[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.

Effects of Er: YAG, Er,Cr: YSGG, and Nd: YAG laser irradiation and adhesive systems on the immediate and long-term bond strength of dentin: a systematic review and meta-analysis.

At present, lasers are increasingly used in the oral clinical field, and research and applications in dental hard tissue treatment are also increasing. The effect of laser etching dentin on the bonding strength of composite resin reported in the literature is still inconclusive. The purpose of this review was to evaluate whether laser etching can improve the immediate and long-term bonding strength of dentin and investigate the effect of different types of adhesives on the bonding strength of dentin. Two reviewers performed a literature search up from January 2012 to November 2021 in four databases: MEDLINE (PubMed), Web of Science, EMBASE, and the Cochrane Library. A total of 25 studies were included in the meta-analysis. The Cochrane Collaboration Bias Risk Assessment tool was used to evaluate the quality of the included literature, and an analysis was carried out using Review Manager Software version 5.3. The aging bond strength of dentin after erbium (Er): yttrium aluminum garnet (YAG) laser treatment was significantly lower than that of dentin in the bur group (P < 0.00001). At the same time, the bond strength of dentin immediately and aging after (Er), chromium-doped (Cr): yttrium scandium gallium garnet (YSGG) laser treatment was lower than that of dentin in the bur group (P < 0.05). There was no significant difference in the immediate and aging bonding strength among samples in the Er: YAG laser, Er, Cr: YSGG laser, and blank control groups (no laser or bur). The aging bond strength of samples after neodymium-doped (Nd): YAG laser treatment was higher than that of samples in the blank control group (P < 0.05); in addition, the performance of self-etching adhesive was slightly better than that of acid etching adhesive. Regardless of the applied surface treatment and the adhesive employed, dentin after aging showed significant bond degradation (P < 0.05). There was high heterogeneity of bond strength between different groups, and the small number of studies and the contradictory results may be the main reasons for this outcome.

In the presence of fluoride, free Sc³âº is not a good predictor of Sc bioaccumulation by two unicellular algae: possible role of fluoro-complexes.

We investigated the effect of fluoride complexation on scandium accumulation by two unicellular algae, Chlamydomonas reinhardtii and Pseudokirchneriella subcapitata. This trivalent metal was selected for its chemical similarities with aluminum and for its convenient radioisotope (Sc-46), which can be used as a tracer in short-term bioaccumulation studies. Scandium surface-bound concentrations (Sc(ads)) and uptake fluxes (J(int)) were estimated in the two algae over short-term (<1 h) exposures at pH 5 and in the presence of 0 to 40 µM F(-). Although the computed proportion of dissolved Sc(3+) dropped from 20% to 0.01% over this [F(-)] range, Sc(ads) and J(int) values for both algae decreased only slightly, suggesting a participation of Sc fluoro-complexes in both processes. Surface adsorption and uptake of fluoride complexes with aluminum have been reported in the literature. These observations are not taken into account by current models for trace metal bioaccumulation (e.g., the biotic ligand model). Results from a previous study, where the effects of pH on Sc uptake were investigated, suggested that Sc hydroxo-complexes were internalized by C. reinhardtii. There is thus growing evidence that the free ion concentration may not be adequate to predict the accumulation of Sc (and potentially of other trivalent metals) in aquatic organisms.

Toxicokinetic study of scandium oxide in rats.

Canada has recently invested in the large-scale exploitation of scandium oxide. However, there are no studies available to date to understand its toxicokinetics in the animal or human body, which is necessary to assess exposure and health risks. The aim of this research was to investigate the toxicokinetics of absorbed scandium oxide (Sc2O3) using the rat as an experimental model. Male Sprague-Dawley rats were injected intravenously with 0.3 or 1 mg Sc2O3/kg body weight (bw). Blood and excreta (urine and feces) were collected sequentially during a 21-day period, and main organs (liver, spleen, lungs, kidneys, brain) were withdrawn at sacrifice on day 21. Inductively coupled plasma-mass spectrometry (ICP-MS) was used for the measurement of Sc element in the different samples. The mean residence time (MRTIV) calculated from the blood profile was 19.7 ± 5.9 h and 43.4 ± 24.6 h at the lower and higher doses, respectively. Highest tissue levels of Sc were found in the lungs and liver; respective lung values of 10.6 ± 6.2% and 3.4 ± 2.3% of the Sc dose were observed at the time of sacrifice while liver levels represented 8.9 ± 6.4% and 4.6 ± 1.1%. Elimination of Sc from the body was not complete after 21 days. Cumulative fecal excretion over the 21-day collection period represented 12.3 ± 1.3% and 5.9 ± 1.0% of the lower and higher Sc doses, respectively, and showed a significant effect of the dose on the excretion; only a small fraction of the Sc dose was recovered in urine (0.025 ± 0.016% and 0.011 ± 0.004% in total, respectively). In addition to an effect of the dose on the toxicokinetics, results highlight the importance of the lung as a site of accumulation and retention of Sc2O3, which raises the question of the risks of effects related to respiratory exposure in workers. The results also question the relevance of urine as a matrix for biological exposure monitoring. A more in-depth inhalation toxicokinetic study would be necessary.

