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At least 775 records · Page 43

Phosphazene diamines

The synthesis of a specific phosphazene diamine was optimized, other phosphorus-containing diamines were prepared, and their effect upon certain characteristics of epoxy resins, prepared via reaction with MY 720, in particular, char yield at elevated temperatures was evaluated. The synthesis of the phosphazene diamine resulting from the interaction of methylenedianline with 4,4'-bis(diphenylphosphino)biphenyl was simplified into a one step process giving 77 percent yield of the pure product. Using this procedure, a related diamine containing bis(diphenylphosphino)methane was obtained in a 70 percent yield. Preparation of another class of phosphorus containing amines based upon p-aminophenyldiphenyl-phosphine was unsuccessful; the inability to produce p-aminophenylithlum was responsible for this failure. Seven epoxy resins employing Araldite MY 720, diaminodiphenylsulfone, and two of the phosphorus containing diamines were prepared, characterized, and their char yield capacity at elevated temperatures assessed. Based on these investigations, the resins containing phosphorus appear to exhibit significantly better char formation characteristics than materials hardened using conventional amines, without impairing the other properties measured.

Paciorek, K. L.↗

Effect of lubricant extreme-pressure additives on surface fatigue life of AISI 9310 spur gears

Surface fatigue tests were conducted with AISI 9310 spur gears using a formulated synthetic tetraester oil (conforming to MIL-L-23699 specifications) as the lubricant containing either sulfur or phosphorus as the EP additive. Four groups of gears were tested. One group of gears tested without an additive in the lubricant acted as the reference oil. In the other three groups either a 0.1 wt % sulfur or phosphorus additive was added to the tetraester oil to enhance gear surface fatigue life. Test conditions included a gear temperature of 334 K (160 F), a maximum Hertz stress of 1.71 GPa (248 000 psi), and a speed of 10,000 rpm. The gears tested with a 0.1 wt % phosphorus additive showed pitting fatigue life 2.6 times the life of gears tested with the reference tetraester based oil. Although fatigue lives of two groups of gears tested with the sulfur additive in the oil showed improvement over the control group gear life, the results, unlike those obtained with the phosphorus oil, were not considered to be statistically significant.

Scibbe, H. W.↗

Lake Champlain Water Resources: Using Earth Observations to Identify Spatial and Seasonal Trends of Harmful Algal Events in Lake Champlain

Lake Champlain provides clean drinking water for 35% of the surrounding watershed and offers recreational opportunities to millions of tourists. However, current levels of cyanobacteria and phosphorus created breeding grounds for harmful algal blooms (HABs). The excess of phosphorus runoff into Lake Champlain over the past decade encouraged toxic cyanobacterial formations, thereby increasing the severity of HABs towards local economy and ecology. In partnership with the Natural Resources Conservation Service (NRCS) Northeast Region, this project utilized Earth observations to identify risk factors associated with toxic algal blooms. The team detected historic algal bloom trends with Sentinel-2 Multispectral Instrument (MSI), Sentinel-3 Ocean and Land Color Instrument (OLCI), Landsat 8 Operational Land Imager (OLI) and Landsat 9 OLI-2. The team also used Sentinel-3 OLCI and the German Aerospace Center’s Earth Sensing Imagery Spectrometer (DESIS) to visualize algal bloom patterns and Landsat 8 OLI, Landsat 9 OLI-2, and Shuttle Radar Topography Mission (SRTM) to identify phosphorus sources within the watershed. The team’s analyses indicated an increase in cyanobacteria blooms during summer months from 2016-2022, with Missisquoi and St. Albans Bay exhibiting the greatest concentrations of toxic events. Furthermore, 16% of the watershed was identified as posing an immediate threat to the lake’s hydrology. The area of greatest concern was the Missisquoi Bay sub-watershed, with 229,044 acres of land prone to excessive phosphorus runoff. Providing this information to the NRCS Northeast Region enabled the organization to quantify risk factors associated with algal blooms and modify mitigation efforts to better target future bloom events.

