Tetra- and Hexavalent Uranium Forms Bidentate-Mononuclear Complexes with Particulate Organic Matter in a Naturally Uranium-Enriched Peatland
Abstract not provided
Mikutta, Christian↗
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Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]{sup +}[F(HF){sub 2.3}]{sup −} Ionic Liquid
A new methodology for gas-phase uranium ion formation is described in which UO{sub 2} is dissolved in neat N-ethyl,N′-methylimidazolium fluorohydrogenate ionic liquid [EMIm{sup +}][F(HF){sub 2.3}{sup −}], yielding a blue-green solution. The solution was diluted with acetonitrile and then analyzed by electrospray ionization mass spectrometry. UF{sub 6}{sup −} (a U(V) species) was observed at m/z = 352, and other than cluster ions derived from the ionic liquid, nothing else was observed. When the sample was analyzed using infusion desorption chemical ionization, UF{sub 6}{sup −} was the base peak, and it was accompanied by a less intense UF{sub 5}{sup −} that most likely was formed by elimination of a fluorine radical from UF{sub 6}{sup −}. Formation of UF{sub 6}{sup −} required dissolution of UO{sub 2} followed by or concurrent with oxidation of uranium from the + 4 to the + 5 state and finally formation of the fluorouranate. Dissolution of UO{sub 3} produced a bright yellow solution indicative of a U(VI) species; however, electrospray ionization did not produce abundant U-containing ions. The abundant UF{sub 6}{sup −} provides a vehicle for accurate measurement of uranium isotopic abundances free from interference from minor isotopes of other elements and a convenient ion synthesis route that is needed gas-phase structure and reactivity studies like infrared multiphoton dissociation and ion-molecule dissociation and condensation reactions. The reactive fluorohydrogenate ionic liquid may also enable conversion of uranium in oxidic matrices into uranium fluorides that slowly oxidize to uranyl fluoride under ambient conditions, liberating the metal for facile measurement of isotope ratios without extensive chemical separations. .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Convenient Syntheses of Trivalent Uranium Halide Starting Materials without Uranium Metal
Low-valent uranium coordination chemistry continues to rely heavily on access to trivalent starting materials, but these reagents are typically prepared from uranium turnings, which are becoming increasingly difficult to acquire. Here we report convenient syntheses of UI 3 (THF) 4 (THF = tetrahydrofuran) and UBr 3 (THF) 4 from UCl 4 , a more accessible uranium starting material that can be prepared from commercially available uranium oxides. UCl 3 (THF) 2 (1), UBr 3 (THF) 4 (2), and UI 3 (THF) 4 (3) were prepared by single-pot reductions from UCl 4 using KH and KC 8 and converted to 2 or 3 by halide exchange with the corresponding Me 3 SiX (where X = Br or I). Reduction of UI 4 (Et 2 O) 2 (4; Et 2 O = diethyl ether) and UI 4 (1,4-dioxane) 2 (5) was also shown to cleanly yield 3. Complex 1 was also synthesized separately by the addition of anhydrous HCl to U(BH 4 ) 3 (THF) 2 , which was prepared by thermal reduction of U(BH 4 ) 4 . All three trivalent uranium halide complexes were isolated in high crystalline yields (typically 85–99%) and their formulations were confirmed by single-crystal X-ray diffraction, elemental analysis, and 1 H NMR and IR spectroscopy. Elemental analysis conducted on triplicate samples of 1–3 exposed to vacuum for different time intervals revealed significant THF loss for all three complexes in as little as 15 min. Altogether, these results offer expedient entry into low-valent uranium chemistry for researchers lacking access to uranium turnings.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A highly efficient uranium grabber derived from acrylic fiber for extracting uranium from seawater
Acrylic fiber can be chemically converted to an am- idoxime and carboxylate containing chelating adsorbent for extraction of uranium from seawater. At an optimized ratio of amidoxime:carboxylate, the chelating fiber in real seawater shows a higher uranium, shorter saturation time and lower vanadium adsorption capacity relative to similar high-surface area chelating fibers developed recently using a radiation-induced grafting method. This simple and low-cost synthesis method can be scaled up to mass produce the chelating fiber for recovering metals from aquatic environments including production of uranium from seawater.
