Inorganic Species Research Articles

Dynamic and Reversible Blending Interface on Polyoxovanadate Electrode for High-Performance Lithium-Ion Batteries.

Solid electrolyte interphase (SEI) plays a critical role in the performance of lithium-ion batteries (LIBs). In contrast to the clear interface between the traditional consecutive electrode materials and SEI, ionic polyoxometalates (POMs) as electrode could bilaterally diffuse with SEI and form a blending interface for superior electrochemical performance. POMs have recently aroused much interest as electrode materials in LIBs due to their structural flexibility, high capacity, and cycling stability. However, the interface evolution between POM-based electrodes and SEI, which is critical for Li+ ion transportation, has rarely been explored. Herein, we choose Li10[V12B18O60H6] (LVB) as an example to investigate the formation and structural evolution of the electrode-electrolyte interface. Time-of-flight secondary ion mass spectrometry together with X-ray photoelectron spectroscopy demonstrates the evolution of a blending layer at the interface containing typical SEI components, a polyanion from LVB and a phosphate anion from decomposition products of LiPF6. In the blending layer, ion migration takes place between the P-related inorganic species and the polyanion during the Li+ insertion/extraction reaction. Such a compatible blending layer favors Li+ transportation and the reversibility of the redox reactions, as supported by a series of electrochemical analyses. This work provides detailed insights into understanding the interface evolution of the LVB electrode and demonstrates the importance of interfacial engineering to induce proper interface layers in the development of high-performance POM-based electrodes for LIBs.

Highly Stable Lithium Metal Batteries Enabled by Tuning the Molecular Polarity of Diluents in Localized High-Concentration Electrolytes.

Electrolyte plays a crucial role in ensuring stable operation of lithium metal batteries (LMBs). Localized high-concentration electrolytes (LHCEs) have the potential to form a robust solid-electrolyte interphase (SEI) and mitigate Li dendrite growth, making them a highly promising electrolyte option. However, the principles governing the selection of diluents, a crucial component in LHCE, have not been clearly determined, hampering the advancement of such a type of electrolyte systems. Herein, the diluents from the perspective of molecular polarity are rationally designed and developed. A moderately fluorinated solvent, 1-(1,1,2,2-tetrafluoroethoxy)propane (TNE), is employed as a diluent to create a novel LHCE. The unique molecular structure of TNE enhances the intrinsic dipole moment, thereby altering solvent interactions and the coordination environment of Li-ions in LHCE. The achieved solvation structure not only enhances the bulk properties of LHCE, but also facilitates the formation of more stable anion-derived SEIs featured with a higher proportion of inorganic species. Consequently, the corresponding full cells of both Li||LiFePO4 and Li||LiNi0.8Co0.1Mn0.1O2 cells utilizing Li thin-film anodes exhibit extended long-term stability with significantly improved average Coulombic efficiency. This work offers new insights into the functions of diluents in LHCEs and provides direction for further optimizing the LHCEs for LMBs.

Modeling the Transport of Inorganic Arsenic Species through Field Soils: Irrigation and Soil Structure Effect

Dissolved arsenic (As) may appear at the tile line level through preferential flow (PF), leading to contamination of shallow water bodies. Limited work on the movement of As forms in field soils urged the need for more research. The PF of arsenate (As(V)) and arsenite (As(III)) compared to chloride (Cl) at constant flow under saturated (10 mm), slightly unsaturated (−10 mm), and unsaturated (−40 mm) pressure heads was evaluated in replicated large field columns varying in subsoil structure. A solute containing As(V), As(III), and Cl was pulsed until the Cl concentration ratio in the drainage samples reached maxima and flushed with solute-free irrigation. HYDRUS-1D software version 4.15 was utilized to fit the breakthroughs of As(V) and As(III) in the dual-porosity physical non-equilibrium model (DP-PNE). The Langmuir equation was used to fit the As(V) and As(III) sorption isotherms, and blue dye staining was used for the marking of flow paths. Dye leaching was observed up to 50 cm or deeper in the soils. Under saturated conditions (+10 mm), Kotli, Guliana, and Mansehra soils showed chemical non-equilibrium (CNE) for As(V) and As(III); however, the extent of CNE was less under unsaturated conditions (−40 mm). These results implied that these well-structured soils had enough large macropores, which cause PF, but at the same time, they were also small enough to retain water and leach solutes under unsaturated conditions (−40 mm). It is concluded that irrigation of contaminated water or dumping solid waste on well-aggregated soil may exhibit PF of dissolved As during and after rains, and additionally As(III), which is more toxic and mobile under reduced conditions, has equal or greater potential for movement.

