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At least 343 records · Page 19

Trade-Offs in Phosphorus Acquisition Strategies of Five Common Tree Species in a Tropical Forest of Puerto Rico

Tree species that are successful in tropical lowlands have different acquisition strategies to overcome soil phosphorus (P) limitations. Some of these strategies belowground include adjustments in fine-root traits, such as morphology, architecture, association with arbuscular mycorrhizal fungi, and phosphatase activity. Trade-offs among P-acquisition strategies are expected because of their respective carbon cost. However, empirical evidence remains scarce which hinders our understanding of soil P-acquisition processes in tropical forests. Here, we measured seven fine-root functional traits related to P acquisition of five common tree species in three sites of the Luquillo Experimental Forest in Puerto Rico. We then described species-specific P-acquisition strategies and explored the changes in fine-root trait expression from 6 months before to 6 months after two consecutive hurricanes, Irma and María, passed over the island. We found that variations in root trait expression were driven mainly by the large interspecific differences across the three selected sites. In addition, we revealed a trade-off between highly colonized fine roots with high phosphatase activity and fine roots that have a high degree of branching. Furthermore, the former strategy was adopted by pioneer species ( Spathodea campanulata and Cecropia schreberiana ), whereas the latter was adopted by non-pioneer species (mostly Dacryodes excelsa and Prestoea montana ). Additionally, we found that root trait expression did not change comparing 6 months before and after the hurricanes, with the exception of root phosphatase activity. Altogether, our results suggest a combination of structural and physiological root traits for soil P acquisition in P-poor tropical soils by common tropical tree species, and show stability on most of the root trait expression after hurricane disturbances.

59 BASIC BIOLOGICAL SCIENCES↗

Phosphorus Cycling in the Red Tide Incubator Region of Monterey Bay in Response to Upwelling

This study explores the cycling of phosphorus (P) in the euphotic zone following upwelling in northeastern Monterey Bay (the Red Tide Incubator region) of coastal California, with particular emphasis on how bacteria and phytoplankton that form harmful algal blooms mediate and respond to changes in P availability. In situ measurements of nutrient concentrations, phytoplankton community composition, and cell-specific alkaline phosphatase (AP) activity (determined via enzyme-labeled fluorescence assay) were measured during three cruises. Upwelling led to a 10-fold increase in dissolved inorganic (DIP) in surface waters, reaching ~0.5μmol L -1 . This DIP was drawn down rapidly as upwelling relaxed over a period of 1 week. Ratios of nitrate to DIP drawdown (~5:1, calculated as the change in nitrate divided by the change in DIP) were lower than the Redfield ratio of 16:1, suggesting that luxury P uptake was occurring as phytoplankton bloomed. Dissolved organic (DOP) remained relatively constant (~0.3μmol L -1 ) before and immediately following upwelling, but doubled as upwelling relaxed, likely due to phytoplankton excretion and release during grazing. This transition from a relatively high DIP:DOP ratio to lower DIP:DOP ratio was accompanied by a decline in the abundance of diatoms, which had low AP activity, toward localized, spatially heterogeneous blooms of dinoflagellates in the genera Prorocentrum, Ceratium, Dinophysis, Alexandrium, and Scrippsiella that showed high AP activity regardless of ambient DIP levels. A nutrient addition incubation experiment showed that phytoplankton growth was primarily limited by nitrate, followed by DIP and DOP, suggesting that P regulates phytoplankton physiology and competition, but is not a limiting nutrient in this region. AP activity was observed in bacteria associated with lysed cell debris and aggregates of particulate organic material, where it may serve to facilitate P regeneration, as well as affixed to the surfaces of intact phytoplankton cells, possibly indicative of close, beneficial phytoplankton–bacteria interactions.

