Thin-film Techniques Research Articles

Risk assessment of Cr, As, and Sb to aquatic communities at the water-sediment interface in the lower Yellow River, China, integrated with the Diffusive Gradients in Thin‐films technique

The dynamic concentrations of labile metals/metalloids, measured by the Diffusive Gradients in Thin-films (DGT) technique, can be used for evaluating the toxicity risk of heavy metals to aquatic organisms in sediments. In this study, the different potential risks of the three sediment compartments, overlying water (W), sediment- water interface (SWI) and sediment (S) were independently assessed by studying the concentrations of Cr, As, and Sb in the sediment and water from the lower Yellow River. Total concentrations of these elements and bioavailable concentrations, using DGTs, were explored and probabilistic risk assessment (PRA) based on a Monte Carlo model was performed. The results show that the total heavy metal concentrations in sediment and overlying water were spatially variable due to influences of natural geography and sediment distribution. The trace elements mean concentrations using DGT were 1.68, 1.69 and 0.73 μg·L−1 for Cr, 0.61, 0.51 and 0.39 μg·L−1 for As, and 0.78, 1.16, and 0.41 μg·L−1 for Sb in W, SWI and S, respectively. Among them, the DGT-labile concentration of As displayed a large spatial variability, indicating a close association with anthropogenic activities. The risk quotient (RQ) categories for single heavy metal toxicity demonstrated to be moderate risk for Cr and almost no risk for As and Sb. The combined biotoxicity probability assessment of the three heavy metals showed that they would cause almost no harmful effects to benthic organisms in the whole ecosystem of the Yellow River.

Orientation-dependent atomic-scale mechanism and defect evolution in β-Ga2O3 thin film epitaxial growth

β-Ga2O3 has been subjected to intense research interest as an ultrawide bandgap semiconductor. The epitaxial growth technique of β-Ga2O3 thin films plays a fundamental and vital role in Ga2O3-based device fabrication. In this work, the epitaxial growth mechanisms of β-Ga2O3 on four low-Miller-index facets, (100), (010), (001), and (2¯01), are systematically explored using large-scale machine-learning molecular dynamics simulations at the atomic scale. The simulations reveal that the migration of the face-centered cubic stacking O sublattice plays a dominant role in the different growth mechanisms between the (100)/(010)/(001) and (2¯01) orientations. The resultant complex combinations of the stacking faults and twin boundaries are carefully identified and show good agreement with experimental observations and ab initio calculations. Our results provide useful insights into the gas-phase epitaxial growth of β-Ga2O3 thin films and suggest possible ways to tailor its properties for specific applications.

In situ, high-resolution evidence for the release of heavy metals from lake sediments during ice-covered and free periods

Heavy metal dynamics at the sediment-water interface (SWI) has attracted plenty of attention due to their meticulous depiction for metal sorption-release processes. However, little is known about their concentration, migration and release characteristics underneath the ice, especially at the millimeter scale. Here we investigated dynamics of labile As, Cd, Cu, Mn, Pb and Zn by the diffusive gradients in thin-films (DGT) technique during ice-covered and ice-free periods in the Lake Xingkai basin. The concentrations of metals were relatively high at the SWI and ranged for As: 0.001~13.42 μg L−1, Cd: 0.01~0.45 μg L−1, Cu: 0.001~2.75 μg L−1, Mn: 5.31~2958.29 μg L−1, Pb: 0.06~1.43 μg L−1, and Zn: 2.92~112.96 μg L−1. Particularly, concentration of Mn was extremely higher than other studies, possibly due to diagenetic process. Labile concentrations of heavy metals in January were significantly lower than those in May, suggesting that elevated temperatures lead to the release of heavy metals from the sediment to the overlying water. Based on the Fick’s first law, the diffusive fluxes as a source of Mn (413.82-1163.25 mg·m-2·d-1) and As (3.53 -8.12 mg·m-2·d-1) indicated that heavy metals were released from sediments to the overlying water. While the diffusive fluxes as a sink of Zn (-1.80-(-2.36) mg·m-2·d-1) and Pb (-0.02-(-0.46) mg·m-2·d-1) to sediments. Redundancy Analysis (RDA) revealed that the main factors influencing the heavy metal migration were dissolved oxygen (45.6% of total explanation, P=0.01) in January, and water temperature (52.9%, P=0.006) in May. This study extends theoretical scope for understanding metal migration and release process, and provides valuable suggestions for lake management during the freezing period.