Photoreforming of fermentation byproducts by TiO2 and Pt/TiO2 to enhance hydrogen production: Insight into a real perspective

This research was focused on evaluating TiO2 and Pt/TiO2 for hydrogen production through the photoreforming of fermentation byproducts in a solution exposed to UV-LED irradiation. It was also proposed a modification of the generalized kinetic model to predict photocatalytic hydrogen production. Hydrogen production in water matrix with Pt/TiO2 was 27.9 times higher than with bare TiO2 (79.5 μmol H2/gcat). Additionally, tests with Pt/TiO2 and phosphate buffer matrix resulted in a 60% decrease in H2 yield; the presence of inorganic species in the buffer reduced the activity of Pt/TiO2 due to the scavenging of the generated reactive species. Photoreforming tests using real fermentative effluent also demonstrated a notable decrease in activity due to the presence of inorganic ions. Regardless of the solvent matrix, Pt acted as an electron trap, thereby enhancing the photocatalytic activity of TiO2. The metallic Pt on TiO2 also generated plasmonic effects that improved photon absorption (2-fold compared to bare TiO2), increasing the effectiveness of incident radiation. Finally, the kinetic model validates the photoreforming approach with high accuracy.

Phosphorus availability and speciation in soils amended with upcycled dairy-waste nutrients

The excessive application of dairy manure to soils to supply plant nutrients can result in increased offsite nutrient transport and degraded water quality. However, by concentrating nutrients from dairy-waste onto biochar or as biosolids, a viable alternative fertilizer can be produced that will benefit soil health, promote carbon sequestration, and decrease nutrient leaching into surface waters. In this study, a greenhouse experiment was conducted to assess soil phosphorus (P) speciation and barley plant growth in soils amended with dairy-waste treated biochar and fermented manure. Phosphorus characterization in the post-harvest soils was determined using selective extractions, 31P-NMR and XANES spectroscopy, and isotopic tracing (P-δ18O). Selective extractions and NMR spectroscopy revealed that most of the P in the amended soils occurred as inorganic species (>85%). XANES spectroscopy further showed that the soil P occurred as either calcium-P minerals (54%–87%) or adsorbed P (0%–46%) species. Analysis by P-δ18O in water and sodium bicarbonate extractions of the treated soils showed that the water-extracted P pool is cycled much faster than the sodium bicarbonate extracted P. Although less than 10% of the total P in the dairy-derived bioproducts was extracted using water, plant productivity in the soils treated with these amendments was the same as that in soils treated with equivalent amounts of conventional nitrogen and P fertilizer. This suggests that dairy-derived bioproducts are good soil amendments to supply nutrients and limit leaching.

Poison in the water: Arsenic's silent assault on fish health.

Arsenic occurs across the world in freshwater and marine environments, menacing the survival of aquatic organisms. Organic and inorganic forms of this substance can be found, in which the inorganic form is more hazardous than the organic form. Most aquatic bodies contain inorganic arsenic species, but organic species are believed to be the dominant form of arsenic in the majority of fish. Natural and anthropogenic both are the sources of water contamination with arsenic. Its bioaccumulation and transfer from one trophic level to another in the aquatic food chain make arsenic a vital environmental issue. Continuous exposure to low concentrations of arsenic in aquatic organisms including fish leads to its bioaccumulation, which may affect organisms of higher trophic levels including large fishes or humans. Humans can be exposed to arsenic through the consumption of fish contaminated with arsenic. Hence, the present review facilitates our understanding about sources of arsenic, its bioaccumulation, food chain transfer, and its effect on the fish health. Also, "Poison in the Water: Arsenic's Silent Assault on Fish Health" serves as a wake-up call to recognize the pressing need to address arsenic contamination in water bodies. By understanding its devastating impact on fish health, we can strive to implement sustainable practices and policies that safeguard our precious aquatic environments and ensure the well-being of both wildlife and human communities that depend on them.

