Rare earth element bioaccumulation and cerium anomalies in biota from the Eastern Canadian subarctic (Nunavik).

Recent increases in the demand for rare earth elements (REE) have contributed to various countries' interest in exploration of their REE deposits, including within Canada. Current limited knowledge of REE distribution in undisturbed subarctic environments and their bioaccumulation within northern species is addressed through a collaborative community-based environmental monitoring program in Nunavik (Quebec, Canada). This study provides background REE values (lanthanides + yttrium) and investigates REE anomalies (i.e., deviations from standard pattern) across terrestrial, freshwater, and marine ecosystems in an area where a REE mining project is in development. Results are characteristic of a biodilution of REE, with the highest mean total REE concentrations (ΣREE) reported in sediments (102 nmol/g) and low trophic level organisms (i.e., biofilm, macroalgae, macroinvertebrates, common mussels, and reindeer lichens; 101-102 nmol/g), and the lowest mean concentrations in higher-level consumers (i.e., goose, ptarmigan, char, whitefish, cod, sculpin and seal; 10-2 - 101 nmol/g). The animal tissues are of importance to northern villages and analyses demonstrate a species-specific bioaccumulation of REE, with mean concentrations up to 40 times greater in liver compared to muscle, with bones and kidneys presenting intermediate concentrations and the lowest in blubber. Further, a tissue-specific fractionation was presented, with significant light REE (LREE) enrichment compared to heavy REE (HREE) in consumer livers (LREE/HREE ≅ 101) and the most pronounced negative cerium (Ce) anomalies (<0.80) in liver and bones of fish species. These fractionation patterns, along with novel negative relationships presented between fish size (length, mass) and Ce anomalies suggest metabolic, ecological, and/or environmental influences on REE bioaccumulation and distribution within biota. Background concentration data will be useful in the establishment of REE guidelines; and the trends discussed support the use of Ce anomalies as biomarkers for REE processing in animal species, which requires further investigation to better understand their controlling factors.

Influence of cerium oxide nanoparticles on dairy effluent nitrate and phosphate bioremediation.

This study investigated, for the first time, the role of cerium oxide nanoparticles (CeO2 NPs) on dairy effluent nitrate and phosphate bioremediation using different inoculum sources. Two inoculum sources (wastewater and sludge) were obtained from the dairy wastewater treatment plant unit. A culture was prepared to be tested in the treatment of nitrate and phosphate effluent, and the role of CeO2 NPs was checked to be completely efficient after 5 days of incubation. The reduction efficiency of nitrate using sludge as inoculum source was improved up to 89.01% and 68.12% for phosphate compared to control. In the case of using wastewater as an inoculum source, the nitrate reduction was improved up to 83.30% and 87.75% for phosphate compared to control. The bacterial richness showed a significant variance (higher richness) between control and other samples. The optimal concentration of CeO2 NPs for inoculum richness and nitrate and phosphate reduction was (sludge: 1 × 10-10 ppm) and (wastewater: 1 × 10-12 ppm). The results revealed that CeO2 NPs could enhance the microbial growth of different inoculum sources that have a key role in dairy effluent nitrate and phosphate bioremediation.

The effects of exogenous cerium on photosystem II as probed by in vivo chlorophyll fluorescence and lipid production of Scenedesmus obliquus XJ002.

