of 238U, 232Th and 40K activities in the sub-surface soil of the study area. The measurements were carried out using a High Purity Germanium (HPGe) detector-based gamma-ray spectrometer with a relative efficiency of 80%. To achieve uniformity in exposure estimations, radium equivalent activity has been calculated. Additionally, the internal hazard index, external hazard index, radioactivity level index and gamma dose rates have been evaluated to estimate the radiation hazard levels in the study area. The comparison of obtained concentrations and hazard indices with global data (UNSCEAR. (2008). Sources, effects and risks of ionizing radiation. United nations scientific committee on the effects of atomic radiation (report to the general assembly, with Annexes).) suggests that this region lies in a relatively high background radiation zone.


Subject(s)
Radiation Monitoring , Radioactivity , Radium , Soil Pollutants, Radioactive , Thorium/analysis , Potassium Radioisotopes/analysis , Soil , Soil Pollutants, Radioactive/analysis , Radium/analysis
10.
Environ Geochem Health ; 46(6): 181, 2024 May 02.
Article in English | MEDLINE | ID: mdl-38695964

ABSTRACT

This study determined natural and artificial radionuclide concentrations to evaluate natural radioactivity and health risk levels of nine travertines in the Yaprakhisar and Balkayasi regions in Turkey. The samples coded B1-M, B2, B5, B7, B8, and B10 represent waste derived from the Yaprakhisar travertines, as well as samples T5-M, T12, and Z1 travertines derived from Balkayasi. The levels of natural and artificial radionuclide concentrations (232Th, 40K, and 137Cs) were measured using a high-purity germanium (HpGe) detector system. The travertine activity ranged from 2.09 to 12.07 Bq kg-1 for 232Th, 4.21 to 13.41 Bq kg-1 for 40K, and 0.42-3.26 Bq kg-1 for 137Cs. The results showed that the activity concentration values for 232Th, 40K, and 137Cs were coherent with the travertine analysis results in the UNSCEAR, 2000; 2008 publications. The values obtained were lower than the average values in the UNSEAR reports. The radiological hazard parameters calculated in this study were absorbed gamma dose rate (D), radium equivalent activity (Raeq), annual gonadal dose equivalent (AGDE), exposure dose (ER), total annual effective dose (AEDEtotal), excess lifetime cancer risk (ELCRtotal), gamma representative level (GRL), internal hazard index (Hin) and external hazard index (Hex).


Subject(s)
Cesium Radioisotopes , Potassium Radioisotopes , Radiation Monitoring , Turkey , Radiation Monitoring/methods , Potassium Radioisotopes/analysis , Cesium Radioisotopes/analysis , Thorium/analysis , Soil Pollutants, Radioactive/analysis , Background Radiation , Humans , Risk Assessment
11.
World J Microbiol Biotechnol ; 40(7): 232, 2024 Jun 05.
Article in English | MEDLINE | ID: mdl-38834810

ABSTRACT

Microbially induced carbonate precipitation (MICP) has been used to cure rare earth slags (RES) containing radionuclides (e.g. Th and U) and heavy metals with favorable results. However, the role of microbial extracellular polymeric substances (EPS) in MICP curing RES remains unclear. In this study, the EPS of Lysinibacillus sphaericus K-1 was extracted for the experiments of adsorption, inducing calcium carbonate (CaCO3) precipitation and curing of RES. The role of EPS in in MICP curing RES and stabilizing radionuclides and heavy metals was analyzed by evaluating the concentration and morphological distribution of radionuclides and heavy metals, and the compressive strength of the cured body. The results indicate that the adsorption efficiencies of EPS for Th (IV), U (VI), Cu2+, Pb2+, Zn2+, and Cd2+ were 44.83%, 45.83%, 53.7%, 61.3%, 42.1%, and 77.85%, respectively. The addition of EPS solution resulted in the formation of nanoscale spherical particles on the microorganism surface, which could act as an accumulating skeleton to facilitate the formation of CaCO3. After adding 20 mL of EPS solution during the curing process (Treat group), the maximum unconfined compressive strength (UCS) of the cured body reached 1.922 MPa, which was 12.13% higher than the CK group. The contents of exchangeable Th (IV) and U (VI) in the cured bodies of the Treat group decreased by 3.35% and 4.93%, respectively, compared with the CK group. Therefore, EPS enhances the effect of MICP curing RES and reduces the potential environmental problems that may be caused by radionuclides and heavy metals during the long-term sequestration of RES.