Enhancing characterization of organic nitrogen components in aerosols and droplets using high-resolution aerosol mass spectrometry

Abstract. This study aims to enhance the understanding and application of the Aerodyne high-resolution aerosol mass spectrometer (HR-AMS) for the comprehensive characterization of organic nitrogen (ON) compounds in aerosol particles and atmospheric droplets. To achieve this goal, we analyzed 75 N-containing organic compounds, representing a diverse range of ambient non-organonitrate ON (NOON) types, including amines, amides, amino acids, N heterocycles, protein, and humic acids. Our results show that NOON compounds can produce significant levels of NHx+ and NOx+ ion fragments, which are typically recognized as ions representative of inorganic nitrogen species. We also identified the presence of CH2N+ at m/z = 28.0187, an ion fragment rarely quantified in ambient datasets due to substantial interference from N2+. As a result, the utilization of an updated calibration factor of 0.79 is necessary for accurate NOON quantification via the HR-AMS. We also assessed the relative ionization efficiencies (RIEs) for various NOON species and found that the average RIE for NOON compounds (1.52 ± 0.58) aligns with the commonly used default value of 1.40 for organic aerosol. Moreover, through a careful examination of the HR-AMS mass spectral features of various NOON types, we propose fingerprint ion series that can aid the NOON speciation analysis. For instance, the presence of CnH2n+2N+ ions is closely linked with amines, with CH4N+ indicating primary amines, C2H6N+ suggesting secondary amines, and C3H8N+ representing tertiary amines. CnH2nNO+ ions (especially for n values of 1–4) are very likely derived from amides. The co-existence of three ions, C2H4NO2+, C2H3NO+, and CH4NO+, serves as an indicator for the presence of amino acids. Additionally, the presence of CxHyN2+ ions indicates the occurrence of 2N-heterocyclic compounds. Notably, an elevated abundance of NH4+ is a distinct signature for amines and amino acids, as inorganic ammonium salts produce only negligible amounts of NH4+ in the HR-AMS. Finally, we quantified the NOON contents in submicron particles (PM1) and fog water in Fresno, California, and PM1 in New York City (NYC). Our results revealed the substantial presence of amino compounds in both Fresno and NYC aerosols, whereas concurrently collected fog water in Fresno contained a broader range of NOON species, including N-containing aromatic heterocycle (e.g., imidazoles) and amides. These findings highlight the significant potential of employing the widespread HR-AMS measurements of ambient aerosols and droplets to enhance our understanding of the sources, transformation processes, and environmental impacts associated with NOON compounds in the atmosphere.

Microfluidic paper-based analytical device for the speciation of inorganic nitrogen species

A microfluidic paper-based analytical device (μPAD) utilizing gas-diffusion separation and solid-phase reduction was developed for the first time for the determination of both ammonium and nitrate, which are the dominant inorganic nitrogen species in environmental waters. The device consists of 3 filter paper layers accommodating the sample, reagent and detection zones. The reagent zone is separated from the detection zone by a semipermeable hydrophobic membrane and acts as a solid-phase reactor where nitrate is reduced to ammonia by Devarda's alloy microparticles, integrated into a μPAD for the first time. The detection zone incorporates the acid-base indicators bromothymol blue (BTB) or nitrazine yellow (NY) and changes colour in two steps. Initially the colour change is caused by ammonia generated by the reaction of ammonium and sodium hydroxide in the sample zone. This colour change is followed by a subsequent colour change as a result of the ammonia produced by the reduction of nitrate by the Devarda's alloy microparticles. The corresponding reflectance value changes are used for the quantification of the two inorganic nitrogen species in the ranges 6.5–100.0 or 2.1–15.0 mg N L−1 for ammonium and 18.2–100.0 or 4.2–15.0 mg N L−1 for nitrate when BTB or NY are used, respectively. Under optimal conditions the limits of quantification of ammonium and nitrate in the case of BTB were determined as 6.5 and 18.2 mg N L−1, respectively, while the corresponding values in the case of NY were found to be 2.1 and 4.2 mg N L−1. The newly developed μPAD was stable for 62 days when stored in a freezer and 1 day at ambient temperature. It was validated with a certified reference material and successfully applied to the determination of ammonium and nitrate in spiked environmental water samples and soil extracts.

Rare earth element behaviors of groundwater in overlying aquifers under the influence of coal mining in northern Ordos Basin, China.