Pan, H B.↗
Bicarbonate Elution of Uranium from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater
Uranium adsorbed on amidoxime-based polyethylene fibers in simulated seawater can be quantitatively eluted using 3 M KHCO 3 at 40°C. Thermodynamic calculations are in agreement with the experimental observation that at high bicarbonate concentrations (3 M) uranyl ions bound to amidoxime molecules are converted to uranyl tris-carbonato complex in the aqueous solution. The elution process is basically the reverse reaction of the uranium adsorption process which occurs at a very low bicarbonate concentration (~10 -3 M) in seawater. The bicarbonate elution is followed by a NaOH treatment to remove natural organic matter adsorbed on the polymer adsorbent, in real seawater experiments. Furthermore, by using the sequential bicarbonate and NaOH elution, the adsorbent is reusable after rinsing with deionized water and the recycled adsorbent shows no loss of uranium loading capacity based on real seawater experiments.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Structure and thermodynamics of uranium-containing iron garnets
Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca 3 U x Zr 2–x Fe 3 O 12 (x = 0.5–0.7), along with the endmember phase, Ca 3 (Zr 2 )SiFe 3+ 2 O 12 , for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57 Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe 3+ . U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Furthermore, our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca 3 U x Zr 2–x Fe 3 O 12 as viable waste form phases for U and other actinides.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium(VI) monosulphide, uranium(VI) η 2 -disulphide, and uranium(IV) phosphine sulphide complexes
Here, three new uranium species (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S), (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(η 2 -S 2 ), and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ) were synthesized and fully characterized by a combination of NMR, IR, and UV/vis–NIR spectroscopies, elemental analysis, and cyclic voltammetry. The solid state structures of (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(η 2 -S 2 ) were also determined. The compound (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) is the first neutral uranium complex with a terminal sulphido ligand, and (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ) is the first uranium compound with a coordinated phosphine sulphide ligand. The phosphine sulphide adduct, (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(S=PMe 3 ), can be synthesized either by reaction of the uranium(IV) complex (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(thf) with S=PMe 3 or by the reaction of the uranium(VI) terminal sulphido complex (C 5 Me 5 ) 2 U(=N-2,6- i Pr 2 -C 6 H 3 )(=S) with PMe 3 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
C–H Bond Addition across a Transient Uranium–Nitrido Moiety and Formation of a Parent Uranium Imido Complex
Uranium complexes in the + 3 and + 4 oxidation states were prepared using the anionic PN – (PN – = (N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) ligand framework. New complexes include the halide starting materials, (PN) 2 U III I (1) and (PN) 2 U IV Cl 2 (2), which both yield (PN) 2 U IV (N 3 ) 2 (3) by reaction with NaN 3 . Compound 3 was reduced with potassium graphite to produce a putative, transient uranium–nitrido moiety that underwent an intramolecular C–H activation to form a rare example of a parent imido complex, [K(THF) 3 ][(PN)U IV (=NH)[ i Pr 2 P(C 6 H 3 Me)N(C 6 H 2 Me 2 CH 2 )]] (4). Here, calculated reaction energy profiles strongly suggest that a C–H insertion becomes unfavorable when a reductant is present, offering a distinctively different reaction pathway than previously observed for other uranium nitride complexes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Efficacy of acetate-amended biostimulation for uranium sequestration: Combined analysis of sediment/groundwater geochemistry and bacterial community structure
Systematic flow-through column experiments were conducted using sediments and ground water collected from different subsurface localities at the U.S. Department of Energy's Integrated Field Research Challenge site in Rifle, Colorado. The principal purpose of this study is to gain a better understanding of the interactive effects of groundwater geochemistry, sediment mineralogy, and indigenous bacterial community structures on the efficacy of uranium removal from the groundwater with/without acetate amendment. Overall, we find that the subtle variations in the sediments' mineralogy, particle size, redox conditions, as well as contents of metal(loid) co-contaminants showed a pronounced effect on the associated bacterial population and composition, which mainly determines the system's performance with respect to uranium removal. Positive relationship was identified between the abundance of dissimilatory sulfate-reduction genes (i.e., drsA), markers of sulfatereducing bacteria, and the sediments' propensity to sequester aqueous uranium. In contrast, no obvious connections were observed between the abundance of common iron-reducing bacteria, e.g., Geobacter spp., and the sediments' ability to sequester uranium. In the sediments with low bacterial biomass and the absence of sulfate-reducing conditions, abiotic adsorption onto mineral surfaces such as phyllosilicates likely played a relatively major role in the attenuation of aqueous uranium; however, in these scenarios, acetate amendment induced detectable rebounds in the effluent uranium concentrations. The results of this study suggest that reductive immobilization of uranium can be achieved under predominantly sulfate-reducing conditions, and provide insight into the integrated roles of various biogeochemical components in long-term uranium sequestration.
