[Level and health evaluation of rare earth elements in human blood and hair in the mining areas in Northwest Hubei].

OBJECTIVE: To investigate the content of rare earth elements(REs)in blood and hair of residents in a RE mining area in Northwest Hubei, and evaluate the impact of REs on the health status of local residents. METHODS: A total of 191 residents from the core area of RE mining areas and 186 residents from non RE mining areas, aged 20-69, were selected. The content of REs in the blood and hair of the survey subjects was measured using inductively coupled plasma mass spectrometry, and compared with existing literature values. At the same time, blood tests and questionnaire surveys will be conducted on the health status of residents to examine whether human RE enrichment can lead to endemic diseases. RESULTS: The average total content of REs in the blood of residents in the mining area was 60.22 ng/mL, which was 3.35 times that of the control area; The average total content of REs in hair was 1197.91 ng/g, which was 6.32 times higher than the control area. As age increasing, the abundance of REs in the blood and hair of both men and women in mining areas increased. The proportion of Yttrium and Scandium in the blood and hair were much higher than that in the soil. Compared to hair, Yttrium and Scandium were more easily enriched in the blood. There was no significant difference in the probability of fatty liver, hepatitis B, hypoglycemia, hypotension, hypertension and heart disease and the average life span between residents in RE mining areas and those in the control area. CONCLUSION: The high daily average dietary intake of REs in residents leads to a relatively large accumulation of REs in human blood and hair, but no significant and substantial human health damage has been found at present.

Trace and rare earth elements in phytoplankton from the Tyrrhenian Sea (Italy).

Plankton plays a very crucial role in bioaccumulation and transfer of metals in the marine food web and represents a suitable bioindicator of the occurrence of trace and rare earth elements in the ecosystem. Trace elements and REEs were analyzed by ICP-MS in phytoplankton samples from the northwestern Mediterranean Sea. Metal concentrations in phytoplankton were found strongly influenced by seasons and depth of collection (- 30 m, - 50 m). Principal component analysis (PCA) has shown that Al, As, Cr, Cu, Ga, and Sn concentrations were related to summer and autumn in samples collected at 30 m depth, while Fe, Mn, Ni, V, and Zn levels related strongly with summer and spring at 50 m depth. Fe, Al, and Zn were the most represented elements in all samples (mean values respectively in the ranges 4.2-8.2, 9.6-13, and 1.0-4.4 mg kg-1) according to their widespread presence in the environment and in the earth crust. Principal component analysis (PCA) performed on REEs showed that mostly all lanthanides' concentrations strongly correlate with summer and autumn seasons (- 30 m depth); the highest ∑REE concentration (75 µg kg-1) was found in winter. Phytoplankton REE normalized profile was comparable to those of other marine biota collected in the same area according to the suitability of lanthanides as geological tracers.

Distribution of rare earth elements and assessment of anthropogenic gadolinium in estuarine habitats: The case of Loire and Seine estuaries in France.

Rare earth elements (REEs), attractive to society because of their applications in industry, agriculture and medicine, are increasingly released into the environment especially in industrialized estuaries. This study compared the REE distribution in the abiotic compartments: water (dissolved phase (<0.45 µm), suspended particulate matter (SPM)) and sediment of the Loire and Seine estuaries (France). A total of 8 and 6 sites were investigated in the Loire and Seine, respectively, as well as 5 additional offshore sites for the Loire. Total REE concentrations were higher in the Loire for the dissolved phase (93.5 ± 63.3 vs 87.7 ± 16.2 ng/L), SPM (173.9 ± 18.3 vs 114.0 ± 17.8 mg/kg dw) and sediments (198.2 ± 27.9 vs 73.2 ± 27.4 mg/kg dw), explained by higher geogenic inputs. Individual REE contributions along with normalization highlighted heavy REE enrichments and Gd positive anomalies in the dissolved phase of the two estuaries, whereas REE distributions in SPM and sediments followed the natural abundance of the REE classes. The calculated Gd anomalies in the dissolved phase were higher in the Seine (9.7 ± 3.4) than in the Loire (3.0 ± 0.8), corresponding to 88.3 ± 5.1 % and 64.4 ± 11.1 % of anthropogenic Gd. This demonstrates a higher contamination of the Seine estuary, certainly due to the difference in the number of inhabitants between both areas involving different amounts of Gd used in medicine. The offshore sites of Loire showed lower total REE concentrations (55.8 ± 5.8 ng/L, 26.7 ± 38.2 mg/kg dw and 100.1 ± 11.7 mg/kg dw for the dissolved phase, SPM and sediments, respectively) and lower Gd anomalies (1.2 ± 0.2) corresponding to only 13.3 ± 3.9 % of anthropogenic Gd, confirming a contamination from the watershed. This study comparing two major French estuaries provides new data on the REE distribution in natural aquatic systems.