Brianne Kendall↗

Quasi-two-dimensional metallic hydrogen in diphosphide at a high pressure

The structural, electronic, phonon, and other characteristics of the normal phases of phosphorus hydrides with stoichiometry PH{sub k} are analyzed. The properties of the initial substance, namely, diphosphine are calculated. In contrast to phosphorus hydrides with stoichiometry PH{sub 3}, a quasi-two-dimensional phosphorus-stabilized lattice of metallic hydrogen can be formed in this substance during hydrostatic compression at a high pressure. The formed structure with H–P–H elements is shown to be locally stable in phonon spectrum, i.e., to be metastable. The properties of diphosphine are compared with the properties of similar structures of sulfur hydrides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Simulating and evaluating best management practices for integrated landscape management scenarios in biofuel feedstock production: Evaluating Best Management Practices for Biofuel Feedstock Production

Sound crop and land management strategies can maintain land productivity and improve the environmental sustainability of agricultural crop and feedstock production. This study evaluates the improvement of water sustainability through an integrated landscaping management strategy, where landscaping design, land management operations, crop systems, and agricultural best management practices (BMPs) play equal roles. The strategy was applied to the watershed of the South Fork Iowa River in Iowa, with a focus on implementing riparian buffers and converting low productivity land to provide cellulosic biomass while benefiting soil and water quality. The Soil and Water Assessment Tool (SWAT) was employed to simulate the impact of integrated landscape design on nutrients, suspended sediments, and flow on the watershed and subbasin scales. First, the study evaluated the representation of buffer strip as a vegetative barrier and as a riparian buffer using trapping efficiency and area ratio methods in SWAT. For the riparian buffer, the area ratio method tends to be more conservative, especially in nitrate loadings, while the trapping efficiency method generates more optimistic results. The differences between the two methods increase with buffer width. The two methods may not be comparable for the field-scale vegetative barrier simulation because of limitations in model spatial resolution. Landscape scenarios were developed to quantify water quality under (1) current land use, (2) partial land conversion to switchgrass, and (3) riparian buffer implementation. Results show that when low productivity land (15.2% of total watershed land area) is converted to grow switchgrass, suspended sediment, total nitrogen, total phosphorus, and nitrate loadings are reduced by 69.3%, 55.5%, 46.1%, and 13.4%, respectively, in the watershed surface streams. The reduction was less extensive when riparian buffer strips (30 m or 50 m) were applied to the stream network at 1.4% of total land area in the watershed. At the subbasin level, the degree of nutrient and suspended sediment reduction varies extensively, ranging from a few percent up to 55%. Results indicate that effective landscape design on current agricultural land can potentially bring marked improvements in water quality and soil erosion control while producing food and fuel feedstock in the South Fork Iowa River watershed. The concept can be integrated with other watershed management programs to improve sustainability of land, water, and the ecosystem.

bioenergy production↗

Identification of the hydrate gel phases present in phosphate-modified calcium aluminate binders

The conversion of hexagonal calcium aluminate hydrates to cubic phases in hydrated calcium aluminate cements (CAC) can involve undesirable porosity changes and loss of strength. Modification of CAC by phosphate addition avoids conversion, by altering the nature of the reaction products, yielding a stable amorphous gel instead of the usual crystalline hydrate products. Here, details of the environments of aluminium and phosphorus in this gel were elucidated using solid-state NMR and complementary techniques. Aluminium is identified in both octahedral and tetrahedral coordination states, and phosphorus is present in hydrous environments with varying, but mostly low, degrees of crosslinking. A {sup 31}P/{sup 27}Al rotational echo adiabatic passage double resonance (REAPDOR) experiment showed the existence of aluminium–phosphorus interactions, confirming the formation of a hydrated calcium aluminophosphate gel as a key component of the binding phase. This resolves previous disagreements in the literature regarding the nature of the disordered products forming in this system.