Rare earth elements (REEs) have been used as tracers to reveal the hydrochemical sources and processes in groundwater systems that are usually modified by anthropogenic inputs. However, the REE behaviors in groundwater affected by mining activities have yet to be fully understood. In combination of REE geochemistry with general hydrochemical and isotopic (δ2H and δ18O) methods, this study investigated the concentration and fractionation of REEs in alkaline groundwater from two coal mines with similar aquifer lithology but different mining histories in the Northern Ordos Basin. One of the coal mines started mining in March 2009 (Ningtiaota coal mine, NTT), while the other started mining in December 2018 (Caojiatan coal mine, CJT). Results show that the primary hydrochemical type is HCO3-Ca in NTT groundwater with pH value ranging between 7.68 and 8.60, while CJT groundwater was dominated by the HCO3-Na type with higher pH of 9.09-10.00. The average values of ΣREEs were lower, and the NASC-normalized pattern reflected more intense fractionation in NTT groundwater than those in CJT groundwater. The evident differences are caused by the distinctions in water-rock interaction, complexation of inorganic species, and adsorption of REEs in NTT and CJT groundwater. Furthermore, these processes were closely related to the pH of groundwater that was different in two coal mines, which is likely linked to the different durations of coal mining activities that led to differences in development of rock fractures and pyrite oxidation. It is expected that REEs, combined with other indicators such as pH, can be used to trace and help better understand the hydrochemical changes in groundwater caused by mining.

A method for measuring the bioaccessibility of polycyclic aromatic hydrocarbons in cell culture media

Airborne polycyclic aromatic hydrocarbons (PAHs) and their derivatives are of particular concern for population health due to their abundance and toxicity via inhalation. Lung toxicity testing includes exposing lung epithelial cell lines to PAHs in a culture medium containing inorganic species, lipids, proteins, and other biochemicals where the cell response is influenced among others by the toxic chemical accessibility in the medium. While inhalation bioaccessibility of PAHs and other toxicants was previously studied in surrogate lung fluids, studies measuring bioaccessibility in cell culture media are rare. In this work, a method was developed to characterize PAH bioaccessibility in a culture medium used for mouse lung epithelial (FE1) cells. Further, the optimised method was tested using commercially available standard reference material of urban particulate matter (PM) as well as polyurethane foam passive air samplers (PUF-PAS). The method provided a high precision and recovery of analytes, indicating no losses during sample processing and analysis. PAHs had non-linear concentration-responses, with the culture medium approaching saturation with PM concentration of 500 μg mL−1. The results showed that phenanthrene, a 3-ring PAH, was significantly more bioaccessible than ≥4-ring congeners in the culture medium (up to ∼2.5 folds; p < 0.05). Finally, using pre-deployed PUF-PAS from a residential and an industrial site, five PAHs were found in the culture medium, including naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene. This work provides a proof of concept to enable future studies to assess the inhalation bioaccessibility of polycyclic aromatic compounds and other airborne pollutants collected using PUF-PAS.

Facile green synthesis route for new ecofriendly photo catalyst for degradation acid red 8 dye and nitrogen recovery

This study novelty is that new photo catalyst prepared from sustainability low cost precursors. Dark red color hydrogel composites have been easily prepared from gelatin biopolymer using a simple sol–gel method. Gelatin doped by cobalt chloride, and silver nanoparticles (SNPs) in the presence of traces amount of sodium dodecyl sulfate surfactant and calcium chloride. Water-insoluble Gelatin composites are thermally stable photocatalysts for the degradation of toxic anionic acid red 8 dye. Promising photodynamic activity confirmed by fluorescence emission at λmax 650 nm. Optical absorption in Vis. light enhanced photo catalytic activity. Silver nanoparticles enhanced crystallinity, and improved optical properties and porosity. Dopants by CoCl2 and silver nanoparticles increased band gap of gelatin composites from (1.82 to 1.95) indicating interfacial charge separation. Low band gaps improved photo catalytic activity. Optical band gaps (Eg) lower than 2.0 eV indicates high catalytic activity in the photo degradation acid red 8 dye using Vis. light, wavelength 650 nm. Percent removal efficiency (%Re) of the dye at 500 ppm initial concentration, pH 1, contact time 30 min., and 0.20 g L−1 dose photo catalyst reached 95%. pH not affects removal efficiency. So, gelatin composites removed AR8 dye by photodegradation mechanism rather than adsorption due to photodynamic activity. Kinetics of photodegradation followed pseudo first order kinetic with rate constant k1 5.13 × 10−2 min.−1 Good electrical conductivity and magnetic properties (effective magnetic moment (µeff 4.11 B.M) improved dye degradation into simple inorganic species. Nutrients NH4+, and NO3− degradation products recovered by using alumina silicate clay via a cation exchange mechanism.

