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At least 433 records · Page 24

Twenty years of dry interim storage of spent nuclear fuel (SNF) in Germany- History and developments - 15575

According to article 6 of the German Atomic Energy Act, storage of nuclear fuel requires a license granted by the competent authority in this field, which is the Federal Office of Radiation Protection. In 1983 a license to store spent nuclear fuel (SNF) and later expanded for vitrified high level waste (HAW) for the interim storage facility in Gorleben was granted. Dry Interim storage at the NPP sites in its actual form started in 2002 in the interim storage facility next to the NPP Lingen. Since this time each NPP erected its own storage facility and three central storage facilities have been built. All of these facilities use dry storage in metallic casks. The actual storage licenses for SNF and the HAW (which is stored in Gorleben and Rubenow) are limited to 40 years starting with the first cask emplacement. As no opening of the cask is intended during the storage period the condition of the inventory and the cask before loading has to be known in detail. This requires for instance detailed knowledge of the history of the SNF loaded as well as supervision of the manufacturing process of the cask. Within the last twenty years several mishaps influenced the regulatory point of view. During a loading campaign in a boiling water reactor traces of pool water remained in the gasket slot and during the drying procedure crystalline boron salts prevented the required tightness. After that event a long-term experiment was started and is still going on which studies the effects of water and minor damages to the gasket. As well changes in the loading procedure have been introduced. The pressure switch used to monitor the pressure in the space between primary and secondary lid has a self surveillance function. This indicated a malfunction 23 times in the last twenty years. Examinations of all events indicated no systematic failure, but a weak point seems to be the plug-in connection. The manufacturer introduced some modifications to improve the system. Introduction of FEM methods in safety analysis to amend the existing methods of testing allowed a new view on and in the cask safety analysis. Progress in this field is closely connected to the available computing capacity and stipulates experts to ongoing improvement. After expiring of the storage license which will be the case for the first cask loaded in 1992 and stored in Ahaus 2032 an extension or a new license can only be granted if the at this time relevant requirements are met. This will require detailed knowledge about the happenings and accidents during the previous storage period. All experience of the periodic safety assessment (PSA) which started in 2013 and accompanying experiments conducted till now and during the licensed storage time will be needed. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Updating the Dry Transfer System - 18110

The Dry Transfer System (DTS) was examined for its ability to be redesigned in order to meet needs associated with repackaging used/spent nuclear fuel (UNF/SNF) from existing storage cask systems into alternative systems, while also incorporating design advances based on some lessons learned from Orano's dry UNF handling facility (T0) located at the La Hague recycling plant. In this redesign, the DTS is envisioned to provide some flexibility through the ability to perform repackaging activities from multiple differently designed cask systems, including those with canisters that will require cutting and welding activities, and potentially with waste packages designed for disposal. The redesigned DTS is also intended to provide some operational flexibility by providing lag storage and include a means for examining UNF/SNF during repackaging, using some features implemented at the T0 facility at La Hague. This paper provides a summary of: the original DTS design, which was evaluated by the NRC and portions of which were cold-tested at Idaho National Lab; the lag storage system designed for the DTS, which is able to flexibly handle different fuel assembly designs while providing structural support for design basis events (e.g., seismic); the incorporation of lessons learned from the La Hague T0 facility into the DTS design to facilitate dry handling of UNF/SNF; and identification of other challenges towards designing a complete system. A revised DTS is envisioned to provide an important tool for the future management of UNF/SNF in preparation for transportation, re-storage, re-transportation, and/or disposal and also provides a means for repackaging UNF/SNF in case recovery from a cask/canister system is necessary (e.g., due to extended storage or a transportation event). (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Novel Mobile Examination and Remediation Facility for On-Site Remediation of Dry Storage Systems - 18389