36 MATERIALS SCIENCE↗

Mass balance implies Holocene development of a low-relief karst patterned landscape

We constructed mass balances of both calcium and phosphorus for two watersheds in Big Cypress National Preserve in southwest Florida (USA) to evaluate the time scales over which its striking landscape pattern developed. This low-relief carbonate landscape is dotted with evenly spaced, evenly sized, shallow surface depressions that annually fill with surface water and thus support wetland ecosystems (e.g. cypress domes) embedded in a pine-dominated upland matrix with exposed bedrock. Local and landscape scale feedbacks between hydrology, ecological dynamics and limestone dissolution are hypothesized to explain this karst dissolution patterning. This hypothesis requires the region to be wet enough to initiate surface water storage, which constrains landscape formation to interglacial periods. The time scale therefore would be relatively recent if creation of the observed pattern occurred in the current interglacial period (i.e. Holocene), and older time scales could reflect inherited patterns from previous inter-glacial periods, or from other processes of abiotic karstification. We then determined phosphorus stocks across four landscape compartments and estimated the limestone void space (i.e., wetland depression volume) across the landscape to represent cumulative calcium export. We calculated fluxes in (e.g., atmospheric deposition) and out (i.e., solute export) of the landscape to determine landscape denudation rates through mass balance. Comparing stocks and annual fluxes yielded independent estimates of landscape age from the calcium and phosphorus budgets. Our mass balance results indicate that the landscape began to develop in the early-mid Holocene (12,000–5000 ybp). Radiocarbon dating estimates implied similar rates of dissolution (~1 m per 3000–3500 years), and were in agreement with Holocene origin. This supports the hypothesis that ecohydrologic feedbacks between hydrology and vegetation occurring during the present interglacial period are sufficient to shape this landscape into the patterns we see today, and more broadly suggests the potential importance of biota in the development of macro-scale karst features.

54 ENVIRONMENTAL SCIENCES↗

A numerical simulation study of gallium-phosphide/silicon heterojunction passivated emitter and rear solar cells

The performance of passivated emitter and rear (PERC) solar cells made of p-type Si wafers is often limited by recombination in the phosphorus-doped emitter. To overcome this limitation, a realistic PERC solar cell is simulated, whereby the conventional phosphorus-doped emitter is replaced by a thin, crystalline gallium phosphide (GaP) layer. The resulting GaP/Si PERC cell is compared to Si PERC cells, which have (i) a standard POCl{sub 3} diffused emitter, (ii) a solid-state diffused emitter, or (iii) a high efficiency ion-implanted emitter. The maximum efficiencies for these realistic PERC cells are between 20.5% and 21.2% for the phosphorus-doped emitters (i)–(iii), and up to 21.6% for the GaP emitter. The major advantage of this GaP hetero-emitter is a significantly reduced recombination loss, resulting in a higher V{sub oc}. This is so because the high valence band offset between GaP and Si acts as a nearly ideal minority carrier blocker. This effect is comparable to amorphous Si. However, the GaP layer can be contacted with metal fingers like crystalline Si, so no conductive oxide is necessary. Compared to the conventional PERC structure, the GaP/Si PERC cell requires a lower Si base doping density, which reduces the impact of the boron-oxygen complexes. Despite the lower base doping, fewer rear local contacts are necessary. This is so because the GaP emitter shows reduced recombination, leading to a higher minority electron density in the base and, in turn, to a higher base conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Sensitivity of CoSi{sub 2} precipitation in silicon to extra-low dopant concentrations. II. First-principles calculations

The paper is the second part of the study on the influence of very low dopant content in silicon on CoSi{sub 2} precipitation during high-temperature cobalt ion implantation into transmission electron microscope samples. It deals with the computational justification of various assumptions used in Paper I when rationalizing the kinetics of cobalt clustering in ion-implanted intrinsic silicon (both undoped and containing low concentrations of phosphorus atoms). In particular, it is proven that divacancies are efficient nucleation centers for the new Co-Si phase. It is shown that the capture of vacancies and divacancies on phosphorus atoms increases their lifetime in silicon matrix, but practically does not affect the mechanism of their interaction with interstitial cobalt atoms. Finally, it is demonstrated that the mobility of phosphorus interstitials at temperatures of our experiment is orders of magnitude higher than might be expected from the published literature data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Upgraded metallurgical-grade silicon solar cells with efficiency above 20%

