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.

Carbon dots with aggregation-induced emission enhancement (AIEE) for detection of Zr4+/ Hf4+ and PTP1B activity.

The frequent use of Zirconium (Zr) and Hafnium (Hf) in modern industries may result in serious environment issues, and thus developing analytical methods to facilitate the control of these two resembled metal elements is urgently needed. However, up to now, rapidly and conveniently detecting Zr4+ and Hf4+ is still full of challenge. In this study, nitrogen and sulfur co-doped carbon dots (N, S-Cdots) with aggregation-induced emission enhancement (AIEE) were prepared and used for turn-on detection of Zr4+ and Hf4+ within 10 min. The photoluminescent intensity of N, S-Cdots showed a good linear correlation with Zr4+ and Hf4+concentrations ranging from 0 to 30 µM with the limit of detection (LOD) of 0.47 and 0.53 µM, respectively. Furthermore, this fluorometric assay was successfully used for quantitative analysis of Zr4+ and Hf4+ in real water samples with satisfactory recoveries in the range of 91.16-108.50% and 90.28-106.49%, respectively. Finally, the developed N, S-Cdots sensing system was used for assay PTP1B activity and screening its inhibitor with Zr4+ as the medium. Our work demonstrated that the as-prepared N, S-Cdots with AIEE can offer a simple and reliable alternative for rapid detection of Zr4+ and Hf4+ in water samples, in addition to being potential useful in phosphatase analysis and drug discovery.

Coupling Sr-Nd-Hf Isotope Ratios and Elemental Analysis to Accurately Quantify North African Dust Contributions to PM2.5 in a Complex Urban Atmosphere by Reducing Mineral Dust Collinearity.

Tracking Saharan-Sahelian dust across the globe is essential to elucidate its effects on Earth's climate, radiation budget, hydrologic cycle, nutrient cycling, and also human health when it seasonally enters populated/industrialized regions of Africa, Europe, and North America. However, the elemental composition of mineral dust arising locally from construction activities and aeolian soil resuspension overlaps with African dust. Therefore, we derived a novel "isotope-resolved chemical mass balance" (IRCMB) method by employing radiogenic strontium, neodymium, and hafnium isotopes to accurately differentiate and quantitatively apportion collinear proximal and synoptic-scale crustal and anthropogenic mineral dust sources. IRCMB was applied to two air masses that transported African dust to Barbados and Texas to track particulate matter (PM) spikes at both locations. During Saharan-Sahelian intrusions, the radiogenic content of urban PM2.5 increased with respect to 87Sr/86Sr and 176Hf/177Hf but decreased in terms of 143Nd/144Nd, demonstrating the ability of these isotopes to sensitively track African dust intrusions even in complex metropolitan atmospheres. The principal aerosol strontium, neodymium, and hafnium end members were concrete dust and soil, soil and motor vehicles, and motor vehicles and North African dust, respectively. IRCMB separated and quantified local soil and distal crustal dust even when PM2.5 concentrations were low, opening a promising source apportionment avenue for urbanized/industrialized atmospheres.

In vivo measurement of pre-operational spallation source workers: baseline body burden levels and detection limits of relevant gamma emitters using high-resolution gamma spectrometry.

As a measure to prepare for long-term internal dose monitoring of workers at the European Spallation Source (ESS) in Lund, Sweden, operated by the European Research Infrastructure Consortium (ERIC), as well as to enhance emergency preparedness against accidental releases, a series of in vivo measurements were conducted using a high-resolution HPGe detector with a 123% relative efficiency (1.332 MeV). This study describes the whole-body counting set-up, calibration procedure, and subsequent validation measurements using conventional NaI(Tl)-scanning-bed geometry on a selection of workers from the ESS. Detection limits for the relevant gamma emitters 7Be, 172Hf, and 182Ta were determined to be 65 Bq, 130 Bq, and 22 Bq, respectively, using a 2400 s acquisition time. The baseline measurements suggest that care must be taken to ensure that the fluctuations in the presence of radon daughters 214Bi and 214Pb are minimised by, for example, ensuring a minimum air exchange between the measuring room and the ambient air, and by demanding that the measured subjects change clothes and shower before measurement. Furthermore, in a monitoring program for internal doses to spallation source workers, the presence of radionuclides originating from non-work-related sources (such as 226Ra from private water wells or 137Cs from intakes of Chernobyl contaminated foodstuffs), or radionuclides from previous work history (such as 60Co within the nuclear power industry), must be considered.