Subject(s)
Bacillaceae , Calcium Carbonate , Extracellular Polymeric Substance Matrix , Metals, Heavy , Thorium , Uranium , Uranium/chemistry , Uranium/metabolism , Calcium Carbonate/chemistry , Thorium/chemistry , Extracellular Polymeric Substance Matrix/metabolism , Extracellular Polymeric Substance Matrix/chemistry , Bacillaceae/metabolism , Metals, Rare Earth/chemistry , Adsorption , Chemical Precipitation
12.
Environ Monit Assess ; 196(2): 190, 2024 Jan 23.
Article in English | MEDLINE | ID: mdl-38261087

ABSTRACT

Soil samples from vegetable farmland in densely populated wards of Nepal were analyzed for natural radionuclide levels, employing a NaI(Tl) 3" [Formula: see text] 3" gamma detector. The study aimed to evaluate the causes of radiation risk, attributing it to soil contamination resulting from the rapid urbanization and concretization that followed the earthquake in 2015. The activity concentration of radium-226, thorium-232, and potassium-40 and the ranges observed are 2.080±0.084-33.675±1.356 Bq kg[Formula: see text], 17.222±0.198-119.949±1.379 Bq kg[Formula: see text], and 11.203 ± 0.325-748.828±21.716 Bq kg[Formula: see text], respectively. The average values obtained for hazard indices are as follows: radium equivalent activity (82.779 Bq kg[Formula: see text]), absorbed dose rate (36.394 nGy h[Formula: see text]), annual effective dose equivalent (0.045 mSv yearr[Formula: see text]), gamma index (0.291), external hazard index (0.224), internal hazard index (0.253), excess lifetime cancer risk (0.159), annual gonadal dose equivalent (243.278 mSv year[Formula: see text]), alpha index (0.054), and activity utilization index (0.716). However, in most places, thorium-232 concentration is greater than those of the world average and recommended values. In specific locations such as Ward 4 in Baluwatar, the soil was found to have concentrations of Ra[Formula: see text] and K[Formula: see text] exceeding recommended limits. Despite this localized concern, the overall analysis of hazard indices across the studied areas revealed that most values were within permissible limits. This suggests that, on a broader scale, radiation exposure may not be a significant concern in the investigated regions. Nonetheless, the study recommends regular monitoring in additional locations to ensure a comprehensive and ongoing assessment of radiation levels.


Subject(s)
Earthquakes , Environmental Monitoring , Thorium , Soil , Risk Assessment
13.
Environ Monit Assess ; 196(3): 330, 2024 Mar 01.
Article in English | MEDLINE | ID: mdl-38427152

ABSTRACT

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.


Subject(s)
Radiation Monitoring , Soil Pollutants, Radioactive , Rivers , Background Radiation , Environmental Monitoring , Thorium/analysis , Radioisotopes/analysis , Soil Pollutants, Radioactive/analysis , India , Risk Assessment , Radiation Monitoring/methods , Potassium Radioisotopes/analysis
14.
Chemistry ; 29(55): e202300636, 2023 Oct 02.
Article in English | MEDLINE | ID: mdl-37526142

ABSTRACT

Transferrin (Tf) is a glycoprotein that transports iron from the serum to the various organs. Several studies have highlighted that Tf can interact with metals other than Fe(III), including actinides that are chemical and radiological toxics. We propose here to report on the behavior of Th(IV) and Pu(IV) in comparison with Fe(III) upon Tf complexation. We considered UV-Vis and IR data of the M2 Tf complex (M=Fe, Th, Pu) and combined experimental EXAFS data with MD models. EXAFS data of the first M-O coordination sphere are consistent with the MD model considering 1 synergistic carbonate. Further EXAFS data analysis strongly suggests that contamination by Th/Pu colloids seems to occur upon Tf complexation, but it seems limited. SAXS data have also been recorded for all complexes and also after the addition of Deferoxamine-B (DFOB) in the medium. The Rg values are very close for apoTf, ThTf and PuTf, but slightly larger than for holoTf. Data suggest that the structure of the protein is more ellipsoidal than spherical, with a flattened oblate form. From this data, the following order of conformation size might be considered:holoTf

Subject(s)
Plutonium , Transferrin , Transferrin/chemistry , Plutonium/chemistry , Thorium/chemistry , Ferric Compounds , Scattering, Small Angle , X-Ray Diffraction
15.
Chem Res Toxicol ; 36(11): 1693-1702, 2023 11 20.
Article in English | MEDLINE | ID: mdl-37871261