59 BASIC BIOLOGICAL SCIENCES↗

Microbial Phosphorus Mobilization Strategies Across a Natural Nutrient Limitation Gradient and Evidence for Linkage With Iron Solubilization Traits

Microorganisms have evolved several mechanisms to mobilize and mineralize occluded and insoluble phosphorus (P), thereby promoting plant growth in terrestrial ecosystems. However, the linkages between microbial P-solubilization traits and the preponderance of insoluble P in natural ecosystems are not well known. We tested the P solubilization traits of hundreds of culturable bacteria representative of the rhizosphere from a natural gradient where P concentration and bioavailability decline as soil becomes progressively more weathered. Aluminum, iron phosphate and organic P (phytate) were expected to dominate in more weathered soils. A defined cultivation medium with these chemical forms of P was used for isolation. A combination of soil chemical, spectroscopic analyses and 16S rRNA gene sequencing were used to understand the in situ ability for solubilization of these predominant forms of P. Locations with more occluded and organic P harbored the greatest abundance of P-mobilizing microorganisms, especially Burkholderiaceae ( Caballeronia and Paraburkholderia spp.). Nearly all bacteria utilized aluminum phosphate, however fewer could subsist on iron phosphate (FePO 4 ) or phytate. Microorganisms isolated from phytic acid were also most effective at solubilizing FePO 4 , suggesting that phytate solubilization may be linked to the ability to solubilize Fe. Significantly, we observed Fe to be co-located with P in organic patches in soil. Siderophore addition in lab experiments reinstated phytase mediated P-solubilization from Fe-phytate complexes. Taken together, these results indicate that metal-organic-P complex formation may limit enzymatic P solubilization from phytate in soil. Additionally, the linked traits of phytase and siderophore production were mostly restricted to specific clades within the Burkholderiaceae . We propose that Fe complexation of organic P (e.g., phytate) represents a major constraint on P turnover and availability in acidic soils, as only a limited subset of bacteria appear to possess the traits required to access this persistent pool of soil P.

59 BASIC BIOLOGICAL SCIENCES↗

Isolation of phosphorus-hyperaccumulating microalgae from revolving algal biofilm (RAB) wastewater treatment systems

Excess phosphorus (P) in wastewater effluent poses a serious threat to aquatic ecosystems and can spur harmful algal blooms. Revolving algal biofilm (RAB) systems are an emerging technology to recover P from wastewater before discharge into aquatic ecosystems. In RAB systems, a community of microalgae take up and store wastewater P as polyphosphate as they grow in a partially submerged revolving biofilm, which may then be harvested and dried for use as fertilizer in lieu of mined phosphate rock. In this work, we isolated and characterized a total of 101 microalgae strains from active RAB systems across the US Midwest, including 82 green algae, 9 diatoms, and 10 cyanobacteria. Strains were identified by microscopy and 16S/18S ribosomal DNA sequencing, cryopreserved, and screened for elevated P content (as polyphosphate). Seven isolated strains possessed at least 50% more polyphosphate by cell dry weight than a microalgae consortium from a RAB system, with the top strain accumulating nearly threefold more polyphosphate. These top P-hyperaccumulating strains include the green alga Chlamydomonas pulvinata TCF-48 g and the diatoms Eolimna minima TCF-3d and Craticula molestiformis TCF-8d, possessing 11.4, 12.7, and 14.0% polyphosphate by cell dry weight, respectively. As a preliminary test of strain application for recovering P, Chlamydomonas pulvinata TCF-48 g was reinoculated into a bench-scale RAB system containing Bold basal medium. The strain successfully recolonized the system and recovered twofold more P from the medium than a microalgae consortium from a RAB system treating municipal wastewater. These isolated P-hyperaccumulating microalgae may have broad applications in resource recovery from various waste streams, including improving P removal from wastewater.

