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At least 1,063 records · Page 59

Effects of Vanadium on Modification of Iron-Rich Intermetallics and Mechanical Properties in A356 Cast Alloys with 1.5 wt.% Fe

Formation of Fe-rich intermetallics and mechanical properties of vanadium-modified A356 cast alloys with 1.5 wt.% Fe were investigated using image analysis, scanning electron microscopy, differential scanning calorimetry, and a tensile test. The results showed that V content has no apparent influence on α-Al grain size in A356 alloys with high Fe content. Also, 0.8 wt.% V is beneficial for improving mechanical properties in A356 cast alloys with high Fe content. Specifically, these results can be attributed to the formation of Chinese script or block α-Fe phases, refined needle-like β-Fe (Al{sub 5}FeSi), and decreased porosities. An excessive amount of V deteriorates mechanical properties of alloys because it leads to VSi{sub 2} formation, large sized iron-rich intermetallics, and increased porosities.

36 MATERIALS SCIENCE↗

Effect of Ca and Sm Combined Addition on the Microstructure and Elevated-Temperature Mechanical Properties of Mg-6Al Alloys

In the present study, the microstructure and elevated-temperature mechanical properties of Mg-6Al, Mg-6Al-4Ca, Mg-6Al-4Sm and Mg-6Al-2Ca-2Sm alloys were investigated. The experimental results showed that the microstructure and elevated-temperature mechanical property of Mg-6Al alloy changed obviously with the different elements addition. By analyzing the results of optical microscope, x-ray diffraction analysis, scanning electron microscope, and transmission electron microscope, it could be determined that there was only Mg{sub 17}Al{sub 12} phase in Mg-6Al alloy, there were Al{sub 2}Ca and (Mg, Al){sub 2}Ca phases in Mg-6Al-4Ca alloy, there were Al{sub 2}Sm and Mg{sub 17}Al{sub 12} phases in Mg-6Al-4Sm alloy, and there were (Mg, Al){sub 2}Ca, Al{sub 2}Ca and Al{sub 2}Sm phases in Mg-6Al-2Ca-2Sm alloy. In addition, the addition of alloying elements including Ca and Sm, especially the composite addition, could significantly improve the tensile properties of Mg-6Al alloy. Compared to Mg-6Al alloy, the tensile strengths of Mg-6Al-2Ca-2Sm alloy at 448, 473 and 498 K were enhanced by 50.32, 87.92, and 94.99%, respectively. Furthermore, when the stretching temperatures were 448 and 473 K, the fracture pattern of Mg-6Al-2Ca-2Sm alloy was the mixture of intergranular fracture and trans-crystalline fracture. However, when the stretching temperature was 498 K, the fracture pattern of Mg-6Al-2Ca-2Sm alloy was the intergranular fracture.

36 MATERIALS SCIENCE↗

Creep Behavior of Friction Stir Processed Haynes 282

Haynes 282 is a nickel-based superalloy designed for use in hot sections of turbines for aircraft and power generation. In these applications, elevated temperature creep performance is critical. To that end, creep behavior of friction stir processed material was carried out to investigate the high-temperature performance of this alloy. Friction stir processing of Haynes 282 was successfully completed, and the processed region was found to be defect-free. Various mechanical property characterization approaches were carried out in post-heat treated condition. Transverse tensile samples repeatedly failed in the base metal indicating 100% joint efficiency. Creep property evaluation was completed at 760 °C and at various stress levels. The creep-rupture lifetime of the processed material was similar to the base metal. Detailed electron microscopy analysis of the failed sample was carried out to understand the microstructural evolution in various locations of the sample during creep.

creep↗

Effect of Aluminizing on the High-Temperature Oxidation Behavior of an Alumina-Forming Austenitic Stainless Steel

Due to their excellent oxidation resistance and creep resistance at elevated temperatures, alumina forming austenitic (AFA) stainless steels have emerged as potential alloys for high temperature applications. In this study, a Reactive Air Aluminizing (RAA) method was used to aluminize the surface of AFA25 stainless steel. The high temperature oxidation behavior of both as-received and aluminized AFA25 was investigated at 850 °C in dry air. The mass gain per unit area was higher for the aluminized AFA25 than for the as-received material. X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS), performed on the oxide scales following the high temperature oxidation tests, confirmed the formation of alumina scale on both as-received and aluminized AFA. However, the aluminized alloy exhibited a thicker alumina scale on the surface, as well as more extensive penetration of the scale into the subsurface region of the alloy.