ABSTRACT

Thorium-232 (232Th) is a radioactive heavy metal that is of increasing interest as a source of nuclear energy. However, upon nuclear incidents, the ingestion or inhalation of Th in major quantities can contribute to chemical and radiological health problems, including accumulation in the bone tissue and an increased risk of developing pancreatic, lung, and hematopoietic cancers. The major mineral component of the bone is hydroxyapatite (HAP)─also the major mineral component of the teeth. As such, the teeth are the first site of exposure upon oral ingestion of Th-contaminated materials, and Th can pose a potential risk to teeth development. In essence, in the case of human contamination, it is critical to identify effective chelating agents capable of removing Th. Using a batch study methodology, this present work investigates the uptake and the removal of Th from synthetic HAP and from teeth samples by diethylenetriamine pentaacetate (DTPA), ethylenediaminetetraacetic acid (EDTA), and other promising chelating agents. Th uptake over synthetic HAP exceeds 98% at physiological pH with <1 min of contact time and uptake exceeds 90% across the entire pH range. Regarding teeth, over 1 mg Th uptaken per gram of tooth is observed after 24 h. The overall effectiveness of chelating agents for the removal of Th from is as follows: DTPA > EDTA > NaF/mouthwash/3,4,3-LI(1,2-HOPO); this trend was observed both in synthetic HAP and Th-impregnated teeth samples.


Subject(s)
Chelating Agents , Thorium , Humans , Edetic Acid , Durapatite , Pentetic Acid
16.
Inorg Chem ; 62(46): 18887-18900, 2023 Nov 20.
Article in English | MEDLINE | ID: mdl-37922372

ABSTRACT

The most effective approach to mitigate the toxic effects of internal exposure of radiometals to humans is metal-ligand (ML) chelation therapy. Thorium (Th)-induced carcinogenesis as well as other health hazards to humans as a result of chronic internal exposure necessitates the development of efficient Th-decorporating agents. In this regard, chemical and biological studies were carried out to evaluate N-(2-Acetamido)iminodiacetic acid (ADA), a comparatively cost-effective, readily available, and biologically safe complexing agent for Th decorporation. In the present work, detailed thermodynamic studies for complexation of ADA with Th(IV) have been carried out to understand Th-ADA interaction, using potentiometry, calorimetry, electrospray ionization mass spectrometry, and theoretical studies, followed by its biological assessment for Th decorporation. Thermodynamic studies revealed the formation of strong Th-ADA complexes, which are enthalpically as well as entropically favored. Interestingly, density functional theory calculations, to obtain a thermodynamically favored mode of coordination, showed the uncommon trend of lower denticity of ADA in ML than in ML2, which has been explained on the basis of stabilization of ML by hydrogen bonding. The same was also reflected in the unusual trend of enthalpy for Th-ADA complexes. Biological experiments using human erythrocytes, whole human blood, and lung cells showed good cytocompatibility and ability of ADA to significantly prevent Th-induced hemolysis. Th removal of ADA from erythrocytes, human blood, and normal lung cells was found to be comparable with that of diethylenetriamine pentaacetate (DTPA), an FDA approved decorporating agent. The present study contributed significant data about Th complexation chemistry of ADA and its Th decorporation efficacy from human erythrocytes, blood, and lung cells.


Subject(s)
Erythrocytes , Thorium , Humans , Thorium/pharmacology , Calorimetry , Cell Death
17.
Inorg Chem ; 62(50): 20721-20732, 2023 Dec 18.
Article in English | MEDLINE | ID: mdl-37590371

ABSTRACT

Thorium-227 (227Th) is an α-emitting radionuclide that has shown preclinical and clinical promise for use in targeted α-therapy (TAT), a type of molecular radiopharmaceutical treatment that harnesses high energy α particles to eradicate cancerous lesions. Despite these initial successes, there still exists a need for bifunctional chelators that can stably bind thorium in vivo. Toward this goal, we have prepared two macrocyclic chelators bearing 1,2-hydroxypyridinone groups. Both chelators can be synthesized in less than six steps from readily available starting materials, which is an advantage over currently available platforms. The complex formation constants (log ßmlh) of these ligands with Zr4+ and Th4+, measured by spectrophotometric titrations, are greater than 34 for both chelators, indicating the formation of exceedingly stable complexes. Radiolabeling studies were performed to show that these ligands can bind [227Th]Th4+ at concentrations as low as 10-6 M, and serum stability experiments demonstrate the high kinetic stability of the formed complexes under biological conditions. Identical experiments with zirconium-89 (89Zr), a positron-emitting radioisotope used for positron emission tomography (PET) imaging, demonstrate that these chelators can also effectively bind Zr4+ with high thermodynamic and kinetic stability. Collectively, the data reported herein highlight the suitability of these ligands for use in 89Zr/227Th paired radioimmunotheranostics.


Subject(s)
Chelating Agents , Radiopharmaceuticals , Thorium , Radioisotopes , Zirconium , Positron-Emission Tomography/methods , Ligands
18.
Arch Toxicol ; 97(6): 1577-1598, 2023 06.
Article in English | MEDLINE | ID: mdl-37022444

ABSTRACT

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.