Most of the spent nuclear fuel (SNF) in dry storage in the United States is safely and securely stored in dual-purpose (i.e., storage and transportation) canisters [1]. However, some of the SNF is stored in storage-only (i.e., non-transportable) packages, or packages that may become nonconforming for continued storage or transportation for a variety of reasons. Currently, the capability to remediate dry storage systems (DSSs) for SNF that are not transportable or that need to be repaired to maintain confinement boundary integrity during storage service does not exist without on-site access to a spent fuel pool. Hence, there is a potential future need for a mobile facility with remediation capabilities that can be used at multiple storage installations. These capabilities would permit needed repairs to an existing DSS to support continued storage or for the dry transfer of fuel to a new conveyance suitable for transport, if necessary. This is a technical paper that does not take into account the contractual limitations under the Standard Contract for Disposal of Spent Nuclear Fuel and/or High-Level Radioactive Waste (Standard Contract) (10 CFR Part 961). Under the provisions of the Standard Contract, DOE does not consider spent nuclear fuel in canisters to be an acceptable waste form, absent a mutually agreed to contract amendment. To the extent discussions or recommendations in this paper conflict with the provisions of the Standard Contract, the Standard Contract provisions prevail. A novel design concept for a Mobile Examination and Remediation Facility (MERF) is proposed with functions and capabilities to remediate a DSS. The proposed MERF would be a multi-purpose facility, remotely operated and computer-controlled with semi-automated equipment to allow trained operators to safely perform remediation activities while keeping worker radiation dose as low as reasonably achievable. It would include a shielded rotating platform with support towers and would use commercial off- the-shelf examination and repair equipment. A slip ring arrangement underneath the rotating platform would allow for the power supply without impeding the continuous rotation and would simplify cable management. The support towers would be mounted on the rotating platform, and each tower would have vertical and horizontal positioning capability for axial and radial tool location. The rotating platform would be attached to the main MERF structure. Capabilities would include visual, surface, and volumetric examinations to fully characterize physical conditions on canister surface before and after a repair; repair techniques, e.g., laser beam welding, friction stir welding, or cold spray, to perform needed remediation activities; and associated equipment for surface preparation such as cutting and grinding equipment. The proposed design would be simple, modular, robust, economically viable, and easily transportable and would have a small footprint. The modular design would present several advantages including compatibility with a variety of different DSSs, on-site assembly, and transportability; it also would be built in interchangeable sections to facilitate decontamination. Further, shielding would be supplemented through interface with the existing transfer cask and storage overpack. Robustness and canister stability would be achieved using pneumatic holders and steel support structures designed with vibration absorbers to reduce impacts and/or a 'pendulum' effect during a seismic event. Thus, the proposed MERF would be designed to: (i) minimize handling of an affected DSS to the extent practicable, (ii) provide radiation shielding and minimize dose to operators and the public during remediation activities, and (iii) enable examination, repair, and repackaging. This paper describes the proposed MERF design concept and capabilities, main components, equipment, different modes of operation, and operating procedures. Structural and safety assessments would need to be performed before final design, licensing, and deployment. The MERF is evaluated with respect to regulatory impact (first of a kind, prior experience), operational impact (safety, security, staffing, ongoing operations, constraints), worker dose (low, medium, high), cost (low, medium, high), schedule (duration, time sequence), and technology readiness level. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cosmic Ray Muon Radiography of Spent Fuel in Dry Storage Casks