Cerium is the most abundant rare earth metal in the earth's crust, and it has deleterious effects on aquatic ecosystems from fertilizer runoff. Scenedesmus obliquus is an oil-rich microalga that grows rapidly and is sensitive to many kinds of toxins. Given that microalgae are useful indicators of eutrophication and toxic stress, it was found that lower concentrations of cerium (0.50-5.00 mg·L-1 ) stimulated algal growth and increased chlorophyll a content, whereas higher concentrations (above 50.00 mg·L-1 ) had an inhibitory effect on algal growth and chlorophyll a content. The algal growth rate and chlorophyll a content peaked at a cerium concentration of 5.00 mg·L-1 . Both the donor and acceptor sides of photosystem II (PSII) reaction centers were sensitive to cerium-induced stress. Specifically, high concentrations of cerium damaged the oxygen evolving complex and PSII reaction center and suppressed electron transport at the donor and receptor side of the reaction center, influencing the absorption, transfer, and application of light energy in S. obliquus XJ002. In addition, we established a simple method to quantify the intracellular lipid content of S. obliquus XJ002, and the optimum staining conditions for Nile red were as follows: volume percentage of dimethyl sulfoxide was 2%, the concentration of Nile red was 2.0 µg·mL-1 , and the staining time of Nile red was 5 min. The addition of cerium resulted in a significant increase in the total lipid content of XJ002. When the concentration of cerium was 50 mg·L-1 , the total lipid content was 16.26% higher than the control group. This information will enhance our ability to utilize microelement fertilizer in biomass accumulation programs and will help to further reveal the key regulatory factors in the lipid metabolism, and would lay the foundation for promoting the research of microalgae bioenergy.

Fates of Au, Ag, ZnO, and CeO2 Nanoparticles in Simulated Gastric Fluid Studied using Single-Particle-Inductively Coupled Plasma-Mass Spectrometry.

The increasing use of engineered nanoparticles (ENPs) in many industries has generated significant research interest regarding their impact on the environment and human health. The major routes of ENPs to enter the human body are inhalation, skin contact, and ingestion. Following ingestion, ENPs have a long contact time in the human stomach. Hence, it is essential to know the fate of the ENPs under gastric conditions. This study aims to investigate the fate of the widely used nanoparticles Ag-NP, Au-NP, CeO2-NP, and ZnO-NP in simulated gastric fluid (SGF) under different conditions through the application of single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS). The resulting analytical methods have size detection limits for Ag-NP, Au-NP, ZnO-NP, and CeO2-NP from 15 to 35 nm, and the particle concentration detection limit is 135 particles/mL. Metal ions corresponding to the ENPs of interest were detected simultaneously with detection limits from 0.02 to 0.1 µg/L. The results showed that ZnO-NPs dissolved completely and rapidly in SGF, whereas Au-NPs and CeO2-NPs showed apparent aggregation and did not dissolve significantly. Both aggregation and dissolution were observed in Ag-NP samples following exposure to SGF. The size distributions and concentrations of ENPs were affected by the original ENP concentration, ENP size, the contact time in SGF, and temperature. This work represents a significant advancement in the understanding of ENP characteristics under gastric conditions.

La, Ce and Nd in the soil-plant system in a vegetation experiment with barley (Hordeum vulgare L.).

Rare earth elements (REEs) have received enormous attention in recent years. However, there are many gaps in the understanding of their behavior in the soil-plant system. The aim of this study is to investigate the behavior of three most common REEs (La, Ce, Nd) in the soil-plant system directly on soil samples using barley (Hordeum vulgare L.) in a vegetation experiment. We attribute the absence of significant changes in plant biomass and photosynthetic pigment content to the reduced availability of REEs in soil samples. The concentration of water-soluble forms of La, Ce and Nd didn't exceed 1 mg/kg, while the concentration of exchangeable forms varied and decreased in a row La > Ce > Nd. The transfer factor (TF) from soil to above-ground biomass was low for all three elements (<1). The stem-to-leaf TF increased with the increase in REEs concentration in soil. The concentration in plant material increased in the row Ce < Nd < La. REEs concentrations in barley leaves didn't exceed 1-3% of the corresponding element concentration in soil samples. REEs concentration in plant tissues is in close direct correlation with the REEs total concentration in soil, water-soluble and exchange forms. REEs concentration in barley leaves is 3-4 times higher than in the stems and for the group with extraneous concentration of 200 mg/kg for La, Ce and Nd was 6.20 ± 1.48, 2.10 ± 0.51, 6.90 ± 3.00 mg/kg, respectively. We show that there were no major changes in barley plants, but further study is needed of the relationship between the absorption of lanthanides by plants and the content of various forms of lanthanides in the soil.