Boosting plant resilience: The promise of rare earth nanomaterials in growth, physiology, and stress mitigation.

Rare earth elements (REE) have been extensively used in a variety of applications such as cell phones, electric vehicles, and lasers. REEs are also used as nanomaterials (NMs), which have distinctive features that make them suitable candidates for biomedical applications. In this review, we have highlighted the role of rare earth element nanomaterials (REE-NMs) in the growth of plants and physiology, including seed sprouting rate, shoot biomass, root biomass, and photosynthetic parameters. In addition, we discuss the role of REE-NMs in the biochemical and molecular responses of plants. Crucially, REE-NMs influence the primary metabolites of plants, namely sugars, amino acids, lipids, vitamins, enzymes, polyols, sorbitol, and mannitol, and secondary metabolites, like terpenoids, alkaloids, phenolics, and sulfur-containing compounds. Despite their protective effects, elevated concentrations of NMs are reported to induce toxicity and affect plant growth when compared with lower concentrations, and they not only induce toxicity in plants but also affect soil microbes, aquatic organisms, and humans via the food chain. Overall, we are still at an early stage of understanding the role of REE in plant physiology and growth, and it is essential to examine the interaction of nanoparticles with plant metabolites and their impact on the expression of plant genes and signaling networks.

Enhancing singlet oxygen production of dioxygen activation on the carbon-supported rare-earth oxide nanocluster and rare-earth single atom catalyst to remove antibiotics.

Singlet oxygen (1O2) is extensively employed in the fields of chemical, biomedical and environmental. However, it is still a challenge to produce high- concentration 1O2 by dioxygen activation. Herein, a system of carbon-supported rare-earth oxide nanocluster and single atom catalysts (named as RE2O3/RE-C, RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y) with similar morphology, structure, and physicochemical characteristic are constructed to activate dissolved oxygen (DO) to enhance 1O2 production. The catalytic activity trends and mechanisms are revealed experimentally and are also proven by theoretical analyses and calculations. The 1O2 generation activity trend is Gd2O3/Gd-C>Er2O3/Er-C>Sm2O3/Sm-C>pristine carbon (C). More than 95.0% of common antibiotics (ciprofloxacin, ofloxacin, norfloxacin and carbamazepine) can be removed in 60 min by Gd2O3/Gd-C. Density functional theory calculations indicate that Gd2O3 nanoclusters and Gd single atoms exhibit the moderate adsorption energy of ·O2- to enhance 1O2 production. This study offers a universal strategy to enhance 1O2 production in dioxygen activation for future application and reveals the natural essence of basic mechanisms of 1O2 production via rare-earth oxide nanoclusters and rare-earth single atoms.

Global natural concentrations of Rare Earth Elements in aquatic organisms: Progress and lessons from fifty years of studies.