Phosphorus dissolution and diffusion from struvite and its impact on phosphorus availability in Acrisol and Cambisol soils

AbstractThere is a growing interest in recovering and recycling phosphorus (P) from waste streams to reduce reliance on finite and non‐renewable phosphate rock in agriculture. Struvite, derived from waste streams, has emerged as a potential alternative P fertilizer. However, its behaviour in soil remains unclear. This study aimed to investigate the behaviour and effectiveness of struvite as a P fertilizer in acidic Acrisol and calcareous Cambisol soils, focusing on the P dissolution from struvite, struvite P diffusion in soil and P availability. Our findings revealed that the P dissolution from struvite in solution is pH‐dependent, with the most dissolution observed at pH 4.5 and significantly less at pH 7.0 and pH 8.5. Consequently, P dissolution from struvite was more rapid in the Acrisol compared with the Cambisol. This was supported by the increased accumulation of water‐soluble P in the Acrisol and acid‐extractable P in the Cambisol within the 0–1 cm concentric soil section surrounding the struvite application site, as demonstrated in the petri dish experiment. However, the Acrisol exhibited a gradual decrease in P diffusion over time, in contrast to the Cambisol, which showed an increasing trend. This can be attributed to the stronger P fixation observed in the Acrisol. The application of struvite resulted in increased soil P availability, as determined by the diffusive gradients in thin films (DGT) technique, particularly in the Acrisol where struvite was concentrated. Furthermore, the presence of organic acids enhanced struvite P availability in both Acrisol and Cambisol soils. These findings contribute to a better understanding of struvite behaviour in different soil environments and provide valuable insights for optimizing its use as a sustainable and efficient P fertilizer.

Development and validation of diffusive gradients in thin-films for in situ monitoring of ionic liquids in waters.

Due to their wide applications, occurrence and "PFAS-like" environmental behaviors, ionic liquids (ILs) represent a new challenge for the environmental monitoring community, who require robust analytical methods that can determine accurately and efficiently their environmentally relevant concentrations. A new passive sampling method based on the diffusive gradients in thin films (DGT) technique was developed for the measurement of imidazole-based ILs in waters using a mixed-mode cation exchange (MCX) resin as the adsorbent. The selected binding gel had a high binding capacity (>170 μg per disc) for ILs. Diffusion coefficients measured using a diffusion cell correlated well with alkyl chain lengths (r2 = 0.95) and retention times (r2 = 0.88), providing a simple and rapid prediction approach for other ILs. The assembled MCX-DGT sampler exhibited a linear accumulation for at least 120 h. MCX-DGT also showed good performance under typical freshwater conditions (pH 5-8, ionic strength 0.001-0.01 M, and humic acid 0-5 mg L-1), while still being problematic for aquatic conditions with higher ionic strength (>0.1 M) or DOM (>10 mg L-1). Laboratory deployment (for up to 3 days) in spiked natural freshwater (SNW) resulted in linear mass uptakes for the short-chain ILs (C2-C8), and their DGT-measured concentrations agreed well with solution concentrations. However, MCX-DGT significantly overestimated the concentrations of the long-chain ILs (C10-C12) when deployed in SNW for one day or more, which is attributed to the strong competitive adsorption of the long-chain ILs by natural organic matter. In situ field evaluation along with grab sampling found no target ILs in a wastewater treatment plant and its receiving river, implying that these new chemicals might not be widely used in South China now. This is the first report on the DGT technique for ILs and might provide an effective tool for monitoring short chain length ILs in the aquatic environment in the near future.