Analysis of cerium oxide and copper oxide nanoparticles bioaccessibility from radish using SP-ICP-MS.

BACKGROUND: The transformation of nanoparticles (NPs) internalized in plant tissues is the human digestive system that can provide a better understanding of the impact of NPs on the human system. The presented methodology was developed to study the bioaccessibility of cerium oxide (CeO2 ) and copper oxide (CuO) NPs from radish after the in vitro simulation of gastrointestinal digestion using single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS). RESULTS: Radish plants were cultivated hydroponically in a growth medium containing: (i) CeO2 NPs and (ii) CuO NPs. Both cerium (Ce) and copper (Cu) were found in all organs of the radish plants after analysis by standalone ICP-MS. This confirms the bioaccumulation of CeO2 and CuO NPs and the translocation of their Ce and Cu to the aerial parts of the plant. Less Ce (4.095 µg g-1 ) has been detected in leaves than in roots (1.156 mg g-1 ) while Cu content in leaves was 5.245 µg g-1 and in roots was 10.41 µg g-1 . Analysis of the digestive extracts obtained after the in vitro simulation of gastro (pepsin) and gastrointestinal (pancreatin) digestion showed that Ce has easy access to human system at least by 73%. CONCLUSION: The size of CeO2 NPs in digestive extracts showed no significant changes. However, the results obtained for CuO NPs digestion were variable and suggested that CuO NPs dissolved during the digestion process. The CuO NPs were observed in roots after the gastrointestinal digestion concluding that CuO NPs recovered after the initial dissolution. © 2020 Society of Chemical Industry.

Biochar-assisted transformation of engineered-cerium oxide nanoparticles: Effect on wheat growth, photosynthetic traits and cerium accumulation.

The extensive use of nano-fabricated products in daily life is releasing a large volume of engineered nanoparticles (ENPs) in the environment having unknown consequences. Meanwhile, little efforts have been paid to immobilize and prevent the entry of these emerging contaminants in the food chain through plant uptake. Herein, we investigated the biochar role in cerium oxide nanoparticles (CeO2NPs) bioaccumulation and subsequent translocation in wheat (Triticum aestivum L.) as well as impact on growth, photosynthesis and gas-exchange related physiological parameters. Results indicated that CeO2NPs up to 500 mg L-1 level promoted the plant growth by triggering photosynthesis, transpiration and stomatal conductance. Higher NPs concentration (2000 mg CeO2NPs L-1) has negatively affected the plant growth and photosynthesis related processes. Conversely, biochar amendment with CeO2NPs considerably reduced (~9 folds) the plants accumulated contents of Ce even at 2000 mg L-1 exposure level of CeO2NPs through surface complexation process and alleviated the phyto-toxic effects of NPs on plant growth. XPS and FTIR analysis confirmed the role of biochar-mediated carboxylate and hydroxyl groups bonding with CeO2NPs. These findings provides an inside mechanistic understanding about biochar interaction with nano-pollutants to inhibit their bioavailability to plant body.

Relatively Low Dosages of CeO2 Nanoparticles in the Solid Medium Induce Adjustments in the Secondary Metabolism and Ionomic Balance of Bean (Phaseolus vulgaris L.) Roots and Leaves.

Nanoparticles (NPs) are known to significantly alter plant metabolism in a dose-dependent manner, with effects ranging from stimulation to toxicity. The metabolic adjustment and ionomic balance of bean (Phaseolus vulgaris L.) roots and leaves gained from plants grown in a solid medium added with relatively low dosages (0, 25, 50, and 100 mg/L) of CeO2 NPs were investigated. Ce accumulated in the roots (up to 287.91 mg/kg dry weight) and translocated to the aerial parts (up to 2.78% at the highest CeO2 dosage), and ionomic analysis showed that CeO2 NPs interfered with potassium, molybdenum, and zinc. Unsupervised hierarchical clustering analysis from metabolomic profiles suggested a dose-dependent and tissue-specific metabolic reprogramming induced by NPs. The majority of differential metabolites belonged to flavonoids and other phenolics, nitrogen-containing low molecules (such as alkaloids and glucosinolates), lipids, and amino acids.