Rashidi, S.↗

Shape transformation of bimetallic Au–Pd core–shell nanocubes to multilayered Au–Pd–Au core–shell hexagonal platelets

Transformation of metallic or bimetallic (BM) nanoparticles (NPs) from one shape to another desired shape is of importance to nanoscience and nanotechnology, where new morphologies of NPs lead to enhancement of their exploitable properties. In this report, we present the shape transformation of Au octahedral NPs to Au–Pd core–shell nanocubes, followed by their transformation to nanostars and finally to multilayered Au–Pd–Au core–shell hexagonal platelets in the presence of T30 DNA. The weaker binding affinity of T30 DNA directs the growth to favor the formation of lower energy {111} facets, changing the morphology from nanocubes to nanostar. The nanostars, exhibiting unusual intermediate morphologies, are comprised two sets of shell layers and have Au core, Pd intermediate shell, and Au outer shell. Similarly, the hexagonal platelets, which also have Au core and inner Pd shell, are encased in an external gold shell. As a result, the formation of multilayered Au–Pd–Au core–shell hexagonal platelets from Au–Pd core–shell nanocubes via the multilayered nanostars is monitored using scanning/transmission electron microscopy analysis.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High temperature microstructural stability and recrystallization mechanisms in 14YWT alloys

In-situ neutron diffraction experiments were performed on room temperature compressed 14YWT nanostructured ferritic alloys at 1100°C and 1150°C to understand their thermally activated static recrystallization mechanisms. The existence of high density of Y-Ti-O rich nano-oxides (<5 nm) shift the recrystallization temperature up due to Zener pinning of the grain boundaries, making these materials attractive for high temperature applications. This study serves to quantify the texture evolution in-situ and understand the effect of particles on the recrystallization mechanisms in 14YWT alloys. We have shown, both experimentally and theoretically, that there is considerable recovery in the 20% compressed sample after 6.5 h annealing at 1100°C while recrystallization occurs within an hour of annealing at 1100°C and 1150°C in the 60% compressed samples. Moreover, the 60% compressed samples show {112}<110> and {112}<111> texture components during annealing, in contrast to the conventional recrystallization textures in body centered cubic alloys. Furthermore, nano-oxide size, shape, density and distribution are considerably different in unrecrystallized and abnormally grown grains. Transmission electron microscopy analysis shows that oxide particles having a size between 5 and 30 nm play a critical role for recrystallization mechanisms in 14YWT nanostructured ferritic alloys.

36 MATERIALS SCIENCE↗

Arsenic attenuation in tailings at a former Cu-W-As mine, SW Finland

Nearly half a century after mine closure, release of As from the Ylöjärvi Cu–W–As mine tailings in groundwater and surface water run-off was observed. Investigations by scanning electron microscopy (SEM), electron microprobe analysis (EMPA), synchrotron-based micro-X-ray diffraction (μ-XRD), micro-X-ray absorption near edge structure (μ-XANES) and micro-extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, and a sequential extraction procedure were performed to assess As attenuation mechanisms in the vadose zone of this tailings deposit. Results of SEM, EMPA, and sequential extractions indicated that the precipitation of As bearing Fe(III) (oxy)hydroxides (up to 18.4 wt.% As 2 O 5 ) and Fe(III) arsenates were important secondary controls on As mobility. The μ-XRD, μ-XANES and μ-EXAFS analyses suggested that these phases correspond to poorly crystalline and disordered As-bearing precipitates, including arsenical ferrihydrite, scorodite, kankite, and hydrous ferric arsenate (HFA). The pH within 200 cm of the tailings surface averaged 5.7, conditions which favor the precipitation of ferrihydrite. Poorly crystalline Fe(III) arsenates are potentially unstable over time, and their transformation to ferrihydrite, which contributes to As uptake, has potential to increase the As adsorption capacity of the tailings. Arsenic mobility in tailings pore water at the Ylöjärvi mine will depend on continued arsenopyrite oxidation, dissolution or transformation of secondary Fe(III) arsenates, and the As adsorption capacity of Fe(III) (oxy)hydroxides within this tailings deposit