Impact of the precursor chemistry and process conditions on the cell-to-cell variability in 1T-1R based HfO2 RRAM devices.

The Resistive RAM (RRAM) technology is currently in a level of maturity that calls for its integration into CMOS compatible memory arrays. This CMOS integration requires a perfect understanding of the cells performance and reliability in relation to the deposition processes used for their manufacturing. In this paper, the impact of the precursor chemistries and process conditions on the performance of HfO2 based memristive cells is studied. An extensive characterization of HfO2 based 1T1R cells, a comparison of the cell-to-cell variability, and reliability study is performed. The cells' behaviors during forming, set, and reset operations are monitored in order to relate their features to conductive filament properties and process-induced variability of the switching parameters. The modeling of the high resistance state (HRS) is performed by applying the Quantum-Point Contact model to assess the link between the deposition condition and the precursor chemistry with the resulting physical cells characteristics.

Rare earths, zirconium and hafnium distribution in coastal areas: The example of Sabella spallanzanii (Gmelin, 1791).

The Zr, Hf, Y and lanthanide (REE) distribution in biological tissues of Sabella spallanzanii and Styela plicata species collected from two harbours from the northern Sicily is studied for providing information regarding the Zr, Hf and REE uptake from the environment. Previous studies determined the fractionation of dissolved REE scavenged on binding sites onto biological surfaces. By comparing the recognised shale-normalised REE patterns of studied samples with evidence from reference data, the observed behaviour of these elements in biological tissues of Sabella spallanzanii and Styela plicata is interpreted to result from the preferential uptake of intermediate REE onto carboxylic sites. Moreover, the relationship observed between the Fe content and Zr/Hf ratio suggests that preferential Hf accumulation occurs via siderophore-like binding sites. Features of the REE bioaccumulation factors (BAF), in addition to the absolute La, Ce and Sm contents and Zr-Hf fractionation, allow definition of the different origins of studied elements in the investigated localities. Higher BAF values for La and Ce associated with larger REE contents and lower Zr/Hf values strongly suggest that the environmental REE distribution in the Termini Imerese harbour is influenced by the delivery of particles from industrial sources and power plants. On the contrary, the REE contents of biological tissues collected in the Cala tourist harbour are affected by the dust dissolution from automotive traffic. These results suggest that the geochemical behaviour of REE and Zr/Hf signature can be used in environmental studies of biological tissues for reconstructing the nature of anthropogenic contaminations.

Large Pt anomaly in the Greenland ice core points to a cataclysm at the onset of Younger Dryas.

One explanation of the abrupt cooling episode known as the Younger Dryas (YD) is a cosmic impact or airburst at the YD boundary (YDB) that triggered cooling and resulted in other calamities, including the disappearance of the Clovis culture and the extinction of many large mammal species. We tested the YDB impact hypothesis by analyzing ice samples from the Greenland Ice Sheet Project 2 (GISP2) ice core across the Bølling-Allerød/YD boundary for major and trace elements. We found a large Pt anomaly at the YDB, not accompanied by a prominent Ir anomaly, with the Pt/Ir ratios at the Pt peak exceeding those in known terrestrial and extraterrestrial materials. Whereas the highly fractionated Pt/Ir ratio rules out mantle or chondritic sources of the Pt anomaly, it does not allow positive identification of the source. Circumstantial evidence such as very high, superchondritic Pt/Al ratios associated with the Pt anomaly and its timing, different from other major events recorded on the GISP2 ice core such as well-understood sulfate spikes caused by volcanic activity and the ammonium and nitrate spike due to the biomass destruction, hints for an extraterrestrial source of Pt. Such a source could have been a highly differentiated object like an Ir-poor iron meteorite that is unlikely to result in an airburst or trigger wide wildfires proposed by the YDB impact hypothesis.