Multifunctional Silane Additive Enhances Inorganic–Organic Compatibility with F‐rich Nature of Interphase to Support High‐Voltage LiNi0.5Mn1.5O4//graphite Pouch Cells

AbstractA novel electrolyte additive, 3, 3, 3‐trifluoropropylmethyldimethoxysilane (TFPMDS), is first proposed to modify both the cathode and the anode of lithium‐ion batteries at the same time. Charging/discharging tests demonstrate that the electrolyte with 1 wt% TFPMDS not only greatly improves the capacity retention of LiNi0.5Mn1.5O4 (LNMO)//Li cell (29.6%→90.8%) and graphite//Li cell (68.1%→98.3%), but also successfully ensures the long‐term cycle stability of LNMO//graphite pouch cell at 4.9 V. Further electrochemical measurements combining with spectroscopic characterization and theoretical calculations indicate that TFPMDS additive displays three principal functions: 1) Be preferentially oxidized to build a robust cathode electrolyte interphase (CEI) enriched in F/Si species with F‐rich nature of strong oxidation‐resistance. 2) Be able to scavenge the hazardous HF, F−, and H+ through its strong binding with these species and thus to protect LNMO at high‐voltage. 3) Be preferentially adsorbed on the graphite surface to form a “framework”, and to co‐construct an elastic solid electrolyte interphase (SEI) after the reduction of ethylene carbonate. Importantly, the Si─O group within TFPMDS is especially important for constructing a “molecular bridge” at the CEI/SEI interphase coupling the inorganic and organic species to improve its compatibility, stability, and elasticity.

Speciation and cycling of iodine in the subtropical North Pacific Ocean

Iodine intersects with the marine biogeochemical cycles of several major elements and can influence air quality through reactions with tropospheric ozone. Iodine is also an element of interest in paleoclimatology, whereby iodine-to-calcium ratios in marine carbonates are widely used as a proxy for past ocean redox state. While inorganic iodine in seawater is found predominantly in its reduced and oxidized anionic forms, iodide (I−) and iodate (IO3−), the rates, mechanisms and intermediate species by which iodine cycles between these inorganic pools are poorly understood. Here, we address these issues by characterizing the speciation, composition and cycling of iodine in the upper 1,000 m of the water column at Station ALOHA in the subtropical North Pacific Ocean. We first obtained high-precision profiles of iodine speciation using isotope dilution and anion exchange chromatography, with measurements performed using inductively coupled plasma mass spectrometry (ICP-MS). These profiles indicate an apparent iodine deficit in surface waters approaching 8% of the predicted total, which we ascribe partly to the existence of dissolved organic iodine that is not resolved during chromatography. To test this, we passed large volumes of seawater through solid phase extraction columns and analyzed the eluent using high-performance liquid chromatography ICP-MS. These analyses reveal a significant pool of dissolved organic iodine in open ocean seawater, the concentration and complexity of which diminish with increasing water depth. Finally, we analyzed the rates of IO3− formation using shipboard incubations of surface seawater amended with 129I−. These experiments suggest that intermediate iodine species oxidize to IO3− much faster than I− does, and that rates of IO3− formation are dependent on the presence of particles, but not light levels. Our study documents the dynamics of iodine cycling in the subtropical ocean, highlighting the critical role of intermediates in mediating redox transformations between the major inorganic iodine species.

Co-encapsulation of organic polymers and inorganic superparamagnetic iron oxide colloidal crystals requires matched diffusion time scales.