In the absence of a permanent repository or reprocessing facilities, highly radioactive spent nuclear fuel bundles are typically placed in long-term storage in above ground casks. These dry storage casks are heavily shielded to prevent the escape of radiation from the contents to the environment. Casks under international safeguards are monitored to detect diversion of spent fuel. The heavy shielding of the cask walls also precludes inspection of cask contents with typical radiographic probes. When international safeguards inspectors need to verify cask contents (which may be necessary to recover from a loss of continuity of knowledge), the casks must be moved back into a cooling pool to be safely opened and visually inspected. This time-consuming procedure is invasive and potentially dangerous. A non-destructive radiographic method to verify a cask's contents in situ would therefore be a useful safeguards tool. Highly energetic cosmic ray muons are an alternative tomographic probe. Since muons are colorless leptons, they do not participate in strong interactions with nucleons, and their large mass suppresses radiative energy loss while passing through materials. These properties allow muons to penetrate dense shielding that defeats more typical probes like photons and neutrons. Measurements of the scattering of muons that pass through objects provide information on the object's internal structure. This summary describes the first measurements using cosmic ray muons to inspect the contents of a partially loaded dry storage cask. We show that partial defects in the cask loading can be identified with this technique. This data shows that cosmic ray muons are an effective radiographic probe of dry storage casks. This technique may be useful for international safeguards inspectors wishing to verify a cask's contents without opening it. The analysis techniques described here allow the column of missing fuel bundles to be determined, but not the row. Recording data from several positions around the cask would allow ambiguities in x-y position to be resolved. Alternatively, a detector could be designed such that it surrounds the cask and provides a full image of the casks interior. Improved measurements and the design of optimized cask imaging instruments are being explored. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Dry Cask Shipments of ATR Spent Nuclear Fuel at INL - 19600

The High Load Charger (HLC) cask will be replacing the Advanced Test Reactor (ATR) spent fuel transfer cask that has been used at Idaho National Laboratory (INL) to wet-transfer spent ATR fuel elements from ATR to Idaho Nuclear Technology and Engineering Center (INTEC) in order to support future plans at both facilities. INTEC intends to discontinue use of the CPP-666 storage pools in compliance with the Idaho Settlement Agreement and the basins will no longer be available to store spent ATR fuel elements. In order to support the core-internals change out in 2021 for ATR, spent ATR fuel elements must be removed from the canal and shipped to INTEC. INL contractors will use the HLC cask for safe, dry transfer of spent Advanced Test Reactor (ATR) fuel elements between the ATR Complex managed by Battelle Energy Alliance, LLC and the Idaho Nuclear Technology and Engineering Center (INTEC) managed by Fluor Idaho, LLC. The HLC cask (also known as the High Load Charging Cask or High Load Charger) is a lead-shielded, stainless steel transfer container originally designed in 1954 by the Idaho Nuclear Corporation to meet the radiation and contamination controls requirements of the time for shipment of spent nuclear fuel. The cask has been modified over the years and is currently used for wet-to-dry transfers at INTEC. It is approved only for out-of-commerce transfers. The cask will arrive at the ATR where eight spent ATR fuel elements will be loaded into two, newly-designed buckets. Each bucket is a quarter section, right-cylinder shape that has four compartments. The cask will be lifted out of the ATR canal allowing most of the water to drain from the cask. Processing the 12,500 kg cask will be completed in ATR and then transported on a tractor trailer to INTEC where the loaded buckets will be removed from the cask. The loaded buckets will undergo a drying process before placing the four buckets into a canister for long-term storage in the Irradiated Fuel Storage Facility (IFSF) at INTEC. A new transportation plan that was submitted to, and approved by, the U.S. Department of Energy to provide the cask safety basis, which describes the hazard analysis and accident analysis for the cask during transport. Supporting accident analysis include criticality, thermal, dose, and drop analyses. Of particular interest for this cask was the drop analysis from which was derived the speed limit for the transport. The drop analysis addressed drops in air onto an unyielding surface and in water onto an energy-absorbing pad for the cask in the ATR facility. These analyses are typically applied as the bounding drop scenarios during transport; however, this resulted in a safety basis speed limit of 12.9 kph. In order to more accurately represent the in-transit accident scenario, LS-DYNA software was procured and the model was updated to more closely represent the potential drop heights and impact surfaces of asphalt and soil for the cask while in transit. This analysis resulted in a safety basis speed limit of 48 kph. This safety basis speed limit is more practical to implement and control. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Impact of Dry Cooler Air-Side Performance on a sCO2 Power Cycle for a CSP Application