Rare Earth Elements (REEs) consist of a coherent group of elements with similar physicochemical properties and exhibit comparable geochemical behaviors in the environment, making them excellent tracers of environmental processes. For the past 50 years, scientific communities investigated the REE concentrations in biota through various types of research (e.g. exploratory studies, environmental proxies). The extensive development of new technologies over the past two decades has led to the increased exploitation and use of REEs, resulting in their release into aquatic ecosystems. The bioaccumulation of these emerging contaminants has prompted scientific communities to explore the fate of anthropogenic REEs within aquatic ecosystems. To achieve this, it is necessary to determine the natural concentration levels of REEs in aquatic organisms and the factors controlling REE dynamics. However, knowledge gaps still exist, and no comprehensive approach currently exists to assess the REE concentrations at the ecosystem scale or the factors controlling these concentrations in aquatic organisms. Based on a database comprising 102 articles, this study aimed to: i) provide a retrospective analysis of research topics over a 50-year period; ii) establish reference REE concentrations in several representative phyla of aquatic ecosystems; and iii) examine the global-scale influences of habitat and trophic position as controlling factors of REE concentrations in organisms. This study provides reference concentrations for 16 phyla of freshwater or marine organisms. An influence of habitat REE concentrations on organisms has been observed on a global scale. A trophic dilution of REE concentrations was highlighted, indicating the absence of biomagnification. Lastly, the retrospective approach of this study revealed several research gaps and proposed corresponding perspectives to address them. Embracing these perspectives in the coming years will lead to a better understanding of the risks of anthropogenic REE exposure for aquatic organisms.

Prospecting for rare earth element (hyper)accumulators in the Paris Herbarium using X-ray fluorescence spectroscopy reveals new distributional and taxon discoveries.

BACKGROUND: Rare earth elements (REEs) are increasingly crucial for modern technologies. Plants could be used as a biogeochemical pathfinder and a tool to extract REEs from deposits. However, a paucity of information on suitable plants for these tasks exists. METHODS: We aimed to discover new REE-(hyper)accumulating plant species by performing an X-ray fluorescence (XRF) survey at the Herbarium of the Muséum national d'Histoire naturelle (MNHN, Paris, France). We selected specific families based on the likelihood of containing REE-hyperaccumulating species, using known taxa that accumulate REEs. A total of 4425 specimens, taken in the two main evolutionary lineages of extant vascular plants, were analysed, including the two fern families Blechnaceae (n = 561) and Gleicheniaceae (n = 1310), and the two flowering plant families Phytolaccaceae (n = 1137) and Juglandaceae (n = 1417). KEY RESULTS: Yttrium (Y) was used as a proxy for REEs for methodological reasons, and a total of 268 specimens belonging to the genera Blechnopsis (n = 149), Dicranopteris (n = 75), Gleichenella (n = 32), Phytolacca (n = 6), Carya (n = 4), Juglans (n = 1) and Sticherus (n = 1) were identified with Y concentrations ranging from the limit of detection (LOD) >49 µg g-1 up to 1424 µg g-1. Subsequently, analysis of fragments of selected specimens by inductively coupled plasma atomic emission spectroscopy (ICP-AES) revealed that this translated to up to 6423 µg total REEs g-1 in Dicranopteris linearis and up to 4278 µg total REEs g-1 in Blechnopsis orientalis which are among the highest values ever recorded for REE hyperaccumulation in plants. It also proved the validity of Y as an indicator for REEs in XRF analysis of herbarium specimens. The presence of manganese (Mn) and zinc (Zn) was also studied by XRF in the selected specimens. Mn was detected in 1440 specimens ranging from the detection limit at 116 µg g-1 up to 3807 µg g-1 whilst Zn was detected in 345 specimens ranging from the detection limit at 77 µg g-1 up to 938 µg g-1. CONCLUSIONS AND IMPLICATIONS: This study led to the discovery of REE accumulation in a range of plant species, substantially higher concentrations in species known to be REE hyperaccumulators, and records of REE hyperaccumulators outside of the well-studied populations in China.

Spatial distribution of rare earth elements and their impact factors in an area with a high abundance of regolith-hosted deposits.