Immunochromatographic Assay based on Sc-TCPP 3D MOF for the rapid detection of imidacloprid in food samples.

In this work, a highly sensitive immunochromatographic test strip (ITS) based on Scandium-Tetrakis (4-carboxyphenyl) porphyrin (TCPP) metal-organic framework nanocubes (ScTMNs) was developed for ultrasensitive and facile visual determination of imidacloprid (IDP). TCPP as the porphyrin-based planar ligand and Sc3+ as the metal center were applied to form the ScTMNs via coordination chelation. Giving the credit to its excellent optical characteristics, strong affinity with monoclonal antibodies, and favorable biocompatibility, the ScTMNs was selected as a signal tag. Under optimized conditions, the ITS exhibited a great liner relationship in the range of 0.04-3 ng/mL and the detection limit was 0.04 ng/mL for the IDP detection. Additionally, IDP was successfully detected in tomatoes, millet, corn and carrot samples with satisfied recoveries. To the best of our knowledge, this is the first time that ScTMNs have been used in immunochromatography which are expected to have potential applications in detection of other substances.

Impact of prompt gamma emission of 44Sc on quantification in preclinical and clinical PET systems.

44Sc is an increasingly investigated positron emitter for use in positron emission tomography (PET) imaging. However, 44Sc is a non-pure positron emitter, since prompt photons are co-emitted during the decay process. This study investigates coincidence energy spectra of 44Sc and its impact on PET quantification on a preclinical and clinical PET system in comparison with 18F. The raw data of the coincidence events revealed characteristic differences comparing the photon energy distribution of 44Sc and 18F. Due to prompt gamma emission of 44Sc, activity recovery is underestimated on PET systems. However, clinical PET imaging of 44Sc with acceptable quantitative accuracy appears feasible by using a single, constant correction factor.

Synthesis of chitosan-acrylic acid/multiwalled carbon nanotubes composite for theranostic 47Sc separation from neutron irradiated titanium target.

A simple and efficient separation method of carrier-free 47Sc from neutron irradiated titanium target using a novel chitosan-acrylic acid/multiwalled carbon nanotubes (CS-AA/MWCNTs) composite was established. The synthesis of the CS-AA/MWCNTs composite was achieved using gamma radiation-induced template polymerization. The grafting efficiency (GE%) of AA on CS onto the surface of f-MWCNTs reached a maximum of~84% under the optimized conditions (30 wt% CS, 1.0 wt% AA, 0.15 wt% f-MWCNTs, >0.2 wt% N,N'-Methylenebisacrylamide (NMBA), and irradiation dose ~25 kGy). Different analyses (FT-IR, SEM, TGA and DTA) were examined for confirming the structural morphology and mechanical properties of the new synthesized composite. Interestingly, the CS-AA/MWCNTs composite depicted a selective adsorption of Sc(III) rather than Ti(IV) ions at pH 5 with adsorption efficiency of ~93.93%. The ionic exchange separation of no-carrier-added (NCA)47Sc(III) from irradiated TiO2 target on CS-AA/MWCNTs composite packed column efficiently eluted 47Sc(III) by 91 ± 0.8% using 1 M HCl solution. The quality control tests (radionuclidic, radiochemical, and chemical purities) for the eluted 47Sc(III) clarified its high purity and validity for cancer theranostics.

Trace elements in stream bed sediments from agricultural catchments (Gascogne region, S-W France): where do they come from?