Parviainen, Annika↗

Source and distribution of naturally occurring arsenic in groundwater from Alberta’s Southern Oil Sands Regions

Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrations in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(-I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.

58 GEOSCIENCES↗

Carbon nanotube coated metal mesh: Bridging nanoscale and macroscale

A novel hybrid structure has been developed by growing carbon nanotubes (CNTs) on a metal mesh that functions as a literally unlimitedly extendable backbone. This hybrid material structure provides a new approach of extending CNTs’ advantageous properties such as ultrahigh thermal and electrical conductivities, high sensitivity to gases, and distinctive wettability for different liquids with chemical inertness to macroscale—otherwise available only in nano- and microscales. In this feasibility work, CNTs were grown on a Type 316 stainless steel (SS) mesh by self-catalytical chemical vapor deposition (CVD) without the need of an externally added catalyst or catalyst support. For the radially aligned and entangled CNT forest on the SS mesh, the average CNT diameter is around 50 nm, while the length varies from 20 to 25 µm. High-resolution transmission electron microscopy analysis revealed the multiwall structure of the CNTs with >30 rolled-up graphitic sheets. Raman spectra of the CNTs showed a dominant G band, indicating a well-ordered graphitic nanostructure. Being highly hydrophobic with a water contact angle of ∼145° and oleophilic, the CNT-coated SS mesh could be used in fluid separation and organic contaminant removal from water. Moreover, CNTs are recognized for their exceptional thermal conductivity and the CNT-coated mesh offers a supportive structure with directly connected CNTs for efficient heat transfer. Proof of concept has been achieved for the CNT-coated mesh’s potentials as a liquid filter and an thermal interface material (TIM). Specifically, the CNT-coated mesh demonstrated the capability of capturing water from a water-organic mixture with a 100 % efficiency while allowing organic liquids to pass through the filter. Furthermore, when used as a TIM, the CNT-coated mesh reduced the interfacial thermal impedance by >30 %.

Carbon nanotubes (CNTS)↗

Influence of heart failure on nucleolar organization and protein expression in human hearts

Highlights: Black-Right-Pointing-Pointer Heart failure alters nucleolar morphology and organization. Black-Right-Pointing-Pointer Nucleolin expression is significant increased in ischemic and dilated cardiomyopathy. Black-Right-Pointing-Pointer Ventricular function of heart failure patients was related with nucleolin levels. -- Abstract: We investigate for the first time the influence of heart failure (HF) on nucleolar organization and proteins in patients with ischemic (ICM) or dilated cardiomyopathy (DCM). A total of 71 human hearts from ICM (n = 38) and DCM (n = 27) patients, undergoing heart transplantation and control donors (n = 6), were analysed by western-blotting, RT-PCR and cell biology methods. When we compared protein levels according to HF etiology, nucleolin was increased in both ICM (117%, p < 0.05) and DCM (141%, p < 0.01). Moreover, mRNA expression were also upregulated in ICM (1.46-fold, p < 0.05) and DCM (1.70-fold, p < 0.05. Immunofluorescence studies showed that the highest intensity of nucleolin was into nucleolus (p < 0.0001), and it was increased in pathological hearts (p < 0.0001). Ultrastructure analysis by electron microscopy showed an increase in the nucleus and nucleolus size in ICM (17%, p < 0.05 and 131%, p < 0.001) and DCM (56%, p < 0.01 and 69%, p < 0.01). Nucleolar organization was influenced by HF irrespective of etiology, increasing fibrillar centers (p < 0.001), perinucleolar chromatin (p < 0.01) and dense fibrillar components (p < 0.01). Finally, left ventricular function parameters were related with nucleolin levels in ischemic hearts (p < 0.0001). The present study demonstrates that HF influences on morphology and organization of nucleolar components, revealing changes in the expression and in the levels of nucleolin protein.