Despite the widespread occurrence of regolith-hosted rare earth elements (REEs) across South China, their spatial distribution characteristics in soils and their impact factors remain largely uncertain. This knowledge gap impedes the exploration of regolith-hosted REE deposits and the assessment of the environmental risks associated with REEs. To address this issue, 180 soil samples were collected from Meizhou City, Guangdong Province, a region known for its high abundance of regolith-hosted REEs. Subsequently, the correlations between REE enrichment/fractionation and various factors, i.e., topography, climate conditions, land use, and landform were analysed using the geo-detector method. The results revealed a highly uneven spatial distribution of REEs and their fractionation features with some regions displaying distinct spatial patterns. Elevation was the dominant factor influencing this distribution, and showed strong correlations with the concentrations of REEs, light REEs (LREEs) and heavy REEs (HREEs); the LREE/HREE ratio; and the positive Ce anomaly (δCe). The negative Eu anomaly (δEu) showed a good correlation with rock type. The enrichment and fractionation of REEs indicated a coupling among the abovementioned factors. For REE enrichment, areas with elevations of 138-148 m, precipitation levels of 1553-1574 mm, annual average land surface temperatures of 30.4-30.5 °C, leaf area index values of 22-29 and surface cutting degree of 21.5-29.9 m showed the highest average abundance within each type (scope) of the predominant factors. These findings highlight the key factors affecting REE distribution, thereby aiding the efficient utilization of regolith-hosted REE resources and the evaluation of their environmental risks.

Practical guidelines for representing and interpreting rare earth abundances in environmental and biological studies.

This paper summarizes the main guidelines for representing rare earth element (REE) abundance patterns, along with a review of the common mistakes or omissions that can alter REE plots and bias interpretations. It is specifically designed for ecotoxicologists and biologists, for whom the study of these elements has become an important field of research in recent years. Prior to applying REE diagrams to the study of living organisms, it is important to understand the rationale that led geochemists and cosmochemists to develop them. Used with the practical recommendations described here, these diagrams have the capacity to highlight fundamental processes taking place in the biosphere.

Elevated levels of environmental radioactivity in fluvial sediment: origin and health risk assessment.

To study the geogenic processes of naturally occurring radioactive materials' (NORMs') distribution, a transboundary Himalayan river (Punarbhaba) is chosen due to its trivial anthropogenic impacts. In explaining the genesis of radionuclides, transition elements (Sc, Ti, V, and Fe), rare-earth-elements (REEs: La, Eu, Ce, Yb, Sm, and Lu), Ta, Hf, Th, and U were analysed in 30 riverbed sediments collected from the Bangladeshi portion of the river. Elemental abundances and NORMs' activity were measured by neutron activation analysis and HPGe-gamma-spectrometry, respectively. Averagen=30 radioactivity concentrations of 226Ra (68.4 Bq kg-1), 232Th (85.7 Bq kg-1), and 40K (918 Bq kg-1) were 2.0-2.3-fold higher, which show elevated results compared to the corresponding world mean values. Additionally, mean-REE abundances were 1.02-1.38-times higher than those of crustal origin. Elevated (relative to earth-crust) ratios of Th/U (=3.95 ± 1.84) and 232Th/40K and statistical demonstrations invoke Th-dominant heavy minerals, indicating the role of kaolinite clay mineral abundance/granitic presence. However, Th/Yb, La/V, Hf/Sc, and Th/Sc ratios reveal the presence of felsic abundances, hydrodynamic sorting, and recycling of sedimentary minerals. Geo-environmental indices demonstrated the enrichment of chemical elements in heavy minerals, whereas radiological indices presented ionizing radiation concerns, e.g., the average absorbed-gamma-dose rate (123.1 nGy h-1) was 2.24-fold higher compared to the threshold value which might cause chronic health impacts depending on the degree of exposure. The mean excess lifetime cancer risk value for carcinogen exposure was 5.29 × 10-4 S v-1, which is ∼2-times greater than the suggested threshold. Therefore, plausible extraction of heavy minerals and using residues as building materials can alleviate the two-reconciling problems: (1) radiological risk management and (2) fluvial navigability.