54 ENVIRONMENTAL SCIENCES↗

Prebiotic phosphorus chemistry reconsidered

The available evidence indicates that the origin of life on Earth certainly occurred earlier than 3.5 billion years ago and perhaps substantially earlier. The time available for the chemical evolution which must have preceded this event is more difficult to estimate. Both endogenic and exogenic contributions to chemical evolution have been considered; i.e., from chemical reactions in a primitive atmosphere, or by introduction in the interiors of comets and/or meteorites. It is argued, however, that the phosphorus chemistry of Earth's earliest hydrosphere, whether primarily exogenic or endogenic in origin, was most likely dominated by compounds less oxidized than phosphoric acid and its esters. A scenario is presented for the early production of a suite of reactive phosphonic acid derivatives, the properties of which may have foreshadowed the later appearance of biophosphates.

NASA Discipline Exobiology↗

Abundant phosphorus expected for possible life in Enceladus’s ocean

Saturn’s moon Enceladus has a potentially habitable subsurface water ocean that contains canonical building blocks of life (organic and inorganic carbon, ammonia, possibly hydro-gen sulfide) and chemical energy (disequilibria for methanogenesis). However, its habit-ability could be strongly affected by the unknown availability of phosphorus (P). Here, we perform thermodynamic and kinetic modeling that simulates P geochemistry based on recent insights into the geochemistry of the ocean–seafloor system on Enceladus. We find that aqueous P should predominantly exist as orthophosphate (e.g., HPO422), and total dissolved inorganic P could reach 1027to 1022mol/kg H2O, generally increasing with lower pH and higher dissolved CO2, but also depending upon dissolved ammonia and silica. Levels are much higher than<10210mol/kg H2Ofrompreviousestimatesand close to or higher than∼1026mol/kg H2O in modern Earth seawater. The high P concentration is primarily ascribed to a high (bi)carbonate concentration, which decreases the concentrations of multivalent cations via carbonate mineral formation, allowing phosphate to accumulate. Kinetic modeling of phosphate mineral dissolution suggests that geologically rapid release of P from seafloor weathering of a chondritic rocky core could supply millimoles of total dissolved P per kilogram of H2Owithin105y, much less than the likely age of Enceladus’s ocean (108to 109y). These results provide further evidence of habitable ocean conditions and show that any oceanic life would not be inhibited by low P availability.

Enceladus ocean↗

Synthesis and thermal decomposition properties of hydrogen-rich phosphorus salts.

Complex metal hydrides continue to be investigated as solid-materials for hydrogen storage. Traditional interstitial metal hydrides offer favorable thermodynamics and kinetics for hydrogen release but do not meet energy density requires. Anionic metal hydrides, and complex metal hydrides like magnesium borohydride have higher energy densities compared to interstitial metal hydrides, but poor kinetics and/or thermodynamically unfavorable side products limit their deployment as hydrogen storage materials in transportation applications. Main-group anionic materials such as the bis(borane)hypophosphite salt [PH2(BH3)2] have been known for decades, but only recently have we begun to explore their ability to release hydrogen. We have developed a new procedure for synthesizing the lithium and sodium hypophosphite salts. Routes for accessing other metal bis(borane)hypophosphite salts will be discussed. A significant advantage of this class of material is the air and water stability of the anion. Compared to metal borohydrides, which reactive violently with water, these phosphorus-based salts can be dissolved in protic solvents, including water, with little to no decomposition over the course of multiple days. The ability of these salts to release hydrogen upon heating has been assessed. While preliminary results indicate phosphine and boron-containing species are released, hydrogen is also a major component of the volatile species observed during the thermal decomposition. Additives such as NaH or KH mixed with the sodium salt Na[PH2(BH3)2] significantly perturb the decomposition reaction and greatly increase the mass loss as determined by thermal gravimetric analysis (TGA). This symbiotic behavior has the potential to affect the hydrogen storage ability of bis(borane)hypophosphite salts.