The Gascogne region (SW of France) is cultivated for more than 75% of the area. 83 samples of stream bed sediments were collected in three main Gascogne river basins (Gers, Save and Touch, left tributaries of the Garonne river) to evaluate the impact of agricultural practices on trace elements behavior. Eight potential harmful elements (PHE) (Cr, Co, Ni, Cu, Zn, As, Cd and Pb), four reference elements for normalization (Sc, Cs, Al and Fe) and four major elements (Mn, Ca, Mg and P) were considered. The average trace element concentrations in the fine fractions (<63 microm) are in the decreasing order: Zn>Cr>Ni>Pb>Cu>Co>As>Sc>Cs>Cd. Geochemical investigations and an original approach combining regression analysis and chemical sequential extraction allowed to select the most adequate reference material (regional molasse) and reference element (Cs) for normalization procedure. The enrichment factor (EF) is generally lower than 2.5, particularly for Cr, Ni, Cu, As, Zn; however, 23% of the sampling stations are more contaminated (2.5

Scandium, yttrium, and lanthanide contents in soil from Serbia and their accumulation in the mushroom Macrolepiota procera (Scop.) Singer.

The mobility (fractionation) of rare earth elements (REEs) and their possible impacts on ecosystems are still relatively unknown. Soil samples were collected from two sites in central Serbia, an unpolluted mountain region (site 1) and a forest near a city (site 2). In order to investigate REE fractions (acid-soluble/exchangeable, reducible, oxidizable, and residual) in soils, BCR sequential extraction was performed. Additionally, the content of REEs was also determined in stipes and caps of the mushroom Macrolepiota procera, growing in the observed sites. Sc, Y, and lanthanide contents were determined by inductively coupled plasma mass spectrometry (ICP-MS), and results were subjected to multivariate data analysis. Application of pattern recognition technique revealed the existence of two distinguished clusters belonging to different geographical sites and determined by greater levels of Sc, Y, and lanthanides in Goc soil compared to Trstenik soil. Additionally, PCA analysis showed that REEs in soil were concentrated in two groups: the first consisted of elements belonging to light REEs and the second contained heavy REEs. These results suggest that the distribution of REEs in soils could indicate the geographical origin and type of soil. The bioconcentration factors and translocation factors for each REE were also calculated. This study provides baseline data on the rare earth element levels in the wild edible mushroom M. procera, growing in Serbia. In terms of bioconcentration and bioexclusion concept, Sc, Y, and REEs were bioexcluded in M. procera for both studied sites.

Estimation of uncertainty arising from different soil sampling devices: the use of variogram parameters.

In the frame of the international SOILSAMP project, funded and coordinated by the National Environmental Protection Agency of Italy (APAT), uncertainties due to field soil sampling were assessed. Three different sampling devices were applied in an agricultural area using the same sampling protocol. Cr, Sc and Zn mass fractions in the collected soil samples were measured by k(0)-instrumental neutron activation analysis (k(0)-INAA). For each element-device combination the experimental variograms were calculated using geostatistical tools. The variogram parameters were used to estimate the standard uncertainty arising from sampling. The sampling component represents the dominant contribution of the measurement uncertainty with a sampling uncertainty to measurement uncertainty ratio ranging between 0.6 and 0.9. The approach based on the use of variogram parameters leads to uncertainty values of the sampling component in agreement with those estimated by replicate sampling approach.

Construction of monoenergetic neutron calibration fields using 45Sc(p, n)45Ti reaction at JAEA.

The 8 and 27 keV monoenergetic neutron calibration fields have been developed by using (45)Sc(p, n)(45)Ti reaction. Protons from a 4-MV Pelletron accelerator are used to bombard a thin scandium target evaporated onto a platinum disc. The proton energies are finely adjusted to the resonance to generate the 8 and 27 keV neutrons by applying a high voltage to the target assemblies. The neutron energies were measured using the time-of-flight method with a lithium glass scintillation detector. The neutron fluences at a calibration point located at 50 cm from the target were evaluated using Bonner spheres. A long counter was placed at 2.2 m from the target and at 60 degrees to the direction of the proton beam in order to monitor the fluence at the calibration point. Fluence and dose equivalent rates at the calibration point are sufficient to calibrate many types of the neutron survey metres.