Validation of microwave acid digestion, diffusive gradients in thin-film preconcentration and inductively coupled plasma optical emission spectrometry methodology for the determination of REEs in natural zeolites.

The determination of rare earth element (REE) content in different natural minerals is of high interest due to their extensive use in modern and sustainable technologies. The REEs occurring in natural zeolites are specific to each deposit. This study presents the validation and evaluation of the measurement uncertainty for the determination of REEs (Ce, Dy, Er, Eu, Gd, La, Lu, Nd, Pr, Sm, Y, and Yb) in natural zeolites using microwave-assisted acid digestion and inductively coupled plasma optical emission spectrometry (ICP-OES) after diffusive gradients in thin-film preconcentration. A mixture of HNO3 : HCl : HF of 3 : 9 : 2 (v/v/v) and microwave digestion provided suitable recoveries for the analysis of two certified reference materials, CRM BCS-CRM 375/1 and CRM OREAS 460. Good linearity over the calibration range of 0-2 μg mL-1, with correlation coefficients of 0.9995-1.0000, was obtained for each REE by ICP-OES. The limits of quantification (LOQS), calculated considering the instrumental LOQs and the sample preparation by microwave digestion, were in the range of 0.20-0.60 mg kg-1. A supplementary step of preconcentration/matrix separation based on the passive sampling by diffusive gradients in thin-films (DGT) technique improved the LOQs by about 20 times after three days of passive accumulation, allowing the measurement of the concentrations of all studied REEs in natural zeolite samples. The proposed methodology is a suitable approach for the measurement of REEs at low concentrations in natural zeolite samples by ICP-OES, and it can be extended to other geological samples. The measurement uncertainty was calculated based on the validation data. The proposed method provides reliable results for the measurement of REEs in natural zeolites and was used to measure the specific concentrations of REEs in natural zeolite samples from three Romanian quarries. The REE concentration can be used as a fingerprint for each deposit.

Development and validation of an in situ high-resolution technique for measuring antibiotics in sediments

Important biogeochemical processes occur in sediments at fine scales. Sampling techniques capable of yielding information with high resolution are therefore needed to investigate chemical distributions and fluxes and to elucidate key processes affecting chemical fates. In this study, a high-resolution diffusive gradients in thin-films (DGT) technique was systematically developed and tested in a controlled sediment system to measure organic contaminants, antibiotics, for the first time. The DGT probe was used to resolve compound distributions at the mm scale. It also reflected the fluxes from the sediment pore-water and remobilization from the solid phase, providing more dynamic information. Through the fine scale detection, a reduction of re-supply was observed over time, which was concentration and location dependent. Compared to the Rhizon sampling method, antibiotic concentrations obtained by DGT probes were less than the pore-water concentrations, as DGT measures the labile fraction of the compounds. The DGT probe was also tested on an intact sediment core sampled from a lake in China and used to measure the distribution of labile antibiotics with depth in the core at the mm scale. Environmental ImplicationThe abuse of antibiotics and widespread of their residues influences the ecosystem, induces the generation of super-bacteria, and finally poses threat to human health. Sediments adsorbs pollutants from the aquatic environment, while may also release them back to the environment. We systematically developed DGT probe approach for measuring antibiotics in sediment in situ in high resolving power, it provides information at fine scale to help us investigate biogeochemical processes take place in sediment and sediment-water interface.

Maduramicin-guided nanotherapy: A polymeric micelles for targeted drug delivery in canine mammary tumors