58 GEOSCIENCES↗
Application of HRGS for forensic characterization of uranium oxides, pure uranium metals and uranium alloys
A nondestructive iterative method for uranium-bearing material characterization with HRGS developed earlier in (J. appl. Rad. Isotopes, 166 (2020) 109433) is applied to determine matrix densities and uranium isotope masses of a variety of uranium materials, namely uranium ore, UO 2 and U 3 O 8 powders, fuel elements in the form of UO2 microspheres, uranium metal and uranium alloys. It is shown that U 3 O 8 powders with uranium mass fraction of about 84% can be distinguished from the powders of UO 2 with uranium mass fraction of about 87%; uranium products in the form of liquid or loose powder with matrix density of 0.5-2.0 g/cm 3 can be distinguished from uranium products in the form of compacted fuel elements with matrix density of 6.0-10.0 g/cm 3 and from pure metal uranium and uranium alloys with matrix density of 14.0- 19.0 g/cm 3 . In fuel microspheres based on UO2 the uranium mass fraction 88.02% measured by HRGS is consistent, within the measurement uncertainties, with the results of isotope dilution mass spectrometry 87.76±0.64 % and also is confirmed by X-ray diffraction technique. The uranium mass fraction of the uranium ore estimated as 0.08% by HRGS is consistent, within the measurement uncertainties, with the value 0.09±0.01% determined with WDXRF. Densities of two different uranium metal samples, estimated as 18.42 g/cm 3 and 19.33 g/cm 3 by HRGS are consistent with values 18.24±0.55 g/cm 3 and 18.86±0.59 g/cm 3 , respectively, obtained by the gas pycnometry technique.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Physical conditions for UO formation in laser-produced uranium plumes
Laser-induced plasma spectroscopy is a powerful method for elemental detection and analysis, however the broadening and merging of densely packed spectral lines can make it especially challenging for studying high-Z elements such as uranium and other actinides. In order to understand the processes occurring in laser-induced plasma, it is necessary to evaluate the variation of its thermodynamic parameters. We performed spatiotemporal diagnostics of uranium species in plasma plumes produced by nanosecond near-infrared laser pulses in low- pressure environment. Spatially- and temporally-resolved emission spectroscopy experiments are supported by modeling of uranium emission and its persistence in the plume. Saha-Eggert equation as well as Boltzmann diagrams generated from numerous U I transitions are used to infer temperature. We report the rst measurements of uranium Stark broadening parameters for U I 499.01 nm and U II 500.82 nm transitions. The Stark widths of selected U transitions were measured by comparing their linewidths with the broadening of O I 777.19 nm line. Electron density was found to be on the order of 1016 cm??3, while the temperature was found to be in the range of 3000{8000 K. In addition to enhancing the fundamental understanding of high-Z plasmas under reduced-pressure environments, the knowledge of Stark broadening parameters could improve modeling capabilities and analytical performance of techniques that rely on emission plasma spectroscopy.
(140.3440) Laser-induced breakdown, (280.4788) Opt↗
Formation of uranium oxy-carbide and uranium carbide via conversion of polymer covered uranium dioxide by laser-based thermal processing
Conventional formation of carbonaceous uranium compounds requires bulk processing using furnace-based approaches. Here, a methodology employing polymer covered uranium dioxide and laser-based heating is explored to enable rapid, localized formation of carbonaceous uranium compounds. Specifically, heating of poly(methyl methacrylate) covered uranium dioxide powder to high temperatures using laser irradiation in argon and methane gaseous environments was investigated. Decomposition of material and reactions induced by laser irradiation were probed in situ by residual gas analysis using a benchtop mass spectrometer. In this study, to determine the effect on the resultant material phase, three different process parameters were varied: gaseous atmosphere, laser power, and laser irradiation time. Material processed under varying conditions was analyzed using powder X-ray diffraction and scanning electron microscopy. This work realized the conversion of uranium dioxide into uranium oxy-carbide(s) and uranium carbide(s) phases, at over 60 wt.%, via the polymer surface application and laser-based thermal decomposition methodology.