Nanoparticles (NPs) that contain both organic molecules and inorganic metal or metal oxide colloids in the same NP core are "composite nanoparticles" which are of interest in many applications, particularly in biomedicine as "theranostics" for the combined delivery of colloidal diagnostic imaging agents with therapeutic drugs. The rapid precipitation technique Flash NanoPrecipitation (FNP) enables continuous and scalable production of composite nanoparticles with hydrodynamic diameters between 40-200 nanometers (nm) that contain hydrophobic superparamagnetic iron oxide primary colloids. Composite NPs co-encapsulate these primary colloids (diameters of 6 nm, 15 nm, or 29 nm), a fluorescent dye (600 Daltons), and poly(styrene) homopolymer (1800, 50 000, or 200 000 Daltons) with NPs stabilized by a poly(styrene)-block-poly(ethylene glycol) (1600 Da-b-5000 Da) block copolymer. Nanoparticle assembly in FNP occurs by diffusion limited aggregation of the hydrophobic core components followed by adsorption of the hydrophobic block of the stabilizing polymer. The hydrodynamic diameter mismatch between the collapsed organic species and the primary colloids (0.5-5 nm versus 6-29 nm) creates a diffusion-aggregation time scale mismatch between components that can lead to nonstoichiometric co-encapsulation in the final nanoparticles; some nanoparticles are composites with primary colloids co-encapsulated alongside organics while others are devoid of the primary colloids and contain only organic species. We use a magnetic capture process to separate magnetic composite nanoparticles from organic-only nanoparticles and quantify the amount of iron oxide colloids and hydrophobic fluorescent dye (as a proxy for total hydrophobic polymer content) in the magnetic and nonmagnetic fractions of each formulation. Analysis of the microstructure in over 1100 individual nanoparticles by TEM imaging and composition measurements identifies the conditions that produce nonstoichiometric composite NP populations without co-encapsulated magnetic iron oxide colloids. Stoichiometric magnetically responsive composite NPs are produced when the ratio of characteristic diffusion-aggregation time scales between the inorganic primary colloid and the organic core component is less than 30 and all NPs in a dispersion contain organic and inorganic species in approximately the same ratio. These rules for assembly of colloids and organic components into homogeneous composite nanoparticles are broadly applicable.

Effect of Fuel Injection Strategies on Performance, Regulated and Unregulated Emissions of a Gasoline Compression Ignition Engine

Abstract Gasoline compression ignition (GCI) mode engines are characterized by partially premixed charge combustion, leading to significant and simultaneous reductions of nitrogen oxides and particulate matter emissions. However, gasoline compression ignition engine operation suffers from a limited operating window. Air preheating and low-research octane number fuels are required to improve the engine performance. This experimental study used a blend of 70% (v/v) gasoline and 30% diesel as test fuel in a direct injection medium-duty compression ignition engine. Experiments were carried out at 5- and 10-bar brake mean effective pressure (BMEP) engine loads at 1500–2500 rpm engine speeds using a triple injection strategy (two pilots and one main injection) for all test conditions. The combustion phasing was kept constant with respect to crank angle to produce a high power output. The investigations examined engine performance and regulated and unregulated emissions. The test engine was initially operated in conventional diesel combustion mode with diesel for baseline data generation. Gasoline compression ignition mode operation demonstrated a remarkable 16% increase in the brake thermal efficiency and a substantial reduction of 65% in nitrogen oxide emissions compared to the baseline conventional diesel combustion mode. The GCI engine exhaust showed higher concentrations of regulated emissions, namely hydrocarbons and carbon monoxide, and unregulated trace emissions, such as methane, acetylene, toluene, inorganic gaseous species, and unsaturated hydrocarbons.

Universality in interior periodic assembly of banded d-(−)-poly(3-hydroxybutyrate) justified with the iridescence test

Periodic assembly in poly(3-hydroxybutyrate) crystallized at selected Tc is analyzed with microscopy 3D interior dissection. Orderly grating-arrayed lamellae in PHB display light-interfering iridescence, resembling nature's structured coloration seen in inorganic minerals or organic species.

Phosphorus speciation under long‐term crop rotation management in a tropical soil

AbstractCrop rotation and soil management practices after native tropical forest conversion may impact the dynamics of inorganic and organic phosphorus (Pi and Po) species in the soil. By combining the state‐of‐the‐art spectroscopic methods P K‐edge X‐ray absorption near edge structure (XANES), 31P liquid nuclear magnetic resonance (31P‐NMR) and chemical P fractionation, this study provides important insights on soil P speciation after conversion of native forest to cropland under distinct managements. A field trial was conducted in a weathered tropical soil to assess Pi and Po changes after conversion of native forest to cropland. The crop rotations were managed under no‐tillage (NT) or minimum tillage (MT) since 2003, and repeated annually until 2015, cropped in the fall–winter and spring seasons, followed by soybean in the summer. Soil XANES analysis in the end revealed that P was predominantly associated with ferrihydrite and hematite, suggesting that P speciation was more strongly influenced by the presence of iron(oxyhydr)oxide than by crop rotations and/or soil management. The conversion of native forest to cropland promoted the mineralization of Po species, leading to re‐adsorption in non‐labile forms and consequently worsening the P cycling in the system. To increase the labile P pools and supply crop P demand, inputs of inorganic fertilizers were required owing to the strong soil P sorption. Our results show that even conservation practices such as MT or NT and complex crop rotations are not sufficient to inhibit the impact of cropland conversion on soil P forms.