60 APPLIED LIFE SCIENCES↗

Effect of nanostructured carbon support on copper electrocatalytic activity toward CO 2 electroreduction to hydrocarbon fuels

The effect of support on electrocatalytic activity of Cu nanoparticles (NPs) towards CO 2 electroreduction to hydrocarbon fuels (CH 4 and C 2 H 4 ) is investigated for three types of nanostructured carbons: single wall carbon nanotubes (SWNT), graphene (GP) and onion-like carbon (OLC). Cu/SWNT, Cu/GP and Cu/OLC composite catalysts are synthesized and characterized by X-Ray diffraction analysis, transmission electron microscopy and electrochemical surface area measurements. Electrocatalytic activities of the synthesized materials, as measured in an electrochemical cell connected to a gas chromatograph, are compared to that of Cu NPs supported on Vulcan carbon. All four catalysts demonstrate higher activity towards C 2 H 4 generation vs CH 4 , with production of the latter mostly suppressed on Cu NPs supported on nanostructured substrates. Onset potentials for C 2 H 4 vs CH 4 generation are shifted positively by 200 mV for Cu/SWNT, Cu/GP, and Cu/OLC catalysts. The Cu/OLC catalyst is found to be superior to the other two nanostructured catalysts in terms of stability, activity and selectivity towards C 2 H 4 generation. Its faradaic efficiency reached 60% at -1.8 V vs Ag/AgCl. The enhanced activity and stability of Cu/OLC catalyst can be attributed to the unique catalyst design, wherein a shell of OLC surrounds the Cu NPs such that the outer layer acts as a filter that protects the Cu surface from adsorption of undesirable species, enhances its electrocatalytic performance, and improves its viability in CO 2 electroreduction reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal structure of magnesium silicate hydrates (M-S-H): The relation with 2:1 Mg–Si phyllosilicates

Two magnesium silicate hydrates (M-S-H) with structural magnesium/silicon ratios of 0.57 ± 0.08 and 1.07 ± 0.13 were synthesized at room temperature, with one year of synthesis duration. Their structure was clarified by considering results from X-ray diffraction, TEM, {sup 29}Si MAS NMR spectroscopy, TGA, and EPMA. A modeling approach appropriate to defective minerals was used because usual XRD refinement techniques cannot be used in the case of turbostratic samples, where coherency between successive layers is lost. M-S-H with Mg/Si ratio of ~ 0.6 appears to be structurally close to nanocrystalline turbostratic 2:1 Mg–Si phyllosilicates. The increase of the Mg/Si ratio from 0.6 to 1.2 occurs by increasing the occurrence of defects in the silicate plan. The layer-to-layer distance evolves from 9.46 Å to 14 Å under air-dried and ethylene glycol conditions, respectively. Crystallites have a mean size of 1.5 nm in the ab plane, and 2.4 nm along c*.

36 MATERIALS SCIENCE↗

Degradation mechanism of blended cement pastes in sulfate-bearing environments under applied electric fields: Sulfate attack vs. decalcification

Applied electric fields, the reason behind stray currents, accelerate the ingress of sulfate into cementitious materials. To identify mitigation approaches, this study investigates the effects of slag and fly ash on sodium sulfate attacks of cement pastes under a constant electric current. The mineralogical alterations induced by the attacks were analyzed using X-ray diffractometry, thermogravimetric analysis, scanning electron microscopy, and thermodynamic modeling. The dissolution of aluminates in the slag and fly ash induced a monosulfate-rich area (>~20 mm from the cathode surface) to form next to the ettringite-rich area on the sample surface (<~20 mm). This effect reduced the availability of SO 4 2– in the pore solution, thereby hindering the penetration of sulfate. Meanwhile, the consumption of portlandite by the pozzolanic reaction lowered the decalcification resistance of the materials. This produced a wide area that endured the decomposition of portlandite and carbonate-AFm. Altogether, blending 30% fly ash did not improve the resistance of the material to either sulfate attacks or decalcification; blending 50% slag can effectively mitigate sulfate ingress, though decalcification may become a governing mechanism in the degradation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roles of Mn and Co in Ni-rich layered oxide cathodes synthesized utilizing a Taylor Vortex Reactor