36 MATERIALS SCIENCE↗
Challenges and opportunities to alloyed and composite fuel architectures to mitigate high uranium density fuel oxidation: Uranium diboride and uranium carbide
Here, the challenges and opportunities to alloyed and composite fuel architectures designed and intended to mitigate oxidation of the fuel during a cladding breach of a water-cooled reactor are discussed in three review manuscripts developed in parallel, with the presented article focused on the oxidation performance of uranium diboride and uranium monocarbide. Several high uranium density fuels are under consideration for deployment as accident tolerant and/or advanced technology nuclear reactor fuels, including UN, U 3 Si 2 , UB 2 , and UC. Presented here is the literature for UB 2 and UC degradation modes, thermodynamics, and oxidation performance of the pure compounds and reported alloyed and composite architectures. Furthermore, this review covers the materials and techniques for the incorporation of additives, dopants, or composite fuel architectures to improve the oxidation behavior for high uranium density fuels for use in LWRs.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Evaluation of a uranium zirconium hydride fuel rod option for conversion of the MIT research reactor (MITR) from highly-enriched uranium to low-enriched uranium
The conversion of the Massachusetts Institute of Technology Reactor (MITR) from the use of highly-enriched uranium (HEU) fuel-plate assemblies to low-enriched uranium (LEU) by replacing the HEU fuel plates with specially designed General Atomics (GA) uranium zirconium hydride (UZrH) LEU fuel rods is evaluated in this paper. The margin to critical heat flux (CHF) in the core, which is cooled by light water at low pressure, is evaluated analytically for steady-state operation. A form of the Groeneveld CHF lookup table method is used and described in detail. A CHF ratio of 1.41 was found in the present analysis at 10 MW with engineering hot channel factors included. Therefore, the nominal reactor core power, and neutron flux performance, would need to be reduced by at least 25% in order to meet the regulatory requirement of a minimum CHF ratio of 2.0.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Assessment of Impacts of Dissolved Organic Matter and Dissolved Iron on the Performance of Amidoxime-Based Adsorbents for Seawater Uranium Extraction
Research on extraction of uranium from seawater has been active in recent years because this technology can provide an additional supply of uranium for nuclear fuel from a much larger uranium reservoir (the oceans) and the processes are more environment friendly. One critical challenge of the development of this technology is to make uranium adsorbents perform well not just in the oversimplified laboratory system (e.g. artificial seawater) but also in the complex real seawater matrix, which is comprised of many competing ions and natural organic substances. Here, we conducted a systematic study using a continuous-flow seawater flume system to assess the potential impacts of dissolved organic matter (DOM) and dissolved iron on the uranium uptake performance (including adsorbent reusability) of amidoxime-based adsorbents. In the 28-day exposure, the adsorbent exposed in dissolved Fe-spiked seawater (low DOM/high Fe) and humic acid-spiked seawater (high DOM/high Fe) showed lower uranium adsorption loadings (73% and 56% of adsorption loading, respectively) than the same adsorbent exposed in seawater without spiking (low DOM/low Fe). Interestingly, the uranium adsorption loading of the reused adsorbent (after uranium stripping by a mild bicarbonate elution) in the dissolved Fe-spiked seawater dropped substantially to only 24% of the loading in the unspiked clean seawater counterpart; while not much change was observed in the performance of adsorbent exposed to the humic acid-spiked seawater. From comparison of FTIR signatures of adsorbent before and after the seawater exposure, we found that the amidoxime ligands in the adsorbent exposed to dissolved Fe-spiked seawater had severer degradation than the adsorbents exposed to humic acid-spiked seawater and unspiked clean seawater. Notably, unlike the adsorbent exposed to dissolved Fe-spiked seawater, the adsorbent exposed to humic acid-spiked seawater didn’t adsorb elevated level of Fe compared to the adsorbent in the unspiked clean seawater. This suggests that the species of Fe in the humic acid-spiked seawater (primarily humic acid bound Fe) didn’t interact with amidoxime-based adsorbent; while the Fe species in the Fe-spiked seawater strongly interacted with adsorbent and caused significant degradation of amidoxime ligands. On the other hand, highly variable uranium adsorption loadings were observed in adsorbent in contact with humic acid-spiked seawater, but not in the adsorbents exposed to dissolved Fe-spiked seawater and seawater without spike. Our observations thus indicate that seawater receiving high inputs of DOM and dissolved Fe, such as coastal waters, is not ideal for efficient extraction of uranium.