Development of a comprehensive understanding of aggregation-settling movement of CeO2 nanoparticles in natural waters.

Parameters such as the settling rate, aggregation rate, and collision frequency in predictive models used to describe the fate of nanoparticles (NPs) are very important for the risk assessment of NPs in the environment. In this study, CeO2 NPs were chosen as the model particles to investigate such parameters through aggregation-settling experiments under environmentally relevant conditions. The results indicate that natural colloids (Ncs) have no effect on the settling of NPs in seawaters, whereas they stabilize the NPs at a low initial particle concentration and promote the heteroaggregation of NPs at a high initial particle concentration in lake waters. In all cases, a suspended sediment absorbs the NPs and Ncs as mixed aggregates, resulting in a rapid settling. Furthermore, the calculation results of the model indicate that the shear force increases the collision frequency of the NPs by 4-5 orders of magnitude higher than that in quiescent waters. However, the break-up effect by the shear force is more obvious, namely, the shear force hinders the aggregation of NPs in natural waters, instead of promoting aggregation. Remarkably, a negative value of the dis-heteroaggregation rate based on the combined von Smoluchowski-Stokes equation can reflect the hindering effect on the aggregation process. The results of this study will provide scientific and accurate guidance for the parameter selection in the existing prediction model and contribute to a prediction of the fate and transport of NPs in the environment.

Novel fluorescein- and pyridine-conjugated schiff base probes for the recyclable real-time determination of Ce3+ and F.

The effect of aminopyridines substituted at different positions on the fluorescence properties deserves to be studied. Since 2-aminopyridyl-based probes have been reported, the effects of 3-aminopyridine and 4-aminopyridine on the performance of fluorescein probes were discussed in here. Two Schiff base fluorescein probes FN-1, FN-2 were designed and synthesized. Among them, since the ligand shows a highly selective and sensitive response to metal charge transfer (LMCT), the fluorescence of FN-1 can be quenched by Ce3+ ions in PBS buffer. At the same time, a specific precipitation reaction between Ce3+ and F- releases the free probe to restore the fluorescence of FN-1. Therefore, FN-1 can be used for the recyclable 'ON-OFF-ON' detection of Ce3+and F-. The detection limits for Ce3+and F- are 4.48 µM and 11.58 µM in concentration range of 0-50 µM and 0-150 µM. However, due to the para position of N and amino groups on 4-aminopyridine, the spatial structure of FN-2 cannot be complexed with ions, resulting in poor selectivity. Polyvinylidene fluoride (PVDF) membrane containing FN-1 were prepared for the real-time qualitative detection of Ce3+and F- in real water samples. FN-1 exhibits high water solubility and biocompatibility and has been successfully applied to biological imaging in vascular smooth muscle cells (VSMCs).

Cerium Oxide Nanoparticles Absorption through Intact and Damaged Human Skin.

Cerium oxide (CeO2) nanoparticles (NPs) are used in polishing products and absorbents, as promoters in wound healing, and as organopesticide decontaminants. While systemic bioaccumulation and organ toxicity has been described after inhalation, data on CeO2 NPs' transdermal permeation are lacking. Our study was an in vitro investigation of the permeation of 17-nm CeO2 NPs dispersed in synthetic sweat (1 g L-1) using excised human skin on Franz cells. Experiments were performed using intact and needle-abraded skin, separately. The average amount of Ce into intact and damaged skin samples was 3.64 ± 0.15 and 7.07 ± 0.78 µg cm-2, respectively (mean ± SD, p = 0.04). Ce concentration in the receiving solution was 2.0 ± 0.4 and 3.3 ± 0.7 ng cm-2 after 24 h (p = 0.008). The Ce content was higher in dermal layers of damaged skin compared to intact skin (2.93 ± 0.71 µg cm-2 and 0.39 ± 0.16 µg cm-2, respectively; p = 0.004). Our data showed a very low dermal absorption and transdermal permeation of cerium, providing a first indication of Ce skin uptake due to contact with CeO2.