Subject(s)
Radiation Injuries , Uranium , Humans , Thorium/toxicity , Thorium/analysis , Uranium/toxicity , Uranium/analysis , Dose-Response Relationship, Radiation
19.
Radiat Environ Biophys ; 62(2): 181-191, 2023 05.
Article in English | MEDLINE | ID: mdl-37029809

ABSTRACT

This paper includes a review of the natural background radiation of the Kingdom of Saudi Arabia. The review deals with natural radioactivity measurements conducted in the past few decades in the Kingdom. The numerous research works reviewed refer to different materials soils processed building material, terrestrial (dwellings) and mining sites. For the measurements, different experimental techniques were adopted. The highest mean specific activity of 238U, 232Th and 40 K in soil samples was found to be 39.0, 25.6, and 343.0 Bq/kg, respectively. While the world average values are 33, 45 and 420 Bq/kg, respectively. For building materials, the highest mean values for 226Ra, 232Th and 40 K were 89, 106 and 773 Bq/kg, respectively. The mean indoor and outdoor dose rates were 455 µGy/y (Riyadh City) and 883 µGy/y (Al-Khamis City), respectively. For the mining sites the mean values for 238U, 226Ra, 228Ra, gross α and gross ß, were 0.12, 0.33, 21, 0.78 and 2.44 Bq/kg, respectively. Based on the available data it is concluded that most of the natural background radiation levels in the measured locations were within acceptable limits, while a few isolated locations showed elevated dose rates. This review suggests that new improved radiological survey methods be employed to cover the entire country, and that areas identified with comparably high dose rates be re-assessed, especially, in dwellings and mining sites.


Subject(s)
Radiation Monitoring , Soil Pollutants, Radioactive , Saudi Arabia , Background Radiation , Radiometry , Radiation Dosage , Soil Pollutants, Radioactive/analysis , Thorium/analysis
20.
Ecotoxicol Environ Saf ; 263: 115210, 2023 Sep 15.
Article in English | MEDLINE | ID: mdl-37418943

ABSTRACT

This study investigated the distribution features of uranium-238 (238U), radium-226 (226Ra), thorium-232 (232Th), and potassium-40 (40K) and evaluated the associated environmental radiological hazards of the topsoil and river sediments in the Jinding lead-zinc (Pb-Zn) mine catchment from Southwest China. The activity concentrations of 238U, 226Ra, 232Th, and 40K ranged from 24.0 ± 2.29-60.3 ± 5.26 Bq.kg-1, from 32.5 ± 3.95-69.8 ± 3.39 Bq.kg-1, from 15.3 ± 2.24-58.3 ± 4.92 Bq.kg-1, and from 203 ± 10.2-1140 ± 27.4 Bq.kg-1, respectively. The highest activity concentrations for all these radionuclides were primarily found in the mining areas and decreased with increasing distance from the mining sites. The radiological hazard indices, including radium equivalent activity, absorbed gamma dose rate in the air, outdoor annual effective dose equivalent, annual gonadal dose equivalent, and excess lifetime cancer, revealed that the highest values were observed in the mining area and downstream, specifically in the vicinity of the ore body. These elevated values exceeded the global mean value but remained below the threshold value, suggesting that routine protection measures for Pb-Zn miners during production activities are sufficient. The correlation analysis and cluster analysis revealed strong associations between radionuclides such as 238U, 226Ra, and 232Th, indicating a common source of these radionuclides. The activity ratios of 226Ra/238U, 226Ra/232Th, and 238U/40K varied with distance, suggesting the influence of geological processes and lithological composition on their transport and accumulation. In the mining catchment areas, the variations in these activity ratios increased indicated the impact of limestone material dilution on the levels of 232Th, 40K, and 238U in the upstream region. Moreover, the presence of sulfide minerals in the mining soils contributed to the enrichment of 226Ra and the removal of 238U caused those activity ratios decreased in the mining areas. Therefore, in the Jinding PbZn deposit, the patterns of mining activities and surface runoff processes in the catchment area favored the accumulation of 232Th and 226Ra over 40K and 238U. This study provides the first case study on the geochemical distributions of natural radionuclides in a typical Mississippi Valley-type PbZn mining area and offers fundamental information on radionuclide migration and baseline radiometric data for PbZn deposits worldwide.


Subject(s)
Radiation Monitoring , Radium , Soil Pollutants, Radioactive , Uranium , Soil , Lead/analysis , Zinc/analysis , Radioisotopes/analysis , Uranium/analysis , Radium/analysis , Thorium/analysis , Soil Pollutants, Radioactive/analysis , Mining
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