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1. Florida mangrove saltmarsh reference surface soils

   https://doi.org/10.6073/pasta/0e08cbe07c84488cb7b9dd16669946d0  

   Lewis, David Bruce ( January 2021 )

   Abstract

   Site description. This data package consists of data obtained from sampling surface soil (the 0-7.6 cm depth profile) in black mangrove (Avicennia germinans) dominated forest and black needlerush (Juncus roemerianus) saltmarsh along the Gulf of Mexico coastline in peninsular west-central Florida, USA. This location has a subtropical climate with mean daily temperatures ranging from 15.4 °C in January to 27.8 °C in August, and annual precipitation of 1336 mm. Precipitation falls as rain primarily between June and September. Tides are semi-diurnal, with 0.57 m median amplitudes during the year preceding sampling (U.S. NOAA National Ocean Service, Clearwater Beach, Florida, station 8726724). Sea-level rise is 4.0 ± 0.6 mm per year (1973-2020 trend, mean ± 95 % confidence interval, NOAA NOS Clearwater Beach station). The A. germinans mangrove zone is either adjacent to water or fringed on the seaward side by a narrow band of red mangrove (Rhizophora mangle). A near-monoculture of J. roemerianus is often adjacent to and immediately landward of the A. germinans zone. The transition from the mangrove to the J. roemerianus zone is variable in our study area. An abrupt edge between closed-canopy mangrove and J. roemerianus monoculture may extend for up to several hundred meters in some locations, while other stretches of ecotone present a gradual transition where smaller, widely spaced trees are interspersed into the herbaceous marsh. Juncus roemerianus then extends landward to a high marsh patchwork of succulent halophytes (including Salicornia bigellovi, Sesuvium sp., and Batis maritima), scattered dwarf mangrove, and salt pans, followed in turn by upland vegetation that includes Pinus sp. and Serenoa repens. Field design and sample collection. We established three study sites spaced at approximately 5 km intervals along the western coastline of the central Florida peninsula. The sites consisted of the Salt Springs (28.3298°, -82.7274°), Energy Marine Center (28.2903°, -82.7278°), and Green Key (28.2530°, -82.7496°) sites on the Gulf of Mexico coastline in Pasco County, Florida, USA. At each site, we established three plot pairs, each consisting of one saltmarsh plot and one mangrove plot. Plots were 50 m^2 in size. Plots pairs within a site were separated by 230-1070 m, and the mangrove and saltmarsh plots composing a pair were 70-170 m apart. All plot pairs consisted of directly adjacent patches of mangrove forest and J. roemerianus saltmarsh, with the mangrove forests exhibiting a closed canopy and a tree architecture (height 4-6 m, crown width 1.5-3 m). Mangrove plots were located at approximately the midpoint between the seaward edge (water-mangrove interface) and landward edge (mangrove-marsh interface) of the mangrove zone. Saltmarsh plots were located 20-25 m away from any mangrove trees and into the J. roemerianus zone (i.e., landward from the mangrove-marsh interface). Plot pairs were coarsely similar in geomorphic setting, as all were located on the Gulf of Mexico coastline, rather than within major sheltering formations like Tampa Bay, and all plot pairs fit the tide-dominated domain of the Woodroffe classification (Woodroffe, 2002, "Coasts: Form, Process and Evolution", Cambridge University Press), given their conspicuous semi-diurnal tides. There was nevertheless some geomorphic variation, as some plot pairs were directly open to the Gulf of Mexico while others sat behind keys and spits or along small tidal creeks. Our use of a plot-pair approach is intended to control for this geomorphic variation. Plot center elevations (cm above mean sea level, NAVD 88) were estimated by overlaying the plot locations determined with a global positioning system (Garmin GPS 60, Olathe, KS, USA) on a LiDAR-derived bare-earth digital elevation model (Dewberry, Inc., 2019). The digital elevation model had a vertical accuracy of ± 10 cm (95 % CI) and a horizontal accuracy of ± 116 cm (95 % CI). Soil samples were collected via coring at low tide in June 2011. From each plot, we collected a composite soil sample consisting of three discrete 5.1 cm diameter soil cores taken at equidistant points to 7.6 cm depth. Cores were taken by tapping a sleeve into the soil until its top was flush with the soil surface, sliding a hand under the core, and lifting it up. Cores were then capped and transferred on ice to our laboratory at the University of South Florida (Tampa, Florida, USA), where they were combined in plastic zipper bags, and homogenized by hand into plot-level composite samples on the day they were collected. A damp soil subsample was immediately taken from each composite sample to initiate 1 y incubations for determination of active C and N (see below). The remainder of each composite sample was then placed in a drying oven (60 °C) for 1 week with frequent mixing of the soil to prevent aggregation and liberate water. Organic wetland soils are sometimes dried at 70 °C, however high drying temperatures can volatilize non-water liquids and oxidize and decompose organic matter, so 50 °C is also a common drying temperature for organic soils (Gardner 1986, "Methods of Soil Analysis: Part 1", Soil Science Society of America); we accordingly chose 60 °C as a compromise between sufficient water removal and avoidance of non-water mass loss. Bulk density was determined as soil dry mass per core volume (adding back the dry mass equivalent of the damp subsample removed prior to drying). Dried subsamples