Uncertainty around the design and control of the supercritical CO2 power cycle must be reduced before this technology can be implemented for large-scale grid support. To better understand the day-to-day performance of an sCO2 cycle, off-design performance calculations must be included for all power block components, and performance assumptions must be removed. This study has expanded the modeled scope to include the air-side performance for the dry cooler and has incorporated discretized heat transfer calculations for both streams through the pre-cooler to better predict off-design performance. This study considered a recompression Brayton cycle in a concentrating solar power application. The cycle model utilized fixed sCO2 turbomachinery maps for the main compressor, recompressor, and expander operating to supply approximately 10 MW gross at the design point. Fixed vendor-supplied fan curves were used to calculate the air-side performance of the dry cooler. The primary heater was modeled considering both the sCO2 and heat transfer fluid streams. Off-design performance was predicted for an ambient temperature range of 0-55℃, a HTF temperature range of 705-735℃, and a HTF mass flow range of 50-105% of the design point value. To understand the importance of modeling the air-side performance, the cycle off-design performance was also calculated using a constant CO2 outlet temperature assumption and a constant approach temperature assumption for the dry cooler. Results show that using these assumptions can significantly alter the power output and cycle efficiency predictions.

14 SOLAR ENERGY↗

Modeling Radiolysis and Chemical Reactions during Dry Storage of Aluminum-clad Spent Nuclear Fuel

After aluminum-clad spent nuclear fuel (ASNF) is removed from the reactor, it is initially stored in spent fuel pools, which are specially designed water-filled basins that provide temporary cooling to reduce the temperature of the fuel assemblies and provide radiation shielding. ASNF continues to generate heat due to the radioactive decay of elements within the fuel, which persists for many years post-shutdown as the residual radioactive products decay into more stable elements. During the wet storage period, an oxyhydroxide layer composed of boehmite/bayerite forms on the surfaces of the aluminum cladding from exposure to water in the pools. Road-ready packaging for long-term disposition of the ASNF involves dry storage in helium backfilled DOE standard canisters (DSCs). When the ASNF is removed from water storage and dried, most of the water is removed, but some physisorbed and chemisorbed water remains in the oxyhydroxide layers. This residual water can produce hydrogen when exposed to radiation from the ASNF during dry storage. Predicting hydrogen accumulation over time in the DSCs is critical for long-term storage considerations. Previous modeling efforts have developed coupled computational fluid dynamics (CFD)-chemical models to simulate temperature, pressure, and gas phase concentrations within the DSCs. These models use the thermal field predicted by CFD as input to a radiolysis model for the gas phase and the surface oxyhydroxide layer chemistry. Given the long storage period of the DSCs and the impracticality of long-term experiments, a simulation-based approach is necessary to assess chemical evolution within the canisters. This study advances the development of a modeling framework designed to simulate the chemical evolution of spent fuel canisters. Both thermal and radiation-driven reactions are considered, with radiation kinetics quantified using G-values. Sensitivity analysis identifies key parameters influencing species composition. Reaction pathway diagrams offer insight into dominant species formation routes, enabling more effective comparisons between model predictions and experimental observations, particularly regarding the production of hydrogen. Results show that the model predicts significant hydrogen gas production with minimal oxygen generation, primarily due to hydrogen formation via boehmite pathways. These findings underscore the importance of accurately characterizing surface-bound species and radiolysis kinetics. A deeper understanding of these mechanisms is critical for evaluating the long-term safety of nuclear waste storage.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗

First of Their Kind: Solar Cells with a Dry-Processed Perovskite Absorber Layer via Powder Aerosol Deposition and Hot-Pressing

Preparing halide perovskite films by solvent-free, powder-based processing approaches currently attracts more and more attention. However, working solar cells employing dry, powder-based halide perovskite thin films, have not been demonstrated so far. Herein, perovskite solar cells are presented where the absorber layer is prepared by transferring readily synthesized perovskite powders into a compact thin film using a fully dry-powder-processing concept. Compact thin films are deposited via an optimized powder aerosol deposition (PAD) process. Pressing at 120 °C further improves the morphology and the optoelectronic film properties. Integrating the perovskite films in a solar cell configuration results in fully working devices, with champion power conversion efficiencies of >6%. While the (optoelectronic) properties of the PAD-processed films are found to be comparable with their solution-processed counterparts, investigations of the solar cell stack suggest deterioration of the electron-transport layer properties due to the PAD process, and the presence of hydrates at the perovskite surface to be important factors that contribute to the limited solar cell efficiency. Herein, perspectives to overcome the identified limitations are outlined, emphasizing the high potential and realizability of efficient perovskite solar cells based on dry-powder-processing approaches in the future.