Intentional hydrolysis to overcome the hydrolysis problem: detection of Ce(iv) by producing oxidase-like nanozymes with F.

Polyvalent metal ions are susceptible to hydrolysis, making their reproducible detection by sensors and biosensors difficult. We herein turned this disadvantage into an advantage to develop a high selectivity colorimetric method for detecting Ce(iv) by intentionally hydrolyzing it through heating, where subsequent addition of F- recovered the activity, allowing a detection limit of 3.8 µM Ce(iv).

Integration of sub-organ quantitative imaging LA-ICP-MS and fractionation reveals differences in translocation and transformation of CeO2 and Ce3+ in mice.

Information on the risk of exposure to cerium oxide (CeO2) nanoparticles (NPs) is limited. To assess risk, we must know where and how such NPs are distributed to the body after exposure, both short- and long-term. In this work, an integrated approach of quantitative LA-ICP-MS bioimaging and fractionation was employed to study the translocation and transformation of CeO2 and Ce3+ in mouse spleen and liver. The complementary information retrieved by the two techniques above on the accumulation of Ce and dissolution/aggregation were found consistent. In brief, a detailed fine scanning of a region of interest in the organ was performed after fast-screening at low spatial resolution. In the spleen, after short-term high-dose exposure, CeO2 NPs was found mainly in the marginal zone and caused an up-regulation of Zn in the white pulp. After long-term low-dose exposure, CeO2 was found in the marginal zone and white pulp. In the liver, CeO2 NPs were mainly distributed in the Kupffer cells and lobule periphery. The high spatial resolution LA maps of H&E-stained liver sections allowed imaging close to cell level; this enabled an estimation of Ce content in Kupffer cells. Furthermore, fractionation by ultrafiltration was also employed to differentiate the ionic and NP species in the organs. This fractionation showed aggregation of Ce ions in spleen, supporting the LA-ICP-MS results. Transmission electron microscopy revealed that long-term CeO2 exposure triggered an immune response to infection in the spleen and confirmed the differential deposition of Ce in the marginal zone. The integrated analyses based on ICP-MS together with histology and TEM investigation suggests that long-term low doses of CeO2 NPs may cause toxicity in the liver and impair functions of the immune system.

Behavior of cerium dioxide nanoparticles in chernozem soils at different exposure scenarios.

Nowadays, widespread application of engineered nanoparticles (ENPs) inevitably leads to their release into the environment. Soils are regarded as the ultimate sink for ENPs. The study on mobility of ENPs in soils is important in the assessment of potential risks related to their toxicity. The behavior of ENPs is dependent not only on parameters of soil but also on exposure scenarios, namely, the amount of ENPs trapped in soil. In the present work, the mobility of cerium dioxide nanoparticles (nCeO2) in soils at different exposure scenarios has been studied. The relationship between mobility of nCeO2 and their concentration in soil in the range from 1 to 1000 µg g-1 is evaluated. It is shown that the mobility of nCeO2 decreases with decreasing their concentration in soil and attains the minimum value at the concentration of nCeO2 below 10 µg g-1. In relative terms, only about 0.1-0.2% of nCeO2 at their concentration in soil 10-1000 µg g-1 are mobile and can migrate in soil profile under saturated conditions. The major portion of nCeO2 (about 99.8%) remains immobile in soil. Evidently, the vertical transport of nCeO2 in soil profile should depend on volume of released suspensions. In the case of small or moderate wet deposition, nanoparticles will accumulate in upper soil horizons, where biological activity is highest, and affect the soil inhabitants (plant roots, earthworms, insects, microorganisms, etc.).

Transport and retention of differently coated CeO2 nanoparticles in saturated sediment columns under laboratory and near-natural conditions.