Comparison of microbial communities in unleached and leached ionic rare earth mines.

The leaching of ionic rare earth elements has caused serious environmental pollution and ecological damage. Microorganisms play a crucial role in soil ecosystems and are one of the most important components of these systems. However, there are fewer studies related to the changes that occur in microbial community structure and diversity before and after leaching in ionic rare earth mines. In this study, Illumina high-throughput sequencing was used to examine the diversity and composition of soil microorganisms on the summit, hillside, and foot valley surfaces of unleached and leached mines after in situ leaching. The results showed that microbial diversity and abundance in the surface soil of the unleached mine were higher than those in the leached mine, and leaching had a significant impact on the microbial community of mining soil. pH was the main factor affecting the microbial community. Proteobacteria, Actinobacteriota, and Chloroflexi were phyla that showed high abundance in the soil. Network analysis showed that microbial interactions can improve microbial adaptation and stability in harsh environments. PICRUSt2 predictions indicate functional changes and linkages in soil microbial communities.

Comparative analysis of rare earth elements concentrations in domestic dogs and Apennine wolves of Central Italy: Influence of biological, nutritional, and lifestyle factors.

Rare Earth Elements (REEs) are strategical elements playing a crucial role in the industry, especially in producing high-tech materials. Therefore, REEs are new contaminants of emerging concerns. However, due to the lack of exposure data on REE occurrence in environmental matrices, especially in European countries, it is still tricky to establish environmental background levels to assess the ecotoxicological risk related to REEs exposure. The present study aimed to evaluate the liver concentrations of REEs in domestic dogs (Canis lupus familiaris) and Apennine wolves (Canis lupus italicus) living in the Abruzzo region, Italy. Moreover, for the scope of the present study, the dog's group was divided according to their sex, age, lifestyle, and diet. Wolves were categorized concerning their sex and genetic characteristics. Liver samples from dogs and wolves were collected during diagnostic necropsies from carcasses, sample mineralization was performed by a microwave digestion system with a single reaction chamber, and simultaneous determination of the presence of REEs was performed by Inductively Coupled Plasma Mass Spectrometer (Q-ICP-MS) using standard mode for all rare earth elements except scandium (Sc) which was acquired in kinetic energy discrimination (KED) mode. Hepatic concentrations of REEs were statistically significantly higher in wolves compared to dogs. Moreover, significant differences in REEs concentrations arose also from the genetic type of wolf, since "pure wolves" had higher liver concentrations of REEs compared to wolf-dog hybrids. Female and adult dogs also showed elevated REEs compared to male and juvenile dogs, while no significant differences were demonstrated for dogs' diet and lifestyle. The results of the present study confirm the exposure of domestic and wild carnivores to REEs, showing also the ability of REEs to accumulate in carnivore livers, suggesting the potential role of this species as an alternative bioindicator.

Modulation of proteins by rare earth elements as a biotechnological tool.

Although rare earth element (REE) complexes are often utilized in bioimaging due to their photo- and redox stability, magnetic and optical characteristics, they are also applied for pharmaceutical applications due to their interaction with macromolecules namely proteins. The possible implications induced by REEs through modification in the function or regulatory activity of the proteins trigger a variety of applications for these elements in biomedicine and biotechnology. Lanthanide complexes have particularly been applied as anti-biofilm agents, cancer inhibitors, potential inflammation inhibitors, metabolic elicitors, and helper agents in the cultivation of unculturable strains, drug delivery, tissue engineering, photodynamic, and radiation therapy. This paper overviews emerging applications of REEs in biotechnology, especially in biomedical imaging, tumor diagnosis, and treatment along with their potential toxic effects. Although significant advances in applying REEs have been made, there is a lack of comprehensive studies to identify the potential of all REEs in biotechnology since only four elements, Eu, Ce, Gd, and La, among 17 REEs have been mostly investigated. However, in depth research on ecotoxicology, environmental behavior, and biological functions of REEs in the health and disease status of living organisms is required to fill the vital gaps in our understanding of REEs applications.