Intensifying weathering and land use in Iron Age Central Africa.

About 3000 years ago, a major vegetation change occurred in Central Africa, when rainforest trees were abruptly replaced by savannas. Up to this point, the consensus of the scientific community has been that the forest disturbance was caused by climate change. We show here that chemical weathering in Central Africa, reconstructed from geochemical analyses of a marine sediment core, intensified abruptly at the same period, departing substantially from the long-term weathering fluctuations related to the Late Quaternary climate. Evidence that this weathering event was also contemporaneous with the migration of Bantu-speaking farmers across Central Africa suggests that human land-use intensification at that time had already made a major impact on the rainforest.

Laser conditioning on HfO2 film monitored by calorimeter.

Conditioning effect on HfO2 single-layer film by quasi-cw laser was investigated. The conditioning process was monitored with laser calorimeter. Experimental results revealed that the HfO2 film absorption decreased as a function of the irradiation dose. Higher laser power accelerated the conditioning process. The conditioning effect could not be explained by water annihilation. AFM pictures of the film surface showed that the structural information in the conditioned region was different from the unconditioned region. Monitoring the in situ absorption, laser calorimeter is a promising tool to investigate the laser conditioning process.

Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of N'-(furan-3-ylmethylene)-2-(4-methoxyphenylamino)acetohydrazide.

Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of furan-2-carbaldehyde 4-methoxy-N-anilinoacetohydrazone were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and (1)H NMR spectra as well as magnetic moment and molar conductivity. Mononuclear complexes are obtained with 1:1 molar ratio except complexes 3 and 9 which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a neutral bidentate one and coordination occurs via the carbonyl oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the enolic oxygen atom, azomethine nitrogen atom and the oxygen atom of furan ring. Moreover, the ligand behaves as a neutral tridentate and coordination occurs via the carbonyl oxygen, azomethine nitrogen and furan oxygen atoms as well as a monobasic bidentate and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complex 10 possesses a square planar geometry. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes.

Simultaneous preconcentration and determination of U(VI), Th(IV), Zr(IV) and Hf(IV) ions in aqueous samples using micelle-mediated extraction coupled to inductively coupled plasma-optical emission spectrometry.

A simple cloud point extraction method followed by inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for simultaneous preconcentration and determination of trace amounts of U(VI), Th(IV), Zr(IV) and Hf(IV) ions in aqueous samples. The metal ions in 50 ml of aqueous solution (containing 0.1 M sodium acetate, pH 6.0) were formed complexes with dibenzoylmethane (DBM). Then, Triton X-114 (0.2%, w/v) was added to the solution. By increasing the temperature of the solution up to 50 degrees C, a phase separation occurred. After centrifugation at 4000 rpm for 6 min, the surfactant-rich phase (sediment phase) was diluted with 1.0 ml of 20:80 (v/v) of methanol/1 M HNO(3). The metal ions were then determined using ICP-OES. Finally, the main factors affecting the cloud point extraction were evaluated and optimized. Under optimized conditions, enhancement factors in the range of 37.0-43.6 were obtained. The calibration graphs were linear in the range of 0.5-1500 microg l(-1) for Th and Zr, 0.5-500 microg l(-1) for Hf and 2.5-1240 microg l(-1) for U with correlation coefficients (r(2)) better than 0.9926. The detection limits were between 0.1 and 1.0 microg l(-1) and the R.S.D. values for seven replicates were lower than 6.1%.

A fast response hafnium selective polymeric membrane electrode based on N,N'-bis(alpha-methyl-salicylidene)-dipropylenetriamine as a neutral carrier.