We present solar cells fabricated with n-type Czochralski–silicon wafers grown with strongly compensated 100% upgraded metallurgical-grade feedstock, with efficiencies above 20%. The cells have a passivated boron-diffused front surface, and a rear locally phosphorus-diffused structure fabricated using an etch-back process. The local heavy phosphorus diffusion on the rear helps to maintain a high bulk lifetime in the substrates via phosphorus gettering, whilst also reducing recombination under the rear-side metal contacts. The independently measured results yield a peak efficiency of 20.9% for the best upgraded metallurgical-grade silicon cell and 21.9% for a control device made with electronic-grade float-zone silicon. The presence of boron-oxygen related defects in the cells is also investigated, and we confirm that these defects can be partially deactivated permanently by annealing under illumination.

36 MATERIALS SCIENCE↗

Anoxia begets anoxia: A positive feedback to the deoxygenation of temperate lakes

Abstract Declining oxygen concentrations in the deep waters of lakes worldwide pose a pressing environmental and societal challenge. Existing theory suggests that low deep‐water dissolved oxygen (DO) concentrations could trigger a positive feedback through which anoxia (i.e., very low DO) during a given summer begets increasingly severe occurrences of anoxia in following summers. Specifically, anoxic conditions can promote nutrient release from sediments, thereby stimulating phytoplankton growth, and subsequent phytoplankton decomposition can fuel heterotrophic respiration, resulting in increased spatial extent and duration of anoxia. However, while the individual relationships in this feedback are well established, to our knowledge, there has not been a systematic analysis within or across lakes that simultaneously demonstrates all of the mechanisms necessary to produce a positive feedback that reinforces anoxia. Here, we compiled data from 656 widespread temperate lakes and reservoirs to analyze the proposed anoxia begets anoxia feedback. Lakes in the dataset span a broad range of surface area (1–126,909 ha), maximum depth (6–370 m), and morphometry, with a median time‐series duration of 30 years at each lake. Using linear mixed models, we found support for each of the positive feedback relationships between anoxia, phosphorus concentrations, chlorophyll a concentrations, and oxygen demand across the 656‐lake dataset. Likewise, we found further support for these relationships by analyzing time‐series data from individual lakes. Our results indicate that the strength of these feedback relationships may vary with lake‐specific characteristics: For example, we found that surface phosphorus concentrations were more positively associated with chlorophyll a in high‐phosphorus lakes, and oxygen demand had a stronger influence on the extent of anoxia in deep lakes. Taken together, these results support the existence of a positive feedback that could magnify the effects of climate change and other anthropogenic pressures driving the development of anoxia in lakes around the world.

54 ENVIRONMENTAL SCIENCES↗

Injection-induced terahertz electroluminescence from silicon p–n structures

Injection-induced terahertz electroluminescence from silicon p{sup +}–n structures is observed at helium temperatures. Structures fabricated by the diffusion of boron into a phosphorus-doped n-Si substrate are studied. Relatively narrow luminescence lines are observed in the luminescence spectra against a broad smooth background. The spectral position of a number of emission lines corresponds to optical transitions between excited donor states and the ground state of phosphorus donors. The intracenter optical transitions of electrons at phosphorus donors are excited as a result of recombination processes occurring in the n-type region of the structure under the injection of nonequilibrium holes. A number of other lines in the terahertz emission spectra are associated with intracenter transitions at acceptor centers, which are also excited as a result of injection. The structureless background in the electroluminescence spectra may be due to terahertz emission upon the intraband energy relaxation of “hot” carriers having an effective temperature exceeding the lattice temperature. These “hot” carriers appear in the structure under injection conditions.