Advances in Understanding the Marine Nitrogen Cycle in the GEOTRACES Era

Because nitrogen availability limits primary production over much of the global ocean, understanding the controls on the marine nitrogen inventory and supply to the surface ocean is essential for understanding biological productivity and exchange of greenhouse gases with the atmosphere. Quantifying the ocean’s inputs, outputs, and internal cycling of nitrogen requires a variety of tools and approaches, including measurements of the nitrogen isotope ratio in organic and inorganic nitrogen species. The marine nitrogen cycle, which shapes nitrogen availability and speciation in the ocean, is linked to the elemental cycles of carbon, phosphorus, and trace elements. For example, the majority of nitrogen cycle oxidation and reduction reactions are mediated by enzymes that require trace metals for catalysis. Recent observations made through global-scale programs such as GEOTRACES have greatly expanded our knowledge of the marine nitrogen cycle. Though much work remains to be done, here we outline key advances in understanding the marine nitrogen cycle that have been achieved through these analyses, such as the distributions and rates of dinitrogen fixation, terrestrial nitrogen inputs, and nitrogen loss processes.

Simultaneously Generating Redox Mediator and Hybrid SEI for Lithium–oxygen Batteries by Lewis Acid Catalyzed Ring‐opening Reaction of Organic Iodine

AbstractFacing high overpotential, severe Li corrosion and degradation of electrolytes caused by the reactive oxygen species, the development of lithium–oxygen batteries is seriously limited. Although the iodine species have been considered to be effective redox mediators (RMs) for lowering the charging overpotential, the shuttling of oxidized I3− may attack the Li metal anode, compromising the number of RMs, cycling stability and energy efficiency. Here the intend to introduce 3‐Iodooxetane (C3H5OI, IOD) into TEGDME‐based electrolyte to form a protective SEI layer on the Li surface for defending against the attack of I3−. However, the iodine in IOD is found difficult to dissociate. To solve this problem, hard Lewis acid, aluminum trichloride (AlCl3) is proposed as the catalytic agent for dissociating the I− and triggering the ring‐opening reaction of the detached C3H5O+ ions. The former can dissociate redox couple I3−/I− while the latter can form oligomers or polymers under the attack of a nucleophile. Meanwhile, AlCl3 can form Al2O3 and LiCl inorganic species. Taking together, the introduction of IOD and AlCl3 into electrolytes can effectively derive reduced overpotential and in situ SEI layers consisting of flexible organics and rigid inorganics, endowing lithium–oxygen batteries over 150 cycles with significantly enhanced stability and lifespan.

Study on the interaction between inherent minerals of coal with refuse derived fuel (RDF) during co-firing

In this paper, refuse derived fuel (RDF) and bituminous coal were co-fired to investigate the particulate matter (PM) yields and the interaction between the inherit minerals in a lab-scale drop tube furnace (DTF). The PM1-10 yields during the co-firing of coal and RDF dramatically decreased by 16.29 %∼28.5 % of the combustion of coal alone. In addition, methane auxiliary combustion inhibited the PM1 yields by 7.95 % at air atmosphere. The Si-rich minerals in coal interreacted with the organic alkali (earth) metals in RDF, massively generating sticky particles with high liquid amount of K-Al-Si and Ca-Al-Si, promoting the transformation of fine grains into coarser mode. Moreover, it was proved that both methane auxiliary combustion and co-firing can reduce the emission of fine particles. The additional heat accelerated the burn of the char at the early stage of combustion, providing adequate time for the interaction between the inorganic species. Through thermodynamic equilibrium calculations of 1500 ∼ 3000 fly ash grains, it was found that co-firing increased the formation of sticky particles by 64.8 %∼70.3 %, resulting in a significant enhancement in capturing fine particles and Na, K vapor. Therefore, the co-firing of coal with RDF offers a promising approach to realize the harmless and resourceful treatment of municipal solid waste (MSW), and inhibit land resource losses caused by landfill