08 HYDROGEN↗

Phosphorus Speciation of Forest-soil Organic Surface Layers using P K-edge XANES Spectroscopy

The phosphorus (P) speciation of organic surface layers from two adjacent German forest soils with different degree of water-logging (Stagnosol, Rheic Histosol) was analyzed by P K-edge XANES and subsequent Linear Combination Fitting. In both soils, {approx}70% of the P was inorganic phosphate and {approx}30% organic phosphate; reduced P forms such as phosphonate were absent. The increased degree of water-logging in the Histosol compared to the Stagnosol did not affect P speciation.

54 ENVIRONMENTAL SCIENCES↗

Diagnosing phosphorus limitations in natural terrestrial ecosystems in carbon cycle models

Abstract Most of the Earth System Models ( ESMs ) project increases in net primary productivity ( NPP ) and terrestrial carbon (C) storage during the 21st century. Despite empirical evidence that limited availability of phosphorus (P) may limit the response of NPP to increasing atmospheric CO 2 , none of the ESMs used in the previous Intergovernmental Panel on Climate Change assessment accounted for P limitation. We diagnosed from ESM simulations the amount of P need to support increases in carbon uptake by natural ecosystems using two approaches: the demand derived from (1) changes in C stocks and (2) changes in NPP . The C stock‐based additional P demand was estimated to range between −31 and 193 Tg P and between −89 and 262 Tg P for Representative Concentration Pathway ( RCP ) 2.6 and RCP8.5 , respectively, with negative values indicating a P surplus. The NPP ‐based demand, which takes ecosystem P recycling into account, results in a significantly higher P demand of 648–1606 Tg P for RCP2 .6 and 924–2110 Tg P for RCP8 .5. We found that the P demand is sensitive to the turnover of P in decomposing plant material, explaining the large differences between the NPP ‐based demand and C stock‐based demand. The discrepancy between diagnosed P demand and actual P availability (potential P deficit) depends mainly on the assumptions about availability of the different soil P forms. Overall, future P limitation strongly depends on both soil P availability and P recycling on ecosystem scale.

54 ENVIRONMENTAL SCIENCES↗

Phosphorus feedbacks constraining tropical ecosystem responses to changes in atmospheric CO 2 and climate

The effects of phosphorus (P) availability on carbon (C) cycling in the Amazon region are investigated using CLM-CNP. Within this paper, we demonstrate that the coupling of P dynamics reduces the simulated historical terrestrial C sink due to increasing atmospheric CO 2 concentrations ([CO 2 ]) by about 26%. Our exploratory simulations show that the response of tropical forest C cycling to increasing [CO 2 ] depends on how elevated CO 2 affects phosphatase enzyme production. The effects of warming are more complex, depending on the interactions between humidity, C, and nutrient dynamics. While a simulation with low humidity generally shows the reduction of net primary productivity (NPP), a second simulation with higher humidity suggests overall increases in NPP due to the dominant effects of reduced water stress and more nutrient availability. Lastly, our simulations point to the need for (1) new observations on how elevated [CO 2 ] affects phosphatase enzyme production and (2) more tropical leaf-scale measurements under different temperature/humidity conditions with different soil P availability.

54 ENVIRONMENTAL SCIENCES↗

Anisotropic Thermal Conductivity of Exfoliated Black Phosphorus

We ascertain the anisotropic thermal conductivity of passivated black phosphorus (BP), a reactive 2D nanomaterial with strong in-plane anisotropy. We measure the room temperature thermal conductivity by time-domain thermoreflectance for three crystalline axes of exfoliated BP. The thermal conductivity along the zigzag direction (86 ± 8 W m -1 K -1 ) is ~2.5 times higher than that of the armchair direction (34 ± 4 W m -1 K -1 ).