Trace element variations in mussels' shells from continent to sea: The St. Lawrence system, Canada.

Rare Earth Elements (REE) and several trace elements abundances in mussel's shells collected along the St. Lawrence River, the Estuary, and the Gulf of St. Lawrence (EGSL) reveal coherent chemical variations, with a sharp contrast between freshwater and seawater bivalves. In freshwater mussel's shells, Rare Earth Elements and Y (REY) patterns are rather flat. Their Mn and Ba concentrations are higher than those of EGSL mussel shells, which are much richer in Sr. Shale-normalized REY abundances in mussel's shells from the EGSL show positive anomalies in La and Y and well-marked negative anomalies in Ce, reflecting those of seawater. Prince Edward Island shells show light REE depletion relative to PAAS, positive La and Y anomalies, and negative Ce anomalies. Our data confirm the lack of detectable Gd pollution in the St. Lawrence River and in the EGSL, as well as Pb pollution at the mouth of the Saguenay Fjord and near Rimouski.

Uptake and transport mechanisms of rare earth hyperaccumulators: A review.

Due to their use in a number of advanced electronic technologies, Rare earth elements (REEs) have recently emerged as a key strategic resource for many nations worldwide. The significant increase in demand for REEs has thus greatly increased the mining of these substances, but this industrial-scale expansion of mining activities also poses potential risks to the surrounding environment, flora, fauna, and humans. Hence efficient REE remediation is one potential remediation process involving in situ clean-up of contaminated soil which has gained much attention in recent years, due to its low cost and lack of secondary pollution. However, some crucial aspects of phytoremediation, such as the precise-mechanisms of absorption, transport, and tolerance of REEs by hyperaccumulators -are poorly understood. This review briefly discusses the environmental risks associated with excess REEs, the efficacy of phytoremediation technologies coupled with, appropriate hyperaccumulator species to migrate REEs exposure. While REEs hyperaccumulator species should ideally be large-biomass trees and shrubs suitable for cropping in subtropical regions areas, such species have not yet been found. Specifically, this review focuses on the factors affecting the bioavailability of REEs in plants, where organic acids are critical ligands promoting efficient transport and uptake. Thus the uptake, transport, and binding forms of REEs in the above-ground parts of hyperaccumulators, especially the transporters isolated from the heavy metal transporter families, are discussed in detail. Finally, having summarized the current state of research in this area, this review proceeds to discuss current knowledge gaps and research directions. With a focus on hyperaccumulators, this review serves as a basis for future phytoremediation strategies of rare earth mining-impacted environments and addresses ecosystem/environmental degradation issues resulting from such mining activity.

Rare earth element behaviors of groundwater in overlying aquifers under the influence of coal mining in northern Ordos Basin, China.

Rare earth elements (REEs) have been used as tracers to reveal the hydrochemical sources and processes in groundwater systems that are usually modified by anthropogenic inputs. However, the REE behaviors in groundwater affected by mining activities have yet to be fully understood. In combination of REE geochemistry with general hydrochemical and isotopic (δ2H and δ18O) methods, this study investigated the concentration and fractionation of REEs in alkaline groundwater from two coal mines with similar aquifer lithology but different mining histories in the Northern Ordos Basin. One of the coal mines started mining in March 2009 (Ningtiaota coal mine, NTT), while the other started mining in December 2018 (Caojiatan coal mine, CJT). Results show that the primary hydrochemical type is HCO3-Ca in NTT groundwater with pH value ranging between 7.68 and 8.60, while CJT groundwater was dominated by the HCO3-Na type with higher pH of 9.09-10.00. The average values of ΣREEs were lower, and the NASC-normalized pattern reflected more intense fractionation in NTT groundwater than those in CJT groundwater. The evident differences are caused by the distinctions in water-rock interaction, complexation of inorganic species, and adsorption of REEs in NTT and CJT groundwater. Furthermore, these processes were closely related to the pH of groundwater that was different in two coal mines, which is likely linked to the different durations of coal mining activities that led to differences in development of rock fractures and pyrite oxidation. It is expected that REEs, combined with other indicators such as pH, can be used to trace and help better understand the hydrochemical changes in groundwater caused by mining.