Toenail mineral concentration and risk of esophageal squamous cell carcinoma, results from the Golestan Cohort Study.

Studies conducted in China linked selenium deficiency to higher risk of esophageal squamous cell carcinoma (ESCC), but this has not been widely tested outside that selenium-deficient region. The aim of this study was to investigate the association between selenium and other mineral concentrations in toenails and risk of ESCC in a region with high incidence rates. In this nested case-control study, we identified 222 cases of ESCC from the Golestan Cohort Study, Iran, which has followed up 50,045 participants since enrollment (2004-2008). We randomly selected one control for each case matched by age and sex, using incidence density sampling. We used toenail samples collected at baseline to measure the concentration of selenium, zinc, chromium, mercury, and scandium using instrumental neutron activation analysis. Multivariate adjusted logistic regression models were used to estimate odds ratios (OR) and 95% confidence intervals. Median nail selenium, zinc, chromium, and mercury levels were 1.01, 74.59, 0.77, and 0.018 µg/g in cases and 1.02, 75.71, 0.71, and 0.023 µg/g in controls, respectively. The adjusted odds ratios comparing each fourth quartile of mineral status versus the first quartile were as follows: selenium = 0.78 (95% CI, 0.41-1.49); zinc=0.80 (95% CI, 0.42-1.53); chromium = 0.91 (95% CI, 0.46-1.80); and mercury=0.61 (95% CI, 0.27-1.38), and all trend tests were non-significant. The nail selenium concentration in our controls reflects relatively high selenium status. No evidence of association between selenium or chromium concentrations in toenails and the risk of ESCC was detected in this population.

Standardisation and precise determination of the half-life of (44)Sc.

The half-life of the positron-emitter (44)Sc has been determined by following the decay rate with two measurement systems; an Ionisation Chamber and a HPGe detector. The combination of seven results gives a value of T1/2=4.042 (25)h, about 2% higher than the recommended value of T1/2=3.97 (4)h (Browne, 2011) and with a lower uncertainty. This radionuclide has also been standardised by coincidence counting, and liquid scintillation counting techniques. A (44)Ti/(44)Sc generator developed at CIEMAT was used to obtain the (44)Sc solutions used in all measurements.

[Determination of ten trace rare earth elements in the sample by atomic emission spectrometry].

This paper describes the determination of trace La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Yb and Lu in the sample, using carbon powder, potassium sulfate, barium sulfate, strontium sulfate, and scandium chloride as buffer, by atomic emission spectrometry (AES). Scandium was selected as internal standard line. Sample separation and chemical treatment were not required. The sample was directly loaded into ordinary electrode. The method is simple, rapid and accurate. The determination requirement and influence factors were studied. A new method was developed for the determination of ten rare earth elements, for which the detection limit is smaller than 0.030%, and the range of the recovery is 94%-105%. The results of these elements in standard sample are in agreement with certified values, and the RSD is smaller than 5% (n = 9). The method has been applied to the determination of ten rare earth elements with satisfactory results.

Use of 48Ca as a stable isotope tracer analyzed by proton activation.

The use of the stable isotope 48Ca as a tracer in biological systems has been studied. Determination of 48Ca concentrations in samples was accomplished by proton activation via the (p,n) reaction with subsequent measurement of gamma-ray spectra from 44-h 48Sc and 4-h 44Sc. With protons of about 5.5 MeV and a Ge(Li) gamma-ray detector, and with no chemical processing of the samples, ratios of these two radioisotopes can be determined with sufficient precision to allow 48Ca tracer studies to be performed with sensitivity at least equivalent to that possible with the common 45Ca radioactive tracer.

A new approach for quantifying cumulative, anthropogenic, atmospheric lead deposition using peat cores from bogs: Pb in eight Swiss peat bog profiles.