36 MATERIALS SCIENCE↗

Depth-resolved sagebrush root metabolomics, rhizosphere microbial communities, and geochemistry at the East River Watershed

This data set consists of results from soil nutrient profile, untargeted metabolomics, mass spec imaging, and amplicon sequencing. Data for soil nutrient profile includes common cations (Ca, Mg, Na, and K etc.) extracted from 3 digesting steps – ammonia acetate (for exchangeable cations), nitric acid (for acid dissolved fraction), and hydrofluoric acid/perchloric acid (HF/HClO4) for whole soil digestion. It also includes concentration of organic carbon, inorganic nitrogen (ammonia and nitrate) and phosphorus (Bray-1 P and nitric acid extract), and total nitrogen and phosphorus. Data for untargeted metabolomics includes metabolomic profile for root exudate/tissues and soil extracts from depths at surface soil to saprolite, that were measured using gas chromatography – mass spectrometry (GC-MS), and liquid chromatography – tandem mass spectrometry (LC-MS/MS). Data for mass spec imaging includes spatial distribution of metabolites that were detected and annotated with Fourier transformation ion cyclotron resonance mass spectrometer (FTICR-MS). Data for amplicon sequencing includes the base paired 16S and ITS ribosomal RNA sequences from Miseq Illumina sequencing. All samples were collected from 2 sampling campaign October 2022 and June 2023. Collectively, these datasets enable a mechanistic evaluation of how nutrient acquisition, especially nitrogen and phosphorus, differs between shallow roots operating in soil and deep roots functioning within the fractured bedrock zone. All files are provided as comma-separated values (CSV) fies (.csv) and (GZIP) file (.gz). The compressed .gz FASTQ files can be read directly in R using the dada2 package as part of the amplicon sequence analysis workflow. This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231. This research was performed on a project award 60563 (https://dx.doi.org/10.46936/expl.proj.2022.60563/60008727) from the Environmental Molecular Sciences Laboratory, a DOE Office of Science User Facility sponsored by the Biological and Environmental Research program under Contract No. DE-AC05-76RL01830.

EARTH SCIENCE > AGRICULTURE > SOILS > CARBON↗

Dated soil C–N–P profiles, water quality, and chamber fluxes across Ohio and Michigan wetlands (2024–2025)

This dataset includes dated soil core chemistry (bulk density, phosphorus, nitrogen and carbon concentrations), water quality, and chamber flux measurements collected from wetlands in the Midwest United States—12 sites in Ohio, one site in Indiana, one site in Michigan—collected in the spring or summer of 2024 or 2025, all in (.csv) format. These data were generated to examine how wetland restoration, management activities, and time since restoration affect biogeochemical processes, carbon sequestration, nutrient accumulation, water quality, and greenhouse gas emissions. Specifically, these data aim to investigate how restored wetlands differ from natural wetlands in terms of carbon, nitrogen, phosphorus dynamics, as well as carbon dioxide and methane fluxes. Also included are surface and porewater quality parameters and chamber flux measurements across these different wetlands. Sampling was conducted at various sites representing a range of restoration stages, from about 4 years post-restoration up to 105 years post-restoration, and also includes a natural wetland used as a reference in Michigan. These data can be used to determine carbon sequestration rates, nutrient cycling, and to enhance our understanding of biogeochemical responses to wetland restoration in temperate ecosystems. This data package contains (1) a csv file (Water_Quality.csv) containing water quality data (dissolved organic carbon, total dissolved nitrogen, and temperature) organized by location; (2) a csv file (Soil_C_N_P_Seq.csv) containing carbon, nitrogen, and phosphorus concentrations at each soil level and time of each soil level, as well as their sequestration rates; (3) a csv file (CH4_CO2_Flux.csv) including methane and carbon dioxide fluxes that were measured with a chamber; (4) a file-level metadata (FLMD.csv) file that lists each file contained in the dataset with associated metadata; (5) a data dictionary (DD.csv) file that contains terms/column headers used throughout the files along with a definition, units, and data type; and (6) a locations metadata file (Location_metadata.csv).