It is reported that layered oxides, composed of nickel, manganese, and cobalt (NMC), are sought after as cathode materials which provide improved energy density, cycle life, and safety in commercial lithium ion batteries (LIBs). Increasing Ni contents higher than 80% can provide even higher practical discharge capacities >200 mAh/g and similar to ~4 V discharge potential vs Li/Li + , making them promising cathodes for next generation LIBs. However, rapid capacity fade during cycling and heat-related safety concerns are delaying their successful transition to industry. We report systematic performance optimization of LiNiO 2 , LiNi 0.9 Mn 0.1 O 2 , and LiNi 0.9 Co 0.1 O 2 high Ni layered oxide cathodes synthesized by utilizing a Taylor Vortex Reactor. Co-free LiNi 0.9 Mn 0.1 O 2 cathode showed 200 mAh/g highest discharge capacity at 0.1 C rate with 84% retention after 103 cycles at 0.3C rate while LiNi 0.9 Co 0.1 O 2 cathode showed higher initial but poor cycle life (225 mAh/g highest discharge capacity at 0.1C rate with only 56% capacity retention after 103 cycles at 0.3 C rate. Synchrotron based X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS) and focused ion beam (FIB) imaging of pristine and cycled cathodes after 103 cycles provided important information on degradation mechanism. The roles of Mn and Co on layered structure formation, charge balance, cationic mixing, and electrochemical performance were elucidated using the crystallographic information from XRD refinement and electronic state analysis from XAS providing valuable information to design future Ni-rich layered oxide cathodes.

25 ENERGY STORAGE↗

Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patterns and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.

58 GEOSCIENCES↗

Petrogenesis, alteration, and shock history of intermediate shergottite Northwest Africa 7042: Evidence for hydrous magmatism on Mars?

We report Northwest Africa (NWA) 7042 is an intermediate, permafic shergottite consisting of two generations of zoned olivine (early olivine Fo 41-76 , and late-stage olivine Fo 46-56 ), complexly zoned pyroxene (En 35-64 Fs 22-46 Wo 5-34 ), maskelynitized feldspar and shock melt (An 5-30 Ab 16-61 Or 1-47 ), and accessory merrillite, apatite, ilmenite, titanomagnetite, Fe-Cr-Ti spinels, pyrrhotite, and baddeleyite. The olivine grains have been pervasively altered resulting in orange-brown stained cores with dark-brown margins, surrounded by significantly less altered overgrowth rims. This textural relationship suggests that the alteration of the cores took place at magmatic temperatures prior to crystallization of the rims on Mars. While this type of olivine alteration is rare in shergottites, it is similar to deuterically altered olivine in basalts and gabbros on Earth, caused by residual water-rich magmatic fluids. Launch-generated shock veins in NWA 7042 crosscut and displace several of the altered olivine grains indicating that the alteration occurred before ejection of the meteorite from Mars. However, NWA 7042 has also been subjected to extensive terrestrial weathering, with terrestrial calcite/barite veins occurring throughout the sample. Transmission electron microscopy analysis of the olivine alteration also reveals an absence of high-temperature phases typically associated with hydrous deuteric alteration on Earth, complicating our interpretation. The potential presence of deuterically altered olivine in NWA 7042 has significant implications, as it is the third martian meteorite where deuteric alteration of olivine has been observed (the others being NWA 10416, ALH 77005). The different mantle sources for the parental melts of these three meteorites would suggest many, if not all martian mantle reservoirs have the potential to produce water-rich magmas.

58 GEOSCIENCES↗