Peat cores taken from eight Swiss peatlands were used to calculate inventories of anthropogenic Pb using either Sc or Zr to quantify Pb derived from rock weathering. The shapes of the Pb/Sc and Pb/Zr profiles suggest that Pb was supplied exclusively by atmospheric deposition at all sites. At one of the sites (Etang de la Gruère), anthropogenic Pb was calculated using both Sc and Zr as the conservative reference element. Lithogenic Pb determined using Sc was twice that obtained using Zr, possibly because Zr resides only in zircons which are dense compared to pyroxene and amphibole which are the main Sc-bearing phases in the earth's crust. However, the inventory of 'natural' Pb (supplied almost entirely by soil dust) is dwarfed by the anthropogenic inventory such that anthropogenic Pb calculated using Sc and Zr agree to within 5%. The total amount of anthropogenic Pb accumulated in the bogs was calculated by simply adding the mass of anthropogenic Pb for each peat slice over the length of each core. Cumulative, anthropogenic Pb calculated in this way ranged from 1.0 to 9.7 g/m2 and showed pronounced regional differences: the site south of the Alps (Gola di Lago in Canton Ticino) with direct exposure to the heavily industrialized region of northern Italy received nearly 10 times more anthropogenic Pb as the sites in more remote alpine regions (Schöpfenwaldmoor in Canton Berne, and Mauntschas in Canton Grisons). The approach used here to calculate cumulative, anthropogenic, atmospheric Pb (CAAPb) is simple and robust, independent of the chronology of Pb deposition, and makes no assumptions about the immobility of Pb within the peat profile. Given the worldwide distribution of peat bogs, it should be possible to undertake continental and global inventories of atmospheric metal deposition, for both the natural and anthropogenic components of most trace metals of environmental interest.

Measurement and distribution of various heavy metals in the Danube River and Danube Canal aquatic communities in the vicinity of Vienna, Austria.

Samples of mud, water, algae and fish were collected from the Danube River and Danube Canal and analysed by neutron activation techniques for various trace metals. The study was conducted over a ten-months time period. Results show no significant variation in levels of Cr, Co, Sb, Zn, Fe and Sc during the period of study. Comparison of the results obtained for the river with those obtained for the canal indicate that, with the exception of one sampling site, there are no statistically significant differences. Generally the values lie in the range accepted as normal for most fresh water systems. One site in the canal was found to have high Cr content in the mud samples at a point where the Vienna River joins the canal.

Rare earth element, Al, and Sc partition between soil and Caatinger wood grown in north-east Brazil by instrumental neutron activation analysis.

Seven representative wood species constituting Caatinger forest in north-east Brazil were chosen to analyze La, Ce, Sm, Eu, Yb, Sc, and Al by instrumental neutron activation analysis (INAA). Soil profiles were prepared where the trees were downed. Then soil and root samples from each horizontal soil layer, as well as the upper part of the wood, ground-level bark, and the bark at 1 m above were collected. In woods, the rare earth element (REE) was found to be mainly accumulated in root, which concentration was in the same order as that of soil. In all samples, concentration of La and Ce were found to be about ten times higher than those of the other REEs. The REE accumulation became higher, in both root and soil, in the order of La, Ce, and Sm. The partition rate of La and Eu was higher from soil to root, whereas Ce tended to be concentrated from root to bark. In the case of bark, there was no tendency of specific REE accumulating from ground level to the upper part. The correlation of La concentration to the other REE was higher in root than that of corresponding soil. Roots also showed higher correlation of REE to Al and Sc than that of soil or bark.

The accumulation of the rare earth elements and of scandium in successive needle age classes of Norway spruce.

The endogenous concentrations of Sc, La, Ce, Sm, Eu, Tb, Yb, and Lu were determined by neutron activation analysis in up to five successive needle age classes of Norway spruce (Picea abies). Trees from nine sites over different bedrocks were sampled individually. Concentration values found are generally much lower than those reported in the literature. This is attributed to the careful removal of any aerosols or soil particles from the needle surface prior to analysis. The concentration of each element increases linearly with the needle age class, i.e., the accumulation can be characterized by just one parameter, the yearly increment. This pattern is followed at small as well as at large concentrations. The accumulation behavior of the investigated elements is identical to that of Si. The relative concentrations of the rare earth elements (REE) in the needles are similar to those in the earth crust. There are significant correlations between the individual REE and between Sc and La.

Nuclear and conventional methods for soil determination in sugar cane industry. Validity of sampling procedure.

Scandium and ash methods' performances were compared in terms of soil content assessment in sugar cane loads, emphasizing the common sampling drawbacks. Both methods are adequate for such determination in controlled conditions. The scandium has demonstrated better analytical characteristics, since it is free from interferences of cane matrix, which decreases the accuracy of the ash method in normal mill conditions.