36 MATERIALS SCIENCE↗

Phosphorus-Rich Colloidal Cobalt Diphosphide (CoP 2 ) Nanocrystals for Electrochemical and Photoelectrochemical Hydrogen Evolution

Developing earth-abundant and efficient electrocatalysts for photoelectrochemical water splitting is critical to realizing a high-performance solar-to-hydrogen energy conversion process. Here in this paper, phosphorus-rich colloidal cobalt diphosphide nanocrystals (CoP 2 NCs) are synthesized via hot injection. The CoP 2 NCs show a Pt-like hydrogen evolution reaction (HER) electrocatalytic activity in acidic solution with a small overpotential of 39 mV to achieve -10 mA cm -2 and a very low Tafel slope of 32 mV dec -1 . Density functional theory (DFT) calculations reveal that the high P content both physically separates Co atoms to prevent H from over binding to multiple Co atoms, while simultaneously stabilizing H adsorbed to single Co atoms. The catalytic performance of the CoP 2 NCs is further demonstrated in a metal–insulator–semiconductor photoelectrochemical device consisting of bottom p-Si light absorber, atomic layer deposition Al–ZnO passivation layers, and the CoP 2 cocatalyst. The p-Si/AZO/TiO 2 /CoP 2 photocathode shows a photocurrent density of -16.7 mA cm -2 at 0 V versus reversible hydrogen electrode (RHE) and an output photovoltage of 0.54 V. The high performance and stability are attributed to the junction between p-Si and AZO, the corrosion-resistance of the pinhole-free TiO 2 protective layer, and the fast HER kinetics of the CoP 2 NCs.

36 MATERIALS SCIENCE↗

New Insights into the High‐Performance Black Phosphorus Anode for Lithium‐Ion Batteries

Abstract Black phosphorus (BP) is a promising anode material in lithium‐ion batteries (LIBs) owing to its high electrical conductivity and capacity. However, the huge volume change of BP during cycling induces rapid capacity fading. In addition, the unclear electrochemical mechanism of BP hinders the development of rational designs and preparation of high‐performance BP‐based anodes. Here, a high‐performance nanostructured BP–graphite–carbon nanotubes composite (BP/G/CNTs) synthesized using ball‐milling method is reported. The BP/G/CNTs anode delivers a high initial capacity of 1375 mA h g −1 at 0.15 A g −1 and maintains 1031.7 mA h g −1 after 450 cycles. Excellent high‐rate performance is demonstrated with a capacity of 508.1 mA h g −1 after 3000 cycles at 2 A g −1 . Moreover, for the first time, direct evidence is provided experimentally to present the electrochemical mechanism of BP anodes with three‐step lithiation and delithiation using ex situ X‐ray diffraction (XRD), ex situ X‐ray absorption spectroscopy (XAS), ex situ X‐ray emission spectroscopy, operando XRD, and operando XAS, which reveal the formation of Li 3 P 7 , LiP, and Li 3 P. Furthermore, the study indicates an open‐circuit relaxation effect of the electrode with ex situ and operando XAS analyses.

Li, Minsi↗

Effect of Phosphorus Modulation in Iron Single‐Atom Catalysts for Peroxidase Mimicking

Abstract Fe–N–C single‐atom catalysts (SACs) exhibit excellent peroxidase (POD)‐like catalytic activity, owing to their well‐defined isolated iron active sites on the carbon substrate, which effectively mimic the structure of natural peroxidase's active center. To further meet the requirements of diverse biosensing applications, SAC POD‐like activity still needs to be continuously enhanced. Herein, a phosphorus (P) heteroatom is introduced to boost the POD‐like activity of Fe–N–C SACs. A 1D carbon nanowire (FeNCP/NW) catalyst with enriched Fe–N 4 active sites is designed and synthesized, and P atoms are doped in the carbon matrix to affect the Fe center through long‐range interaction. The experimental results show that the P‐doping process can boost the POD‐like activity more than the non‐P‐doped one, with excellent selectivity and stability. The mechanism analysis results show that the introduction of P into SAC can greatly enhance POD‐like activity initially, but its effect becomes insignificant with increasing amount of P. As a proof of concept, FeNCP/NW is employed in an enzyme cascade platform for highly sensitive colorimetric detection of the neurotransmitter acetylcholine.

Ding, Shichao↗