Canine mammary tumors (CMT) can severely compromise the life quality of the affected dogs through local recurrence, distant metastases and ultimately succumb to death. Recently, more attention has been given to the potential antimetastatic effect of maduramicin (MAD) on breast cancer. However, its poor aqueous solubility and toxicity to normal tissues limit its clinical application. Therefore, to address the drawbacks of MAD and enhance its anticancer and antimetastatic effects, MAD-loaded TPGS polymeric micelles (MAD-TPGS) were prepared by a thin-film hydration technique. The optimized MAD-TPGS exhibited excellent size distribution, stability and improved water solubility. Cellular uptake assays showed that TPGS polymer micelles could enhance drug internalization. Moreover, TPGS synergistically improved the cytotoxicity of MAD by targeting mitochondrial organelles, improving reactive oxygen species levels and reducing the mitochondrial transmembrane potential. More importantly, MAD-TPGS significantly impeded the metastasis of tumor cells. In vivo results further confirmed that, in addition to exhibiting excellent biocompatibility, MAD-TPGS exhibited greater antitumor efficacy than free MAD. Interestingly, MAD-TPGS displayed superior suppression of CMT metastasis via tail vein injection compared to oral administration, indicating its suitability for intravenous delivery. Overall, MAD-TPGS could be applied as a potential antimetastatic cancer agent for CMT.

Designing and Synthesis of an Anti-Candida parapsilosis Thymoquinone Lipid Formulation

Background: Candida parapsilosis complex, as an opportunistic pathogen, can cause various infections, especially in immunocompromised patients. Objectives: This study investigated a novel thymoquinone-liposomal nanoparticle to increase the stability of thymoquinone with antifungal effects against C. parapsilosis isolates. Methods: The thymoquinone was encapsulated in liposomal nanoparticles using a thin-film hydration technique and then analyzed by transmission electron microscopy (TEM), particle size, zeta potential, and UV-visible spectrophotometer. Also, the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) assay was used on peripheral blood mononuclear cells (PBMCs) for cell metabolic activity. The antifungal activity of thymoquinone-liposomal nanoparticle against 15 clinical isolates of C. parapsilosis and the reference strain was examined based on the M27-A3 guideline. Results: The synthesized thymoquinone-liposomal nanoparticle was approved by the TEM, particle size, zeta potential, and UV-Vis. The thymoquinone-liposomal nanoparticle showed no toxic effect on PBMCs following the MTT assay. The minimum inhibitory concentration (MIC) range of free thymoquinone and liposomal formulations with inhibitory effects on Candida isolates was 50 to 6.25 and 150 to 18.75 µg/mL, respectively. The MIC50 and MIC90 values of free thymoquinone and thymoquinone-liposomal nanoparticle were 25 and 50, and 75 and 150 µg/mL. Conclusions: The synthesized thymoquinone-liposomal nanoparticle shows significant antifungal activity against C. parapsilosis isolates compared to free thymoquinone. However, because of its hydrophilicity and hydrophobicity, biocompatibility, particle size, non-toxic effect, and higher cell viability, the thymoquinone-liposomal nanoparticle is a more effective approach for treating fungal infections.

In silico exploration of venlafaxine, a potential non-tricyclic antidepressant in a liposomal formulation for nose-to-brain drug delivery

Objective Non-tricyclic antidepressants (non-TCAs) work by preventing the intake of norepinephrine and serotonin. Therefore, the aim of this study was to identify a potent non-TCAs and to develop liposomal formulation, characterize and to determine the drug release study across model of dialysis membrane via in vitro and in silico techniques. Methods The in silico docking analysis identified venlafaxine (VLF) as the best non-TCAs with the depressant targets (PDB ID: 3PBL and 4BVN). VLF-loaded liposomal formulation was prepared by the thin-film hydration technique and characterized by physicochemical properties, including entrapment efficacy, in vitro drug release, particle size analysis, and FTIR. Moreover, this article also compares VLF and VLF-loaded with liposome carriers (LPs) based on nose-to-brain drug delivery approaches to treating depression. Results Drug release profiles of the optimal liposomal formulation of VLF-LPs were examined in the high entrapment efficiency 94.13 ± 1.20% was attained at 224 nm, composed of spherical particles having a mean particle size of 191 ± 2.0 nm, a polydispersity index of 0.281 ± 0.06 and zeta potential of −20.3 mV. The best formulation of VLF-LPs was more effective than oral VLF treatment, as shown by the in vitro drug release data. Conclusion The results show that the VLF-LPs formulation is a promising potential platform for application in nose-to-brain drug delivery. Thus, highlighting the robustness of the intranasal drug delivery system with enhanced pharmaceutical properties, efficacy, and bioavailability for the anti-depression effect.