An insight into REEs recovery from spent fluorescent lamps: Evaluation of the affinity of an NH4-13X zeolite towards Ce, La, Eu and Y.

The constantly increasing demand of Rare Earth Elements (REEs) made them to be part of the so-called "critical elements" indispensable for the energy transition. The monopoly of only a few countries, the so-called balance problem between demand and natural abundance, and the need to limit the environmental costs of their mining, stress the necessity of a recycling policy of these elements. Different methods have been tested for REEs recovery. Despite the well-known ion-exchange properties of zeolites, just few preliminary works investigated their application for REEs separation and recycle. In this work we present a double ion exchange experiment on a NH4-13X zeolite, aimed at the recovery of different REEs from solutions mimicking the composition of liquors obtained from the leaching of spent fluorescent lamps. The results showed that the zeolite was able to exchange all the REEs tested, but the exchange capacity was different: despite Y being the more concentrated REE in the solutions, the cation exchange was lower than less concentrated ones (16 atoms p.u.c. vs 21 atoms for Ce and La solutions), suggesting a possible selectivity. In order to recover REEs from the zeolite, a second exchange with an ammonium solution was performed. The analyses of the zeolites show that almost all of Ce and Eu remain in the zeolite, while nearly half of La and Y are released. This, once again, suggests a possible selective release of REEs and open the possibility for a recovery process in which Rare Earths can be effectively separated.

Variability of rare earth and heavy metal elements in a representative alluvial depositional system.

Heavy metals (Ni, Cr, W, Cd, and Pb) and rare earth elements (REE) were investigated in the flood plain sediments of an island of the lower Yangtze River near Nanjing to determine how the vertical distribution of heavy metals could be affected by natural sedimentation processes and anthropogenic contamination. Stratigraphic analyses of magnetic susceptibility and the mean grain size distribution of the deposits enabled us to identify layers associated with a relatively high influx of suspended sediments that resulted in sudden changes in the concentrations of heavy metals. The results show that layers associated with high sediment influx (0.8 m depth) displayed low concentrations of Cr, Ni, W, and Cd that were mainly lithogenic in origin. The Post Archean Australian Shale (PAAS) normalized REE patterns in the flood plain cores were enrichment in Ce and Eu relative to PAAS, indicating that the sediments were most likely derived from a mixture of sediments and not from an anthropogenic source. Sharp increases in Y/Ho ratios, as well as heavy metal (Cd, Cr, Ni, and W) and Y concentrations were observed in the uppermost layer that could have been deposited from the rapid transport of sediment-laden, contaminated waters. The temporal (vertical) trends in Pb concentrations may be strongly influenced by coal burning. Elevated Pb concentrations (350 ppm and 1000 ppm) correlate with high magnetic susceptibility (> 200 m3 × kg-1) and the history of thermal power plant (1910-2002) activity. The anthropogenic inputs of Pb were, however, not diluted by high suspended sediment loads, which supports the argument that Pb was derived from fly ash.

Associations between maternal urinary rare earth elements during pregnancy and birth weight-for-gestational age: Roles of cord blood vitamin D levels.