In this study a new hafnium selective sensor was fabricated from polyvinylchloride (PVC) matrix membrane containing neutral carrier N,N'-bis(alpha-methyl-salicylidene)-dipropylenetriamine (Mesaldpt) as a new ionophore, sodium tetraphenyl borate (NaTPB) as anionic discriminator and dioctyl phthalate (DOP) as plasticizing solvent mediator in tetrahydrofuran solvent. The electrode exhibits Nernstian response for Hf(4+) (Hafnium(IV)) over a wide concentration range (2.0 x 10(-7) to 1.0 x 10(-1)M) with the determination coefficient of 0.9966 and slope of 15.1+/-0.1 mVdecades(-1). The limit of detection is 1.9 x 10(-7)M. The electrode has a fast response time of 18s and a working pH range of 4-8. The proposed membrane shows excellent discriminating ability towards Hf(4+) ion with regard to several alkali, alkaline earth transition and heavy metal ions. It can be used over a period of 1.5 months with good reproducibility. It is successfully applied for direct determination of Hf(4+) in solutions by standard addition method for real sample analysis.

Measurement of absolute intensities of some prompt gamma-lines from the 91Zr, 143Nd, 177Hf and 116,118-120,122,124Sn(n,gamma) reactions and isomeric cross-sections of 123m,125mSn by in-beam gamma-spectroscopy method.

The previously unknown absolute intensities of 28 prompt gamma-rays from the thermal neutron capture in 91Zr, 143Nd, 177Hf and 116,118-120,122,124Sn were measured by an in-beam gamma-spectroscopy method at the WWR-M reactor (PNPI, Gatchina). Cross sections of the production of isomers 123m,125mSn were also measured.

Simultaneous determination of Zr(IV) and Hf(IV) by CE using precolumn complexation with a [PW(11)O(39)](7-) ligand.

A CE method was developed for the simultaneous determination of Zr(IV) and Hf(IV) at trace levels. A lacunary Keggin-type [PW(11)O(39)](7-) ligand reacted quantitatively with a mixture of trace amounts of Zr(IV) and Hf(IV) to form the so-called ternary Keggin-type anions [P(Zr(IV)W(11))O(40)](5-) and [P(Hf(IV)W(11))O(40)](5-) in 0.010 M monochloroacetate buffer (pH 2.2). Since both ternary anions possessed different electrophoretic mobilities and high molar absorptivities in the UV region, Zr(IV) and Hf(IV) were determined simultaneously with direct UV detection at 258 nm. Each peak height was linearly dependent on the concentration of Zr(IV) or Hf(IV) in the range of 5.0x10(-7)-1.0x10(-5) M; a detection limit of 2x10(-7) M was achieved. The utility of the proposed CE method was demonstrated for the simultaneous determination of Zr(IV) and Hf(IV) in natural water samples with satisfactory results.

Application of principle component analysis-artificial neural network for simultaneous determination of zirconium and hafnium in real samples.

Determination of zirconium and hafnium were done by applying singular value decomposition and a feed forward Neural Network Algorithm with back propagation of error. The determination of trace amounts of mixtures of Zr(IV) and Hf(IV) in various matrices (river, tap and industrial wastewater) were investigated by PC-ANN using the complexes formed between Alizarin Red S, Zr and Hf. The results showed that measurement is possible in the ranges of 0.03-3.4 and 0.2-7.0 microg ml-1 for Zr(IV) and Hf(IV), respectively. The detection limits were 0.02 and 0.08 microg ml-1 for Zr(IV) and Hf(IV), respectively. The results also show very good agreement between true and predicted concentration values and have the ability to use in routine analysis.

[Determination of trace zirconium and hafniumin sample by atomic emission spectrometry].

This paper describes the determination of trace Zr and Hf in the sample using carbon powder and titanium oxide as the buffer by Atomic Emission Spectrometry (AES). Titanium was selected for the internal standard line. Sample separation and chemical treatment were not required. The sample was directly loaded into an ordinary electrode. The method is simple, rapid and accurate. The conditions for the determination, and the factors of influence have been studied. A new method has been developed for the determination of zirconium and hafnium. The analytical lines of Zr and Hf were 327.3 and 286.6 nm respectively. The internal standard line of Ti was 308.8 nm. The linear range of the determination of Zr and Hf was 0-0.50% and 0-0.25% respectively. The detection limit of Zr and Hf was 0.0010% and 0.010% respectively. The range of the recovery of zirconium and hafnium was 96.67%-105.0%. The results for these elements in standard sample are in agreement with certified values with a precision of 3.61% RSD for Zr (n = 9), and 4.82% RSD for Hf (n = 9). The method has been applied to the determination of Zr and Hf with satisfactory results.