Where surface-functionalized engineered nanoparticles (NP) occur in drinking water catchments, understanding their transport within and between environmental compartments such as surface water and groundwater is crucial for risk assessment of drinking water resources. The transport of NP is mainly controlled by (i) their surface properties, (ii) water chemistry, and (iii) surface properties of the stationary phase. Therefore, functionalization of NP surfaces by organic coatings may change their fate in the environment. In laboratory columns, we compared the mobility of CeO2 NP coated by the synthetic polymer polyacrylic acid (PAA) with CeO2 NP coated by natural organic matter (NOM) and humic acid (HA), respectively. The effect of ionic strength on transport in sand columns was investigated using deionized (DI) water and natural surface water with 2.2 mM Ca2+ (soft) and 4.5 mM Ca2+ (hard), respectively. Furthermore, the relevance of these findings was validated in a near-natural bank filtration experiment using HA-CeO2 NP. PAA-CeO2 NP were mobile under all tested water conditions, showing a breakthrough of 60% irrespective of the Ca2+ concentration. In contrast, NOM-CeO2 NP showed a lower mobility with a breakthrough of 27% in DI and < 10% in soft surface water. In hard surface water, NOM-CeO2 NP were completely retained in the first 2 cm of the column. The transport of HA-CeO2 NP in laboratory columns in soft surface water was lower compared to NOM-CeO2 NP with a strong accumulation of CeO2 NP in the first few centimeters of the column. Natural coatings were generally less stabilizing and more susceptible to increasing Ca2+ concentrations than the synthetic coating. The outdoor column experiment confirmed the low mobility of HA-CeO2 NP under more complex environmental conditions. From our experiments, we conclude that the synthetic polymer is more efficient in facilitating NP transport than natural coatings and hence, CeO2 NP mobility may vary significantly depending on the surface coating.

Synthesis and spectral analysis of fluorescent probes for Ce4+ and OCl- ions based on fluorescein Schiff base with amino or hydrazine structure: Application in actual water samples and biological imaging.

Two Schiff base fluorescein probes (FDA, FDH) based on fluorescein-aldehyde and nitroaniline derivatives were synthesized. The effects of amino and hydrazine substituents in fluorescein backbones were examined via fluorescence and absorbance spectra. In the presence of Ce4+, the fluorescence of FDA was quenched due to the ligand to metal charge transfer (LMCT). Hypochloric acid can react with the CN bond, and blocking the photo induced electron transfer (PET) of FDH leads to enhancement of the fluorescence. FDA showed detection limits for Ce4+ and OCl- as low as 63 nM in concentration range of 0-4 µM. FDH showed detection limits for OCl- as low as 0.8 µM in concentration rang 0-100 µM. Polyvinylidene fluoride (PVDF) membrane containing the probes was prepared for the real-time qualitative detection of Ce4+ and OCl- in real water samples. The probes were successfully applied to biological imaging in vascular smooth muscle cells (VSMCs) and are expected to find applications in biosensing.

Iron plaque reduces cerium uptake and translocation in rice seedlings (Oryza sativa L.) exposed to CeO2 nanoparticles with different sizes.

This study aims to assess the role of iron plaque (IP) on cerium (Ce) uptake and translocation by rice after CeO2 nanoparticles (NPs) exposure over a 4 days period. A hydroponic experiment was performed under two IP levels (low and high) combined with two CeO2 NPs size (14 nm and 25 nm). It was found that CeO2 NPs as the main form was absorbed by rice due to limited NPs dissolution in hydroponic solution. IP significantly reduced surface-Ce, root-Ce and shoot-Ce accumulation, irrespective of CeO2 NPs sizes. The reduced uptake of Ce was more obvious in NP25 than NP14. Ce accumulations decreased with increasing IP amounts. In IP treatments, the interactive attraction between NPs and root surface was weakened through the enhancement of hydrodynamic diameters and the reduction of ζ-potential of CeO2 NPs in solution, as well as the reduction of |ζ| values of rice root, which reduced the Ce bioaccumulation in rice. PCA indicated the negative correlation between surface-Ce (IP-C-Ce and IP-A-Ce) and NPs size, and between shoot-Ce/root-Ce and IP-Fe/tissue-Fe. IP also decreased Ce translocation from root to shoot. A full life study indicated the reduction effect of IP on surface-Ce, root-Ce, shoot-Ce and grain-Ce accumulations. These findings are significant as they imply that the IP formation is a promising approach for preventing Ce accumulation in rice, which would regulate Ce uptake by rice in the following growth stages and decrease the health risk of CeO2 NPs exposure in agricultural environment.