Inherently Selective Atomic Layer Deposition for Optical and Sensor Applications: Microreactor Direct Atomic Layer Processing (μDALP™)

In parallel to additive manufacturing leading the revolution in traditional manufacturing, the same principles can revolutionize traditional thin film deposition techniques. Where lithography and vapor phase deposition techniques struggle, for example, with rapid iterations for prototyping or incompatibility with the used chemistry, additive manufacturing can shine. Indeed, several approaches are in development for 3D nanopriting1,2,3.Atomic Layer Deposition, and in more general Atomic Layer Processing, offers a unique opportunity for localized 3D processing/printing due to its two-step process. While simple in theory, due to well-developed examples of Spatial Atomic Layer Deposition (SALD), in practice miniturization of SALD requires substantial effort into the creation of suitable micro-nozzles. Uniquely, ATLANT 3D has developed proprietary Spatial ALD micronozzles, naming the process microreactor Direct Atomic Layer Processing - µDALPTM.The µDALPTM process undergoes the same cyclic ALD process but, thanks to the in-house microreactor development, is only done in a localized area. The microreactor or micronozzle confines the flows of gases used for ALD within a µm-scale area on the substrate, wherein the reactive species adsorb on the surface to deposit one monolayer of the desired material. Similarly, to spatial ALD, the creation of this monolayer then hinges on the movement of the substrate.4 Since the µDALPTM process is based on physical separation, it is theoretically compatible with any ALD process. As such, the material capabilities can match traditional ALD and exceed other special or patterning thin film techniques, such as lithography, which can be costly and time-consuming, especially for rapid prototyping required for innovation.Films deposited with ATLANT 3D technology have been shown to produce high-quality, crystalline, atomically precise thin films.1 It has been used to fabricate temperature (Fig.1) and capacitive sensors with sensitivities that meet or exceed those of devices made using conventional vapor phase deposition techniques.5 Low-cost rapid prototyping facilitated by ATLANT 3D technology of such devices enables design innovation and optimization not possible with other thin film deposition techniques.ATLANT 3D platform provides flexibility in deposition geometry (Fig.2) that enables a range of optical applications that require high-precision fabrication techniques. Optically transparent films can be used as localized thin protective layers for device encapsulation, as well as for atomic corrections of defects. Alternating deposition materials enable multilayer mirror fabrication of custom dimensions. Smooth thickness gradients can be used to manufacture ultrathin optical lenses. Overlapping depositions with discrete steps enable the manufacturing of binary lenses and phase masks. Growth rate enhancement in rastered direct processing mode using ATLANT 3D technology can produce periodic grating structures.1 Conformal coatings on complex surfaces can act as functionalization layers or seed layers for further material deposition through e.g. electrochemical processes.[1] Kundrata I. et al., ALD/ALE 2022 [Int. Conf.], 2022 [2] de la Huerta C. A. M. et al., arXiv, 2020, 0523. [3] Winkler, R. et al., J. Appl. Phys., 2019, 125, 210901[4] Paul Poodt., JVSTA., 2012, 30, 010802[5] Kundrata, I. et al., Small Methods., 2022, 6 (5), 2101546 Figure 1

Insight into the availability and desorption kinetics of Se and Cd in naturally-rich soils using diffusive gradients in thin-films technique