were obtained for determination of soil organic matter (SOM), mineral texture composition, and extractable and total carbon (C) and nitrogen (N) within the following week. Sample analyses. A dried subsample was apportioned from each composite sample to determine SOM as mass loss on ignition at 550 °C for 4 h. After organic matter was removed from soil via ignition, mineral particle size composition was determined using a combination of wet sieving and density separation in 49 mM (3 %) sodium hexametaphosphate ((NaPO_3)_6) following procedures in Kettler et al. (2001, Soil Science Society of America Journal 65, 849-852). The percentage of dry soil mass composed of silt and clay particles (hereafter, fines) was calculated as the mass lost from dispersed mineral soil after sieving (0.053 mm mesh sieve). Fines could have been slightly underestimated if any clay particles were burned off during the preceding ignition of soil. An additional subsample was taken from each composite sample to determine extractable N and organic C concentrations via 0.5 M potassium sulfate (K_2SO_4) extractions. We combined soil and extractant (ratio of 1 g dry soil:5 mL extractant) in plastic bottles, reciprocally shook the slurry for 1 h at 120 rpm, and then gravity filtered it through Fisher G6 (1.6 μm pore size) glass fiber filters, followed by colorimetric detection of nitrite (NO_2^-) + nitrate (NO_3^-) and ammonium (NH_4^+) in the filtrate (Hood Nowotny et al., 2010,Soil Science Society of America Journal 74, 1018-1027) using a microplate spectrophotometer (Biotek Epoch, Winooski, VT, USA). Filtrate was also analyzed for dissolved organic C (referred to hereafter as extractable organic C) and total dissolved N via combustion and oxidation followed by detection of the evolved CO_2 and N oxide gases on a Formacs HT TOC/TN analyzer (Skalar, Breda, The Netherlands). Extractable organic N was then computed as total dissolved N in filtrate minus extractable mineral N (itself the sum of extractable NH_4-N and NO_2-N + NO_3-N). We determined soil total C and N from dried, milled subsamples subjected to elemental analysis (ECS 4010, Costech, Inc., Valencia, CA, USA) at the University of South Florida Stable Isotope Laboratory. Median concentration of inorganic C in unvegetated surface soil at our sites is 0.5 % of soil mass (Anderson, 2019, Univ. of South Florida M.S. thesis via methods in Wang et al., 2011, Environmental Monitoring and Assessment 174, 241-257). Inorganic C concentrations are likely even lower in our samples from under vegetation, where organic matter would dilute the contribution of inorganic C to soil mass. Nevertheless, the presence of a small inorganic C pool in our soils may be counted in the total C values we report. Extractable organic C is necessarily of organic C origin given the method (sparging with HCl) used in detection. Active C and N represent the fractions of organic C and N that are mineralizable by soil microorganisms under aerobic conditions in long-term soil incubations. To quantify active C and N, 60 g of field-moist soil were apportioned from each composite sample, placed in a filtration apparatus, and incubated in the dark at 25 °C and field capacity moisture for 365 d (as in Lewis et al., 2014, Ecosphere 5, art59). Moisture levels were maintained by frequently weighing incubated soil and wetting them up to target mass. Daily CO_2 flux was quantified on 29 occasions at 0.5-3 week intervals during the incubation period (with shorter intervals earlier in the incubation), and these per day flux rates were integrated over the 365 d period to compute an estimate of active C. Observations of per day flux were made by sealing samples overnight in airtight chambers fitted with septa and quantifying headspace CO_2 accumulation by injecting headspace samples (obtained through the septa via needle and syringe) into an infrared gas analyzer (PP Systems EGM 4, Amesbury, MA, USA). To estimate active N, each incubated sample was leached with a C and N free, 35 psu solution containing micronutrients (Nadelhoffer, 1990, Soil Science Society of America Journal 54, 411-415) on 19 occasions at increasing 1-6 week intervals during the 365 d incubation, and then extracted in 0.5 M K_2SO_4 at the end of the incubation in order to remove any residual mineral N. Active N was then quantified as the total mass of mineral N leached and extracted. Mineral N in leached and extracted solutions was detected as NH_4-N and NO_2-N + NO_3-N via colorimetry as above. This incubation technique precludes new C and N inputs and persistently leaches mineral N, forcing microorganisms to meet demand by mineralizing existing pools, and thereby directly assays the potential activity of soil organic C and N pools present at the time of soil sampling. Because this analysis commences with disrupting soil physical structure, it is biased toward higher estimates of active fractions. Calculations. Non-mobile C and N fractions were computed as total C and N concentrations minus the extractable and active fractions of each element. This data package reports surface-soil constituents (moisture, fines, SOM, and C and N pools and fractions) in both gravimetric units (mass constituent / mass soil) and areal units (mass constituent / soil surface area integrated through 7.6 cm soil depth, the depth of sampling). Areal concentrations were computed as X × D × 7.6, where X is the gravimetric concentration of a soil constituent, D is soil bulk density (g dry soil / cm^3), and 7.6 is the sampling depth in cm.
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2. In situ identification of surface sites in Cu–Pt bimetallic catalysts: Gas-induced metal segregation