Uranium, Seawater, amidoxime-based adsorbents, dis↗
Plume dynamics and gas-phase molecular formation in transient laser-produced uranium plasmas
The dynamics of expansion, thermodynamics, and chemical reactions in laser-produced plasmas is of general interest for all laser ablation applications. This study investigates the complex morphology and behavior of reactive species in nanosecond laser-produced uranium plasmas. Comparing plasma morphology in various inert and reactive ambient gases provides information about the role of gas-phase chemistry in plume hydrodynamics. Background gases including nitrogen and argon foster collisional interactions leading to more significant plume confinement and the increase in persistence of uranium species. On the other hand, environments containing reactive gases such as oxygen promote chemical reactions between the plasma and ambient species. By comparing the expansion dynamics of uranium plumes in nitrogen, air, and argon, we discover that chemical reactions modify the hydrodynamics of the plume at later times of its evolution in the air background. Furthermore, we observe that varying the concentration of oxygen in the fill gas promotes different reaction pathways that lead to the formation of uranium oxides. The reaction pathways from atoms to diatomic to polyatomic molecules strongly vary with ambient oxygen concentration. Lower oxygen concentrations enhance the formation of uranium monoxide from atomic uranium, whereas higher oxygen concentrations tend to depopulate both atomic uranium and uranium monoxide concentrations through the formation of more complex uranium oxides.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Uranium recovery from seawater using amidoxime-based braided polymers synthesized from acrylic fibers
Global demand for nuclear energy is expected to rise in the coming decades. To meet these growing needs, new uranium resources must be explored. One of the potential alternatives to traditional uranium mining is oceanic uranium. The capture and recovery of uranium from the ocean has been under investigation for some time, with many recent studies focused on amidoxime based adsorbents. These adsorbents while able to achieve high uranium recovery capacities are, nevertheless, expensive to produce and adsorb a significant amount of hard to remove vanadium. The purpose of this study is to evaluate the adsorption performance of amidoxime based polymer braids synthesized from acrylic fibers which are designed to significantly cut polymer synthesis and conditioning costs. Adsorption experiments were performed in a recirculating raceway flume system at environmental conditions, approximately 10.8 oC, with 40-micron prefiltered seawater over 28 days for small and large sized LCW polymer braids. For both braid sizes, the adsorption of vanadium was far lower on the LCW materials than on Oak Ridge National Laboratory’s amidoxime based AF1 and AI8 small braids, with the LCW small braids outperforming both materials with respect to uranium adsorption under similar conditions. Adsorption modeling was used to simulate the performance at higher temperatures based on 20oC experiments previously performed with similar materials. Simulation results indicated that the small LCW braids would have a less significant advantage with respect to uranium adsorption over both AF1 and AI8 at 20oC and adsorb slightly less uranium than AF1 at 31oC. Vanadium adsorption by LCW small braids was less than one third of vanadium adsorption by either AF1 or AI8 for all temperatures. This behavior indicates that the LCW materials are able to achieve comparable uranium adsorption to other amidoxime adsorbents previously developed, while being cheaper to produce and adsorbing significantly less vanadium.
Wiechert, Alexander I.↗
Uranium Resource Recovery from Desalination Plant Feed and Reject Water Using Amidoxime Functionalized Adsorbent
With global demand for nuclear power expected to rise, new nuclear fuel resources must be explored to ensure the viability and sustainability of nuclear power. Uranium recovery from seawater is one potential source, though the low concentration of uranium in seawater is a significant obstacle. As a concentrate of seawater, desalination brine reject would have a significantly higher uranyl concentration. In this work, the adsorption of uranium and competing ions in brine reject is investigated. Adsorption experiments were performed over 84 days in 5-gallon batch tanks with amidoxime adsorbents and samples taken from the feed seawater and reverse osmosis brine reject of the Tampa Bay Desalination Plant. The aqueous concentration and adsorbed mass of uranium, zinc, copper, iron, vanadium, calcium, and magnesium were determined through inductively coupled plasma mass spectroscopy. Aqueous adsorption modeling was used to simulate speciation and adsorption of these ions under the experimental conditions. The adsorbed mass of uranium in seawater was 6.22 mg/g adsorbent which declined to 3.95 mg/g in brine. This is a result of increased competition from iron and vanadium whose adsorbed masses increased from 1.06 to 3.00 mg/g and 1.05 to 2.67 mg/g, respectively. Good agreement between experimental and predicted results was obtained for all ions in seawater. Uranium adsorption was overpredicted in brine which may be attributed to the presence of other competing ions and the system not being at equilibrium. Furthermore, results demonstrate that the influence of competing ions, such as those of iron and vanadium, on uranium adsorption would need to be reduced for brine reject to become a significant uranium resource.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