14 SOLAR ENERGY↗

Aqueous spray-drying synthesis of alluaudite Na 2+2x Fe 2–x (SO 4 ) 3 sodium insertion material: studies of electrochemical activity, thermodynamic stability, and humidity-induced phase transition

In pursuit of high-energy density sodium insertion materials, polyanionic frameworks can be designed with tuneable high-voltage operation stemming from inductive effect. Alluaudite Na 2 Fe 2 (SO 4 ) 3 polysulfate forms one such earth-abundant compound registering the highest Fe 3+ /Fe 2+ redox potential (ca. 3.8 V vs. Na/Na + ). While this SO 4 -based system exhibits high voltage operation, it is prone to thermal decomposition and moisture attack leading to hydrated derivatives, making its synthesis cumbersome. Also, the Na–Fe–S–O quaternary system is rich with (anhydrous to hydrated) phase transitions. Herein, we demonstrate scalable aqueous-based spray drying synthesis of alluaudite Na 2+2x Fe 2–x (SO 4 ) 3 sodium insertion material involving the formation of bloedite Na 2 Fe(SO 4 ) 2 ·4H 2 O as an intermediate phase. Moreover, a reversible phase transition from alluaudite to bloedite under controlled conditions of temperature and relative humidity is reported for the first time. Thermochemistry measurements revealed the enthalpies of formation (ΔH° f ) of alluaudite and bloedite are exothermic. Hydrated bloedite (ΔH° f = –117.16 ± 1.10 kJ/mol) was found to be significantly more energetically stable than anhydrous alluaudite (ΔH° f = –11.76 ± 1.25 kJ/mol). The calorimetric data support the observed synthesis and transformation (hydration-dehydration) pathways. Spray drying route led to spherical morphology delivering capacity ~80 mAh/g. Spray drying can be extended for rapid economic synthesis of sulfate class of battery materials.

25 ENERGY STORAGE↗

The carbon economy of drought: comparing respiration responses of roots, mycorrhizal fungi, and free-living microbes to an extreme dry-rewet cycle

The effects of drying and wetting on soil carbon processes are regulated by the responses of plants, plant-associated microbes, and free-living microbes. Whether these groups respond similarly to drying and wetting is not clear, however, making it difficult to predict the net effect of drought on soil carbon processes. We imposed a drought-rewetting event on mesocosms planted with maple ( Acer saccharum Marshall; arbuscular mycorrhizal fungi host) or oak ( Quercus alba L.; ectomycorrhizal fungi host) saplings. In each mesocosm, we used mesh to create chambers separating roots, mycorrhizal fungi hyphae, and free-living microbes. We compared respiration and carbon degrading enzyme activity across chambers throughout the dry-rewetting cycle. As a result, respiration from all chambers declined during drought, and chambers differed in their drought-sensitivity. In maple mesocosms, respiration from the Hyphae+Microbes chamber was the most drought-resistant; in oak mesocosms respiration from the Microbes chamber was the most drought-sensitive. Respiration did not recover after rewatering, indicating a persistent drought legacy. In contrast, enzyme activity returned to control functioning after 2 weeks of well-watered conditions. Our results suggest that belowground biota differ in their sensitivity to and recovery from drought, which affects the carbon processes differently. An improved ability to partition carbon fluxes into biotic sources can help to constrain predicted carbon fluxes under future climate scenarios.