Earth Science > Atmosphere > Atmospheric Chemistry↗

Godzilla mineral dust and La Soufrière volcanic ash fallout immediately stimulate marine microbial phosphate uptake

During the “Godzilla” dust storm of June 2020, unusually high fluxes of mineral dust traveled across the Atlantic from the Sahara Desert, reaching the Caribbean Basin, Gulf Coast, and southeastern United States. Additionally, an eruption of the La Soufrière volcano on St. Vincent in April 2021 generated substantial ashfall in the southeastern Caribbean. While many studies have analyzed mineral dust’s ability to relieve nutrient limitation of phosphorus (P) in the P-stressed North Atlantic, less is known about the impact of extreme events and other natural aerosols on fluxes of P into seawater and from seawater into marine microbial cells. We quantified P and iron (Fe) content in mineral dust from the Godzilla dust storm and volcanic ash from the La Soufrière eruption collected at Ragged Point, Barbados. We also performed seawater incubations to assess the marine microbial response to aerosol deposition. Using environmentally-relevant concentrations of atmospheric particles for within the ocean’s mixed layer allowed us to draw realistic conclusions about how these deposition events impacted P cycling in situ. Volcanic ash has lower P content than mineral dust, and P in volcanic ash is far less soluble (~1%) than assumed in current atmospheric deposition models. Adding mineral dust and the volcanic ash leachate in concentrations representing different deposition scenarios increased soluble reactive phosphorus (SRP) concentrations in coastal seawater by ~7-32 nM. Phosphate uptake rate was stimulated in coastal seawater after either mineral dust or volcanic ash deposition at aerosol concentrations relevant to the Godzilla dust event, with ash eliciting the fastest uptake rate. Furthermore, high concentrations of both the mineral dust and volcanic ash led to slightly elevated alkaline phosphatase activity (APA) compared to the relevant controls, indicating higher potential for use of dissolved organic phosphorus (DOP) as a P source. Quantifying these aerosols’ impacts on P cycling is a significant step towards achieving a better understanding of their potential roles in relieving nutrient limitation and fueling the biological carbon pump.

54 ENVIRONMENTAL SCIENCES↗

Phase diagram of the system Ti-P

Physicochemical determination of interaction between titanium and phosphorus in mixture containing up to 45 atomic percent phosphorus - phase diagram of titanium phosphorus system

PHASE DIAGRAM↗

TALSPEAK EXTRACTION SYSTEM UNDER VARIABLE LOADING CONDITIONS - PART 2: SPECIATION STUDIES

The reported investigation was performed to gain structural information on the organic phase complex species in the Trivalent Actinide-Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Komplexes (TALSPEAK) process under various loading conditions. In conjunction with the distribution studies of the TALSPEAK system constituents, presented in Part 1 of this investigation, loaded bis(2-ethylhexyl) phosphoric acid (HDEHP)/isooctane was evaluated using various spectroscopic techniques including NMR, FTIR and visible absorbance spectroscopy. Liquid-liquid distribution and vapor pressure osmometry (VPO) aggregation results correlate with observed changes in the spectroscopic signatures as a function of organic phase loading and water partitioning. Explicit FTIR spectral interpretation of the HDEHP spectra is complex due to overlapping phosphorus absorbance bands, and in this work a combination of the spectroscopic techniques was utilized to elucidate the phosphorus-lanthanide complex structure and changes in speciation due to aggregation. The results from this research will benefit an overall improved prediction of the TALSPEAK process performance under flow conditions.

99 GENERAL AND MISCELLANEOUS↗

Topotactic Synthesis of Phosphabenzene-Functionalized Porous Organic Polymers: Efficient Ligands in CO 2 Conversion

Progress toward the preparation of porous organic polymers (POPs) with task-specific functionalities has been exceedingly slow—especially where polymers containing low-oxidation phosphorus in the structure are concerned. In this work, a two-step topotactic pathway for the preparation of phosphabenzene-based POPs (Phos-POPs) under metal-free conditions is reported, without the use of unstable phosphorus-based monomers. The synthetic route allows additional functionalities to be introduced into the porous polymer framework with ease. As an example, partially fluorinated Phos-POPs (F-Phos-POPs) were obtained with a surface area of up to 591 m 2 g –1 . After coordination with Ru species, a Ru/F-Phos-POPs catalyst exhibited high catalytic efficiency in the formylation of amines (turnover frequency up to 204 h –1 ) using a CO 2 /H 2 mixture, in comparison with the non-fluorinated analogue (43 h –1 ) and a Au/TiO 2 heterogeneous catalysts reported previously (<44 h –1 ). This work describes a practical method for synthesis of porous organic phosphorus-based polymers with applications in transition-metal-based heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