Cadmium (Cd) contamination of selenium (Se)-rich soils may jeopardize the nutritional benefits of Se-biofortified crops. This study employed diffusive gradients in thin-films (DGT) technique and DIFS (DGT-induced fluxes in soils) model to understand the interdependency and driving factors of Se and Cd distribution and desorption kinetics across 50 soils from south China with naturally elevated levels. DGT-labile Se was the highest (up to 2.66 μg L−1) in non-carbonate/shale-derived soils, while Cd was maximal (5.53 μg L−1) in carbonate-based soils, reflecting soil background concentrations and soil characteristics. Over one-third of the soils showed labile Se:Cd molar ratio below 0.7, suggesting Cd phytotoxicity risks. The DIFS-derived response times (Tc) and desorption rate constants (k−1) suggested that Se was resupplied to the soil solution faster than Cd in soils with higher pH and SOM level, but Se resupply was still restricted due to the rapid depletion of its labile pool. As the first study of Se and Cd release kinetics in soils, our results reveal dependence on soil parent materials, with low labile Se:Cd soils presenting greater Cd hazards. By elucidating Se and Cd lability and interactions in soils, our findings help to inform management strategies to balance reduced Cd risk with adequate Se availability.

A critical review of the quantification, analysis and detection of radionuclides in the environment using diffusive gradients in thin films (DGT): advances and perspectives

Abstract This critical review explores the quantification, analysis, and detection of radionuclides in the environment using the diffusive gradients in thin films (DGT) technique. Radionuclides, unstable isotopes emitting ionising radiation, are present in the environment due to natural and anthropogenic sources for which concerns are raised about their impact on human health and ecosystems. DGT offers a unique passive sampling approach for understanding the behaviour of radionuclides and other trace elements. This review provides insights into method development, real case scenarios, advantages, limitations, and future perspectives of DGT in radionuclide analysis. In terms of method development, various isotopes have been analysed with varying significance based on origin, concentration, risks, and persistence. Notably, U, Th, Pu, Am, Cm, 99Tc, 226Ra, 137Cs, 134Cs, 232U, 237Np, and 152Eu have been measured, revealing their diverse roles in environmental radioactivity. Real case scenarios illustrate applications in uranium mining, water quality monitoring, and metal speciation studies, shedding light on mobility, bioavailability, and ecological impacts. DGT’s advantages include in-situ monitoring, time-averaged mean concentrations, and comprehensive speciation insights. Challenges include potential influences from biofouling, temperature changes and specifically the possible degradation of the binding and diffuse layer due to ionising radiation in long term exposures. In addition, the distinction between fully labile free metal ions and partially labile metal-ligand complexes introduces a potential limitation in the DGT technique, hence being an opportunity for future studies. Looking forward, DGT is expected to contribute to radiation dose modelling, environmental risk assessment, and water quality monitoring, with ongoing developments enhancing its utility and accuracy.

Shaped Magnetogel Microparticles for Multispectral Magnetic Resonance Contrast and Sensing.

Multispectral magnetic resonance imaging (MRI) contrast agents are microfabricated three-dimensional magnetic structures that encode nearby water protons with discrete frequencies. The agents have a unique radiofrequency (RF) resonance that can be tuned by engineering the geometric parameters of these microstructures. Multispectral contrast agents can be used as sensors by incorporating a stimulus-driven shape-changing response into their structure. These geometrically encoded magnetic sensors (GEMS) enable MRI-based sensing via environmentally induced changes to their geometry and their corresponding RF resonance. Previously, GEMS have been made using thin-film lithography techniques in a cleanroom environment. While these approaches offer precise control of the microstructure, they can be a limitation for researchers who do not have cleanroom access or microfabrication expertise. Here, an alternative approach for GEMS fabrication based on soft lithography is introduced. The fabrication scheme uses cheap, accessible materials and simple chemistry to produce shaped magnetic hydrogel microparticles with multispectral MRI contrast properties. The microparticles can be used as sensors by fabricating them out of shape-reconfigurable, "smart" hydrogels. The change in shape causes a corresponding shift in the resonance of the GEMS, producing an MRI-addressable readout of the microenvironment. Proof-of-principle experiments showing a multispectral response to pH change with cylindrical shell-shaped magnetogel GEMS are presented.

Mapping Phosphorus Availability in Soil at a Large Scale and High Resolution Using Novel Diffusive Gradients in Thin Films Designed for X-ray Fluorescence Microscopy.