54 ENVIRONMENTAL SCIENCES↗

Molecular formula composition of β-caryophyllene ozonolysis SOA formed in humid and dry conditions

Here, we studied the molecular formula composition of six β-caryophyllene SOA samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under various reaction conditions. The SOA samples were generated in dry or low relative humidity (RH) chamber conditions with or without cyclohexane. All of the studied SOA mass spectra have three distinct clusters of hundreds of negative ions referred to as Group I (100 < m/z < 400), Group II (400 < m/z < 700) and Group III (700 < m/z < 1 000) compounds. C 14-16 H 22-28 O 2-11 , C 28-29 H 42-48 O 6-16 and C 42-43 H 68-70 O 14-16 were observed as highly abundant organic compounds in the compound class of Group I, II and III, respectively. The relative intensities of most analytes were higher in humid conditions compared to those in dry conditions, indicating the importance of water-dependent reactions and the catalytic role of water both in the presence and absence of cyclohexane. In addition, molecular formulas with higher average carbon numbers were observed in humid SOA than in dry SOA in the absence of cyclohexane, suggesting a decrease of cleavage reactions in humid condition. This study characterizes β-caryophyllene ozonolysis SOA based on ultrahigh mass resolution and demonstrates the significance of humidity in terms of the molecular distributions and relative abundances of the analytes. We also discuss the possible mechanism for the formation of Group I-III compounds based on the current understanding of SOA formation in the atmosphere.

54 ENVIRONMENTAL SCIENCES↗

Improving the particle dry deposition scheme in the CMAQ photochemical modeling system

Dry deposition of atmospheric aerosols in large-scale models is a critical, but highly uncertain, sink process with a strong dependence on particle size, meteorological conditions, and land surface properties. This study investigates the particle dry deposition scheme implemented in the standard Community Multiscale Air Quality (CMAQ) model v5.2.1, characterizes its underlying parameterized components with comparison to a similar scheme in a contemporary regional-scale model, and proposes two updated schemes that are then evaluated with available ambient particle deposition velocity (V d ) measurements. Both updated schemes reduce the surprisingly strong dependence of deposition velocity on the aerosol mode width, with one scheme further introducing a dependence on vegetation coverage that is broadly consistent with variability in observations between vegetated and non-vegetated surfaces. Compared to the base scheme, the updated scheme with vegetation dependence increases V d for submicron particles and decreases it for larger particles by an average of 37% and –66%, respectively. This scheme performs statistically better than the base scheme, reducing fractional biases by 56%–97% for vegetated land-use types and has roughly equivalent performance over water. The base and updated schemes are tested with three annual CMAQ (v5.2.1) simulations for the year 2011; predicted ambient aerosol concentrations are evaluated with routine monitoring network observations and predicted dry deposition fluxes are evaluated with data from the Clean Air Status and Trends Network (CASTNET). The updated scheme with vegetation dependence reduces negative fractional biases for PM 10 by 41% and positive fractional biases for PM 2.5 organic carbon by 15%. This scheme has been incorporated into the most recent publicly accessible versions of CMAQ (v5.3 and beyond) to replace the scheme used in previous versions of CMAQ (v4.5 through v5.2.1).

54 ENVIRONMENTAL SCIENCES↗

Estimating viscoelastic compliance of desiccating cementitious materials using drying prism tests

Highlights: • Determining relative humidity and degree of reaction of desiccating cementitious materials via an integrated method • Extracting moisture diffusion coefficient of cement mortar using the mass loss data of the prism specimens • Estimating uniaxial viscoelastic compliance of cement mortar using the shrinkage strain data of the prism specimens An integrated modeling approach to determining internal relative humidity and degree of reaction of desiccating cementitious materials has been developed. By simultaneously accounting for both self-desiccation and external drying, the model is capable of predicting the evolution of material properties of desiccating cementitious materials. Using the mass loss data of the prism specimens, the moisture diffusion coefficient of a nonlinear model for cement mortar was determined. Additionally, a previous poroviscoelastic shrinkage model was modified and extended. Through comparison of predicted and measured axial strain of the prism specimens, the viscoelastic compliance of cement mortar was extracted. The present work revealed that it is possible to use a simple drying prism test to fit the moisture diffusion coefficient and creep compliance of cementitious materials, though the comparison of the extracted viscoelastic compliance with measured compliance was only reasonable if the outer layer of the drying mortar was presumed to have microcracking.