Toxicological Aspect of Some Selected Medicinal Plant Samples Collected from Djelfa, Algeria Region.

Instrumental neutron activation analysis (INAA) has been used to determine the concentration of some toxic chemical elements in a variety of aromatic plants samples collected from Djelfa region. In the present work, eight medicinal plants were examined, such as Artemisia herba-alba Asso., Artemisia compestris L., Laurus nobilis L., Origanum vulgare L., Mentha spicata L., Rosmarinus officinalis L., Mentha pulegium L., and Pistacia lentiscus L. The levels of toxic elements were compared to their daily total intake; Arsenic was present in all plant species examined, with a concentration ranging from 0.18 to 5.44 µg g- 1. Bromine was also detected in all the medicinal plant species, with high concentrations, compared to arsenic except in the case of Laurus nobilis that has the highest concentration of arsenic. Cerium, cobalt, chromium, and antimony were presented in all plant species. The exactitude of the results was assessed by analyzing the certified reference material of SRM-NIST 1573a and CRM GB07605 (GSV4). These data analysis for this medicinal plant can be useful for therapeutics and pharmaceutical purposes.

Luminescence and Cationic-Size-Driven Site Selection of Eu3+ and Ce3+ Ions in Ca8Mg(SiO4)4Cl2.

In this work, the morphology, composition, crystal, and electronic structure of Ca8Mg(SiO4)4Cl2 (CMSOC) prepared by a high-temperature solid-state reaction technique are characterized first. To investigate the site occupancies of Eu3+ and Ce3+ in CMSOC, the emission spectra under well-chosen wavelength excitations and the corresponding excitation spectra by monitoring of the specific wavelength emissions are measured in detail for singly doped samples with different concentrations. Two kinds of Eu3+ or Ce3+ luminescence spectra are found. On the basis of the chemical environments of two Ca2+ sites and dielectric chemical bond theory, the sites of these two kinds of Eu3+ and Ce3+ luminescence spectra are respectively assigned. Because energy transfer between the two types of luminescent centers, concentration-dependent emission-wavelength shifting, and luminescence concentration quenching are negligible, the emission spectra of Eu3+ and Ce3+ give us a hint of their occupation preferences on two Ca2+ sites. The results indicate that, with an increase of the doping concentration, the Eu3+ ions with smaller cationic size show an occupation preference on the smaller Ca2+(1) sites, but the Ce3+ ions with larger cationic size are inclined to enter the larger Ca2+(2) sites. These opposite occupation preferences of Eu3+ and Ce3+ in CMSOC are thought to be the cationic-size-driven site selection.

Investigation of rare earth elements in urine and drinking water of children in mining area.

To compare the contents of rare earth elements in urine and drinking water of children in the mining and control areas and evaluate the health risk of children in the mining area.Urine and drinking water of 128 children in the mining area and 125 children in the control area were collected from June to July 2015. The contents of rare earth elements were determined using inductively coupled plasma mass spectrometry.The detection rates of rare earth elements, including yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), and samarium (Sm), in the urine of children in the exposed group were all 100%, except for samarium (98%); the rates in the control group were 85.7%, 100%, 100%, 98%, 98%, and 59.2%, respectively, and the remaining elements were not detectable. The concentrations of Y, La, Ce, Pr, Nd, and Sm in the urine of children in the exposed group were significantly higher than that in the control group (P < .01). In addition, the composition ratio of lanthanum was higher than that in the control group. The detection rates of lanthanum and Ce in the drinking water of children in the exposed group were 1.44% and 0.72%, respectively. The others were not detectable; the rates in the control group were all 0%.The pollution caused by the presence of Y, La, Ce, Pr, Nd, and Sm in the mining area might affect the health of children in the area, but drinking water might not be the cause.