A novel binding layer (BL) as part of the diffusive gradients in thin films (DGT) technique was developed for the two-dimensional visualization and quantification of labile phosphorus (P) in soils. This BL was designed for P detection by synchrotron-based X-ray fluorescence microscopy (XFM). It differs from the conventional DGT BL as the hydrogel is eliminated to overcome the issue that the fluorescent X-rays of P are detected mainly from shallow sample depths. Instead, the novel design is based on a polyimide film (Kapton) onto which finely powdered titanium dioxide-based P binding agent (Metsorb) was applied, resulting in superficial P binding only. The BL was successfully used for quantitative visualization of P diffusion from three conventional P fertilizers applied to two soils. On a selection of samples, XFM analysis was confirmed by quantitative laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The XFM method detected significant differences in labile P concentrations and P diffusion zone radii with the P fertilizer incubation, which were explained by soil and fertilizer properties. This development paves the way for fast XFM analysis of P on large DGT BLs to investigate in situ diffusion of labile P from fertilizers and to visualize large-scale P cycling processes at high spatial resolution.

The coupled effect of sediment resuspension and microbiota on phosphorus release and transformation in a simulated aquatic ecosystem

Plant microbial involvement in phosphorus (P) release and transformation during resuspension events in bottom aquatic systems remains poorly understood. Laboratory experiments were used in this study to explore the release and transformation of P from sediments and the microbiota involved. Dissolved and labile P were obtained by high-resolution dialysis and the diffusive gradients in thin films (DGT) technique, respectively. The bacterial community was investigated using a scanning electron microscope and 16S rRNA high throughput sequencing technique. Finally, the diffusion fluxes dynamics of phosphorus were calculated using the DGT-induced fluxes in sediments and soils (DIFS) model. These results showed that sustained disturbance can balance dissolved P concentrations in the resuspension layer (overlying water) and enhance the stability of P transformation and release processes. Notably, the bacterial community within the deeper sediment layer (Below 10 mm sediment depth) significantly influences P interception. Acidobacteria and Neobacteria were identified as the key bacterial genera responsible for phosphorus adsorption of plant roots at speeds of 150 rad/min (R150). In addition, as the sediment depths increased, a slower decrease in R curves fitted with the DIFS model, which indicated a continuous resupply process from solid phase to pore water, especially below R150. This study provides theoretical references for managing shallow lakes with frequent sediment resuspension.

Nanoporous antireflection coating for high-temperature applications in the infrared

Antireflection (AR) coatings are essential to the performance of optical systems; without them, surface reflections increase significantly at steep angles and become detrimental to the functionality. AR coatings apply to a wide range of applications from solar cells and laser optics to optical windows. Many times, operational conditions include high temperatures and steep angles of incidence (AOIs). The implementation of AR coatings is extremely challenging in these conditions. Nanoporous coatings made from high-temperature-tolerant materials offer a solution to this problem. The careful selection of materials is needed to prevent delamination when exposed to high temperatures, and an optimal optical design is needed to lower surface reflections at both the normal incidence and steep AOIs. This paper presents nanoporous silicon dioxide and hafnium dioxide coatings deposited on a sapphire substrate using oblique angle deposition by electron beam evaporation, a highly accurate deposition technique for thin films. Developed coatings were tested in a controlled temperature environment and demonstrated thermal stability at temperatures up to 800°C. Additional testing at room temperature demonstrated the reduction of power reflections near optimal for AOIs up to 70° for a design wavelength of 1550 nm. These findings are promising to help extend the operation of technology at extreme temperatures and steep angles.

In Situ Evaluation of Cr(VI) Bioavailability and Rhizosphere Effects in Reduced Cr-Contaminated Soil Based on Diffusive Gradients in Thin Films Technique