36 MATERIALS SCIENCE↗

Fast synthesis of La-substituted apatite by the dry mechanochemical method and analysis of its structure

Compared to pure apatite, La-substituted apatites have improved thermal, mechanical and biological characteristics. In this article, a fast synthesis of La-substituted apatites by a dry mechanochemical method is presented. Structural studies by X-ray diffraction and Fourier transform infrared spectroscopy indicated the formation of a single-phase nanosized product after 30 min of high-energy ball milling of the reaction mixtures. The dry mechanochemical method is technologically attractive for the preparation of La-substituted apatites, as it allows reducing the processing time down to half an hour and does not require prolonged high-temperature annealing normally used in the synthesis practice of the substituted apatite. As the mechanochemically synthesized samples are nanosized, it is difficult to determine the details of their crystal structure by the Rietveld refinement method. Therefore, a series of the mechanochemically synthesized samples with different concentrations of lanthanum were annealed at 1000 °C for 5 h. It was found that the annealed powders are microcrystalline La-substituted apatites Ca{sub 10−x}La{sub x}(PO{sub 4}){sub 6}O{sub x}(OH){sub 2−x}, where 0 ≤ x ≤2. In their structure, the Ca{sup 2+} ions are replaced by the La{sup 3+} ions localized near the Ca2 sites, and the OH{sup -} groups are replaced by the O{sup 2-} ions in the hexagonal channels. - Highlights: • a new approach to the synthesis of La-substituted apatites is proposed. • dry mechanochemical method allows reducing the synthesis time down to 30 min. • the product of synthesis is single-phase with an average crystallite size of 20 nm. • the parameters and volume of the unit cell increase with dopant concentration. • La-substituted apatites are Ca{sub 10−x}La{sub x}(PO{sub 4}){sub 6}O{sub x}(OH){sub 2−x}, where 0 ≤ x ≤ 2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrophobicity control by a supercritical drying technique in a sol–gel process with hybrid materials

Highlights: • Sol–gel route is combined with polymerization without using modifier. • Supercritical drying control is the key to obtain super-hydrophobic surfaces. • The whole fabrication is technologically controllable and with low costs. • The production rate is higher than 90%. • The method provides a cost-effective way for industry applications. - Abstract: We successfully synthesized one type of cheap super-hydrophobic hybrid porous materials in a sol–gel process. In this route, hydrophilic polymers and TEOS-base sol are used as precursors, the ultraviolet ray-initiated polymerization and supercritical fluid drying techniques are combined together to fulfill this task. All fabricated samples exhibit lotus-leaf-like surface structures with super-hydrophobicity. The underlying mechanisms are carefully investigated using a field-emission scanning electron microscopy (FESEM) and an X-ray photoelectron spectroscopy (XPS). We found that a well-controlled drying process is crucial to the formation of such super-hydrophobic surfaces. As high as 90% production rate is obtained in our route and thus, it might provide a cost-effective way to produce super-hydrophobic hybrid materials for industry applications.

36 MATERIALS SCIENCE↗

Synthesis of nickel oxide nanospheres by a facile spray drying method and their application as anode materials for lithium ion batteries

Graphical abstract: NiO nanospheres prepared by a facile spray drying method show high lithium ion storage performance as anode of lithium ion battery. - Highlights: • NiO nanospheres are prepared by a spray drying method. • NiO nanospheres are composed of interconnected nanoparticles. • NiO nanospheres show good lithium ion storage properties. - Abstract: Fabrication of advanced anode materials is indispensable for construction of high-performance lithium ion batteries. In this work, nickel oxide (NiO) nanospheres are fabricated by a facial one-step spray drying method. The as-prepared NiO nanospheres show diameters ranging from 100 to 600 nm and are composed of nanoparticles of 30–50 nm. As an anode for lithium ion batteries, the electrochemical properties of the NiO nanospheres are investigated by cyclic voltammetry (CV) and galvanostatic charge/discharge tests. The specific reversible capacity of NiO nanospheres is 656 mA h g{sup −1} at 0.1 C, and 476 mA h g{sup −1} at 1 C. The improvement of electrochemical properties is attributed to nanosphere structure with large surface area and short ion/electron transfer path.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Multi-scale integration of satellite remote sensing improves characterization of dry-season green-up in an Amazon tropical evergreen forest