Prenatal exposure to rare earth elements (REEs) may contribute to adverse birth outcomes in previous studies. Cord blood vitamin D has been suggested to modify or mediate the effects of environmental exposures. However, none has investigated these roles of cord blood vitamin D in the associations of prenatal exposure to REEs with fetal growth. Maternal trimester-specific urinary concentrations of 13 REEs, cord blood total 25-hydroxyvitamin D at delivery, and birth weight (BW)-for-gestational age (GA) were determined in 710 mother-newborn pairs from Wuhan, China. Higher maternal average urinary concentrations of europium (Eu), gadolinium (Gd), dysprosium (Dy), holmium (Ho), erbium (Er), and ytterbium (Yb) across three trimesters, either individually or jointly, were significantly associated with lower BW-for-GA Z-scores and higher odds of small for gestational age (SGA) [ß = -0.092; 95 % confidence interval (CI): -0.149, -0.035 for BW-for-GA Z-scores, and odds ratio = 1.60; 95 % CI: 1.14, 2.24 for SGA involved in each unit increase in weighted quantile sum index of REEs mixture]. When stratified by cord blood vitamin D levels, the associations mentioned above persisted in participants with relatively low vitamin D levels (<13.94 µg/L, the first tertile of distribution), but not among those with relatively high levels (≥13.94 µg/L) (all p-values for interaction < 0.05). The mediation analyses taking account of exposure-mediator interaction showed that the relationships between REEs (as individual and mixture) exposure and lower BW-for-GA were partly mediated through decreasing cord blood vitamin D levels. The proportions mediated by cord blood vitamin D levels were 24.48 % for BW-for-GA Z-scores and 29.05 % for SGA corresponding to the REEs mixture exposure. Conclusively, our study revealed that prenatal exposures to Eu, Gd, Dy, Ho, Er, and Yb were related to fetal growth restriction. Cord blood vitamin D might alleviate toxic effects of these REEs and its reduction might partly mediate REE-induced fetal growth restriction.

The association between levels of samarium, hafnium, tungsten and rhenium in seminal plasma and the risk of idiopathic oligo-astheno-teratozoospermia in men of childbearing age.

Oligo-astheno-teratozoospermia (OAT) is a global public health problem, which affects 30% men of childbearing age. Meanwhile, with the rapid development of industry and economy, the contents of rare earth elements (REEs) in the environment are increasing. However, little is known about the associations between REEs levels and OAT risk. To evaluate the associations between the levels of four REEs (samarium (Sm), hafnium (Hf), tungsten (W), rhenium (Re)) in seminal plasma and OAT risk, from October 2021 to November 2022, semen samples from 924 men of childbearing age (460 controls and 464 cases) were collected from the reproductive center of the First Affiliated Hospital of Anhui Medical University. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to measure the levels of Sm, Hf, Re and W in seminal plasma. Bayesian kernel machine regression (BKMR) was conducted to explore the joint effects of levels of four REEs in seminal plasma on the risk of OAT and select the one exerting a major role; generalized linear regression models (GLM) with log link function were employed to investigate the association of every REE level in seminal plasma and OAT risk; sankey diagram and linear regression models were utilized to describe the associations between the levels of four REEs and the indexes of sperm quality. The levels of four REEs in seminal plasma were higher in the case group than levels in the control group (pSm = 0.011, pHf = 0.040, pW = 0.062, pRe = 0.001, respectively). In BKMR analysis, the OAT risk increased when the overall levels of four REEs were higher than their 55th percentile compared to all of them at their 50th percentile, and Re level played a major role in the association. Additionally, Re level in seminal plasma was positively associated with  the OAT risk in the single element model after adjustment of covariates (medium vs. low: OR (95% CI) = 1.55 (1.10, 2.18); high vs. low: OR (95% CI) = 1.69 (1.18, 2.42)). Lastly, the sankey diagram and linear regression models revealed that Sm level was negatively associated with the PR%, total sperm count and total progressively motile sperm count; Hf level was negatively associated with the PR%; W and Re levels were negatively associated with the PR% and total motility, and Re level was positively associated with abnormal morphology rate. Men of childbearing age with OAT had higher levels of Sm, Hf and Re in seminal plasma than those in the control group. An increasing trend for the OAT risk was observed with an increase in mixture levels of Sm, Hf, W and Re, and Re exposure level played a major role in the association whether in BKMR model or single element model. Additionally, the levels of these four REEs were negatively associated with the indexes of sperm quality.