The transformation between Cr(III) and Cr(VI) occurs in Cr-contaminated soil, which can be regulated by root-soil interactions, under natural conditions. In situ investigation of the effectiveness of different reductants in reducing Cr(VI) to Cr(III), and thereby the reoccurrence risk in reduced Cr-contaminated soil, can improve the understanding of Cr biogeochemistry and toxicity. Traditional and high-resolution diffusive gradients in thin films (DGT) were used to measure Cr(VI) availability and rhizosphere effect controlling the chemical behaviors of Cr(VI) in the rice rhizosphere microdomain. The Cr(VI) concentration in the soil solution (Csoln) of the rhizosphere region varied according to the reductant type and followed the order: Molasses > CaS4 >Fe(II). Rice root activity increased the Csoln in the rhizosphere region by 2.16 μg/L, 1.90 μg/L, and 1.08 μg/L for Fe(II), CaS4, and Molasses treatments, respectively. The Cr(VI) concentration measured by DGT (CDGT) in the reduced Cr-contaminated soils increased from 0.96–1.17 μg/L in the bulk region to 1.23–1.76 μg/L in rhizosphere region. The variation in the effective concentration of Cr(VI) (CE) was similar to that of Csoln in the rice rhizosphere microdomain. Csoln accounted for 14.71–19.36% of the CE, further suggesting that bioavailable Cr(VI) mainly originated from the replenishment from the solid phase. The sequence of the average Cr(VI) flux in the reduced Cr-contaminated soil was Molasses, CaS4, and Fe(II). Except for Molasses, there was no obvious Cr(III) in Fe(II) and CaS4. For Fe(II), a higher phosphate flux in the rhizosphere microdomain hindered Cr(VI) uptake. High-resolution imaging provides a theoretical basis for the bioavailability evaluation and remediation of Cr-contaminated soil. Compared with CaS4 and Molasses, Fe(II) was the most effective reductant for remediating Cr-contaminated soils.

Femtosecond laser thinning for resistivity control of tungsten ditelluride thin-films synthesized from sol-gel deposited tungsten oxide

In this work we present a route for fabricating WTe2 thin-films together with femtosecond laser post processing, enabling to finely control the conductivity. First, we produce amorphous films of WO3 on Si by spin-coating a sol-gel precursor followed by a consolidating annealing and a reduction process in partial H2 atmosphere, leading to porous metallic tungsten cluster layers. To achieve WTe2, the films were exposed to the chalcogen vapours by isothermal closed space vapor transport. The formation of a tungsten ditelluride film composed of piled crystals could be confirmed and a gradient of surface rich Te identified through hard X-ray photoelectron spectroscopy. Finally, it is demonstrated that resistivity can be changed from 0.2 mΩ.m to 1 mΩ.m, while keeping the material characteristics. An anisotropic conductivity can be induced by direct selective thinning with fs laser writing (350 fs pulse duration, 515 nm laser wavelength) of 1D stripes. The obtained results, demonstrate that laser processing is a promising thin-film post-processing technique that can be applied to 2D transition metal dichalcogenide thin films.

Reliability evaluation of a novel metal oxide-aluminum glycerol film capacitor using nonlinear degradation modeling with dependency considerations

Capacitors are components predominantly used to stabilize voltage, store energy, and lower electrical ripples. To improve the flexibility and capacitance of capacitors, we were motivated to develop hybrid film capacitors using two emerging thin film techniques, atomic and molecular layer deposition (ALD and MLD). Validation of its operational reliability in a power module or an electrical system is critical to facilitate its adoption. Equivalent series resistance (ESR) and capacitance are key performance characteristics (PC) of a capacitor, whose degradation path and process are nonlinear and dependent. Few studies have implemented the Wiener process (WP), to capture the dependency between the PC, based on the assumption of a normally distributed performance loss, notwithstanding that the performance loss may not be normally distributed. To address this concern as well as improve the accuracy of reliability prediction, a reliability framework is proposed. The gamma distribution is found to better fit the incremental PC degradation used in this work. The derived reliability model captured the non-linearity in the PC degradation path as well as its dependency using a selected Copula function. Akaike information criterion (AIC) was used to determine the most suitable Copula. Reliability estimation based on dependency consideration shows the least mean square error (MSE) compared to reliability estimate using a model that considers only one PC or assumes independent PCs. In addition, the hybrid capacitor was compared with an aluminum oxide dielectric layer capacitor, and the result was discussed.