   https://doi.org/10.1063/5.0130431  

   Han, Tongxin ; Li, Yuanyuan ; Cao, Yueqiang ; Lee, Ilkeun ; Zhou, Xinggui ; Frenkel, Anatoly I. ; Zaera, Francisco ( December 2022 , The Journal of Chemical Physics)

   The effect of gases on the surface composition of Cu–Pt bimetallic catalysts has been tested by in situ infrared (IR) and x-ray absorption spectroscopies. Diffusion of Pt atoms within the Cu–Pt nanoparticles was observed both in vacuum and under gaseous atmospheres. Vacuum IR spectra of CO adsorbed on CuPt x /SBA-15 catalysts (x = 0–∞) at 125 K showed no bonding on Pt regardless of Pt content, but reversible Pt segregation to the surface was seen with the high-Pt-content (x ≥ 0.2) samples upon heating to 225 K. In situ IR spectra in CO atmospheres also highlighted the reversible segregation of Pt to the surface and its diffusion back into the bulk when cycling the temperature from 295 to 495 K and back, most evidently for diluted single-atom alloy catalysts (x ≤ 0.01). Similar behavior was possibly observed under H 2 using small amounts of CO as a probe molecule. In situ x-ray absorption near-edge structure data obtained for CuPt 0.2 /SBA-15 under both CO and He pointed to the metallic nature of the Pt atoms irrespective of gas or temperature, but analysis of the extended x-ray absorption fine structure identified a change in coordination environment around the Pt atoms, from a (Pt–Cu):(Pt–Pt)more »coordination number ratio of ∼6:6 at or below 445 K to 8:4 at 495 K. The main conclusion is that Cu–Pt bimetallic catalysts are dynamic, with the composition of their surfaces being dependent on temperature in gaseous environments.« less
3. Magnetization–structure–composition phase diagram mapping in Co-Fe-Ni alloys using diffusion multiples and scanning Hall probe microscopy

   https://doi.org/10.1038/s41598-022-05121-1  

   Shamsutdinov, Girfan ; Zhao, Peng ; Bhattiprolu, Sreenivas ; Zhao, Ji-Cheng ; Nadgorny, Boris ( February 2022 , Scientific Reports)

   Transition metal alloys are essential for magnetic recording, memory, and new materials-by-design applications. Saturation magnetization in these alloys have previously been measured by conventional techniques, for a limited number of samples with discrete compositions, a laborious and time-consuming effort. Here, we propose a method to construct complete saturation magnetization diagrams for Co–Fe–Ni alloys using scanning Hall probe microscopy (SHPM). A composition gradient was created by the diffusion multiple technique, generating a full combinatorial materials library with an identical thermal history. The composition and crystallographic phases of the alloys were identified by integrated energy dispersive X-ray spectroscopy and electron backscatter diffraction. “Pixel-by-pixel” perpendicular components of the magnetic field were converted into maps of saturation magnetization using the inversion matrix technique. The saturation magnetization dependence for the binary alloys was consistent with the Slater-Pauling behavior. By using a significantly denser data point distribution than previously available, the maximum of the Slater-Pauling curve for the Co–Fe alloys was identified at ~ 32 at% of Co. By mapping the entire ternary diagram of Co–Fe–Ni alloys recorded in a single experiment, we have demonstrated that SHPM—in concert with the combinatorial approach—is a powerful high-throughput characterization tool, providing an effective metrology platform to advance the search formore »new magnetic materials.