In tropical forests, leaf phenology-particularly the pronounced dry-season green-up-strongly regulates biogeochemical cycles of carbon and water fluxes. However, uncertainties remain in the understanding of tropical forest leaf phenology at different spatial scales. Phenocams accurately characterize leaf phenology at the crown and ecosystem scales but are limited to a few sites and time spans of a few years. Time-series satellite observations might fill this gap, but the commonly used satellites (e.g. MODIS, Landsat and Sentinel-2) have resolutions too coarse to characterize single crowns. To resolve this observational challenge, we used the PlanetScope constellation with a 3m resolution and near daily nadir-view coverage. We first developed a rigorous method to cross-calibrate PlanetScope surface reflectance using daily BRDF-adjusted MODIS as the reference. We then used linear spectral unmixing of calibrated PlanetScope to obtain dry-season change in the fractional cover of green vegetation (GV) and non-photosynthetic vegetation (NPV) at the PlanetScope pixel level. We used the Central Amazon Tapajos National Forest k67 site, as all necessary data (from field to phenocam and satellite observations) was available. For this proof of concept, we chose a set of 22 dates of PlanetScope measurements in 2018 and 16 in 2019, all from the six drier months of the year to provide the highest possible cloud-free temporal resolution. Our results show that MODIS-calibrated dry-season PlanetScope data (1) accurately assessed seasonal changes in ecosystem-scale and crown-scale spectral reflectance; (2) detected an increase in ecosystem-scale GV fraction (and a decrease in NPV fraction) from June to November of both years, consistent with local phenocam observations with R 2 around 0.8; and (3) monitored large seasonal trend variability in crown-scale NPV fraction. Finally, our results highlight the potential of integrating multi-scale satellite observations to extend fine-scale leaf phenology monitoring beyond the spatial limits of phenocams.

54 ENVIRONMENTAL SCIENCES↗

Continuous dry fermentation of swine manure for biogas production

Highlights: • Continuous dry fermentation of swine manure for biogas production is feasible. • The feedstock TS concentration exerted a significant impact on biogas production. • Influences of ammonia and digestate liquidity were investigated in this study. • The results showed that the feedstock TS of swine manure should not exceed 30%. - Abstract: A down plug-flow anaerobic reactor (DPAR) was designed for the feasibility study on continuous dry fermentation of swine manure without any additional stirring. Using fresh swine manure as the feedstock with TS concentration (w/w) of 20%, 25%, 30%, and 35%, stable volumetric biogas production rates of 2.40, 1.92, 0.911, and 0.644 L·(L d){sup −1} and biogas yields of 0.665, 0.532, 0.252, and 0.178 L g{sup −1}VS were obtained respectively, and the TS degradation rates were 46.5%, 45.4%, 53.2%, and 55.6%, respectively. With the increase of feedstock TS concentration, the concentration of ammonia nitrogen grew up to the maximum value of 3500 mg L{sup −1}. Biogas production was obviously inhibited when the concentration of ammonia nitrogen was above 3000 mg L{sup −1}. The maximal volumetric biogas production rate of 2.34 L·(L d){sup −1} and biogas yield of 0.649 L g{sup −1}VS were obtained with TS concentration of 25% at 25 °C without inhibition. Liquidity experiments showed that TS concentration of digestate could be less than 15.8%, and the flow rate of digestate more than 0.98 m s{sup −1} when the feedstock TS concentration was less than 35%, which indicated the digestate could be easily discharged from a DPAR. Therefore, it is feasible to conduct a continuous dry fermentation in a DPAR using fresh swine manure as the feedstock with TS concentration less than 35%, whereas the feedstock TS concentration should not exceed 30% to achieve the maximal biogas production rate and biogas yield.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