Comparative X-ray standing wave analysis of metal-phosphonate multilayer films of dodecane and porphyrin molecular square.

The nanoscale structures of multilayer metal-phosphonate thin films prepared via a layer-by-layer assembly process using Zr(4+) and 1,12-dodecanediylbis(phosphonic acid) (DDBPA) or porphyrin square bis(phosphonic acid) (PSBPA) were studied using specular X-ray reflectivity (XRR), X-ray fluorescence, and long-period X-ray standing wave (XSW) analysis. The films were prepared in 1, 2, 3, 4, 6, and 8 layer series on both Si(001) substrates for XRR and on 18.6 nm period Si/Mo layered-synthetic microstructure X-ray mirrors for XSW. After functionalizing the SiO(2) substrate surfaces with a monolayer film terminated with phosphonate groups, the organic multilayer films were assembled by alternating immersions in (a) aqueous solutions containing Zr(4+)or Hf(4+) (final metal layer only) cations and then (b) organic solvent solutions of PO(3)-R-PO(3)(4-), where R was DDBPA or PSBPA spacer molecule. The Hf(4+) cation served as the marker for the top surface of the films, whereas the Zr(4+) cation was present in all other layers. The PSBPA also contained Zn and Re atoms at its midline which served as heavy-atom markers for each layer. The long-period XSW generated by the 0th- (total external reflection) through 4th-order Bragg diffraction conditions made it possible to examine the Fourier transforms of the fluorescent atom distributions over a much larger q(z) range in reciprocal space which permitted simultaneous analysis of Hf, Zn/Re, and Zr atomic distributions.

Evolution of planetary cores and the Earth-Moon system from Nb/Ta systematics.

It has been assumed that Nb and Ta are not fractionated during differentiation processes on terrestrial planets and that both elements are lithophile. High-precision measurements of Nb/Ta and Zr/Hf reveal that Nb is moderately siderophile at high pressures. Nb/Ta values in the bulk silicate Earth (14.0 +/- 0.3) and the Moon (17.0 +/- 0.8) are below the chondritic ratio of 19.9 +/- 0.6, in contrast to Mars and asteroids. The lunar Nb/Ta constrains the mass fraction of impactor material in the Moon to less than 65%. Moreover, the Moon-forming impact can be linked in time with the final core-mantle equilibration on Earth 4.533 billion years ago.

Internal dosimetry for inhalation of hafnium tritide aerosols.

Metal tritides with low dissolution rates may have residence times in the lungs which are considerably longer than the biological half-time normally associated with tritium in body water, resulting in long-term irradiation of the lungs by low energy beta particles and bremsstrahlung X rays. Samples of hafnium tritide were placed in a lung simulant fluid to determine approximate lung dissolution rates. Hafnium hydride samples were analysed for particle size distribution with a scanning electron microscope. Lung simulant data indicated a biological dissolution half-time for hafnium tritide on the order of 10(5) d. Hafnium hydride particle sizes ranged between 2 and 10 microns, corresponding to activity median aerodynamic diameters of 5 to 25 microns. Review of in vitro dissolution data, development of a biokinetic model, and determination of secondary limits for 1 micron AMAD particles are presented and discussed.

Preferential localization of hafnium in nodular lymphatic cells. Study by electron microprobe.

In a previous work we used the electron microprobe to study the intracellular localization of zirconium after administration of soluble salt at low doses. That element was concentrated in nodular lymphatic cells. In the present work using the same methods we studied hafnium, another element in group IVb of the periodic table, which has chemical properties similar to zirconium. After administration at low doses of soluble salt of hafnium, this element was similarly concentrated in nodular lymphatic cells and was as zirconium uniquely localized in the lysosomes of macrophages where it is associated with phosphorus.