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4. Bandgap Engineering in 2D Lateral Heterostructures of Transition Metal Dichalcogenides via Controlled Alloying

   https://doi.org/10.1002/smll.202106600  

   Nugera, Florence A. ; Sahoo, Prasana K. ; Xin, Yan ; Ambardar, Sharad ; Voronine, Dmitri V. ; Kim, Un Jeong ; Han, Yoojoong ; Son, Hyungbin ; Gutiérrez, Humberto R. ( January 2022 , Small)

   2D heterostructures made of transition metal dichalcogenides (TMD) have emerged as potential building blocks for new‐generation 2D electronics due to their interesting physical properties at the interfaces. The bandgap, work function, and optical constants are composition dependent, and the spectrum of applications can be expanded by producing alloy‐based heterostructures. Herein, the successful synthesis of monolayer and bilayer lateral heterostructures, based on ternary alloys of MoS_2(1−x)Se_2x–WS_2(1−x)Se_2x, is reported by modifying the ratio of the source precursors; the bandgaps of both materials in the heterostructure are continuously tuned in the entire range of chalcogen compositions. Raman and photoluminescence (PL) spatial maps show good intradomain composition homogeneity. Kelvin probe measurements in different heterostructures reveal composition‐dependent band alignments, which can further be affected by unintentional electronic doping during the growth. The fabrication of sequential multijunction lateral heterostructures with three layers of thickness, composed of quaternary and ternary alloys, is also reported. These results greatly expand the available tools kit for optoelectronic applications in the 2D realm.
5. Synthesis of colloidal MnAs _x Sb _1−x nanoparticles: compositional inhomogeneity and magnetic consequences

   https://doi.org/10.1039/D1TC02479E  

   Hettiarachchi, Malsha A. ; Su’a, Tepora ; Abdelhamid, Ehab ; Pokhrel, Shiva ; Nadgorny, Boris ; Brock, Stephanie L. ( October 2021 , Journal of Materials Chemistry C)

   The ternary manganese pnictide phases, MnAs 1− x Sb x , are of interest for magnetic refrigeration and waste heat recovery due to their magnetocaloric properties, maximized at the Curie temperature ( T C ), which varies from 580–240 K, depending on composition. Nanoparticles potentially enable application in microelectronics (cooling) or graded composites that can operate over a wide temperature range, but manganese pnictides are synthetically challenging to realize as discrete nanoparticles and their fundamental magnetic properties have not been extensively studied. Accordingly, colloidal synthesis methods were employed to target discrete MnAs x Sb 1− x nanoparticles ( x = 0.1–0.9) by arrested precipitation reactions of Mn 2 (CO) 10 with (C 6 H 5 ) 3 AsO and (C 6 H 5 ) 3 Sb in coordinating solvents. The MnAs x Sb 1− x particles are spherical in morphology with average diameters 10–13 nm (standard deviations <20% based on transmission electron microscopy analysis). X-Ray fluorescence spectroscopy measurements on ensembles showed that all phases had an excess of Sb relative to the targeted composition, whereas energy dispersive spectroscopic mapping data of single particles revealed that the nanoparticles are inhomogeneous, adopting a core–shell structure, with the amorphous shell rich in Mnmore »and O (and sometimes Sb) while the crystalline core is rich in Mn, As, and Sb. Magnetization measurements of the nanoparticle ensemble demonstrated the presence of both ferromagnetic and paramagnetic phases. By combining the magnetization measurements with precision chemical mapping and simple modeling, we were able to unambiguously attribute ferromagnetism to the MnAs x Sb 1− x crystalline core, whereas paramagnetism was attributed to the amorphous shell. Magnetization measurements at variable temperatures were used to determine the superparamagnetic transition of the nanoparticles, although for some compositions and particle sizes the blocking temperature exceeded room temperature. Preliminary magnetic studies also revealed a conventional dependence between core size and coercivity, in spite of variable compositions of the nanoparticles, an unexpected result.« less