Magnetic Resonance Absorption Research Articles

Insights about the effect of metal–organic framework hybridization with graphene-like materials

Abstract Hybrids based on the copper-based metal–organic framework HKUST-1 and graphene-like materials (GL) have been synthesized at different concentrations of GL, and investigated by means of solid state nuclear magnetic resonance (ssNMR) and x-ray absorption techniques (NEXAFS and XANES) with the aim of elucidating the effect of the hybridization on the structural properties of HKUST-1. The comparative analysis of ssNMR and x-ray absorption spectra recorded on parent materials (GL and pure HKUST-1) and on the hybrids indicates that the overall structural features of HKUST-1 are preserved in the presence of increasing GL amounts (up to 30 wt.%) and confirms that the framework development is not massively altered by the presence of graphene-related materials (GRMs) in the synthetic medium.

Electronic and Molecular Structures of a Series of Nickel Bis-1,1-Dithiolates.

A series of homoleptic Ni bis-1,1-dithiolates, [Ni(S2C2RR')2]2- (R=CN, R'=CN, CO2Et, CONH2, Ph, Ph-4-Cl, Ph-4-OMe, Ph-4-NO2, Ph-3-CF3, Ph-4-CF3, Ph-4-CN; R=NO2, R'=H; R=R'=CO2Et) have been synthesized from the reaction of the alkali metal salt of the ligand and nickel chloride, and isolated as tetraphenylphosphonium or tetrabutylammonium salts. The complexes were characterized by X-ray crystallography, high-resolution mass spectrometry, and infrared (IR), nuclear magnetic resonance (NMR) and electronic absorption spectroscopies. The molecular structures show a rigidly square planar Ni(II) center linking two four-membered chelate rings whose dimensions are constant across the series. The electronic effect of the ligand substituent is revealed in the 13C NMR and electronic spectra, and corroborated by density functional calculations. Electron withdrawing groups deshield the low-field CS2 resonance, and the signature charge transfer band in the visible region is red-shifted. These observables have been accurately reproduced computationally, and revealed the Ni contribution to the ground state diminishes with decreasing electron withdrawing capacity of the ligand substituent. In contrast to 1,2-dithiolates, the redox inactivity afforded by 1,1-dithiolates stems from the smaller chelate ring and substantially reduced sulfur content that is key to stabilizing the radical form.

A novel means to generate high pressure.

Diamond anvil cells are the most popular means of generating pressures above 2GPa. However, in many experiments, such as nuclear magnetic resonance and x-ray absorption, the metallic pressurizing gasket (which confines much of the sample) represents an occluding barrier that requires a low Z gasket material (e.g., Be), a split gasket, or other means to enable better coupling of the sample to electromagnetic radiation. In this paper, we demonstrate a novel method for generating high pressures that confines the sample just above the plane of the gasket by using a diamond with a laser hole drilled into the center of the tip. The sample is then confined by the hole, which is sealed by a flat gasket that fits over the hole. When load is applied to the diamonds, metal flows from the deformed gasket into the hole thereby pressurizing the sample similarly to how a piston pressurizes gas inside a cylinder. The pressurized sample is above the metallic gasket plane just inside the tip of the diamond, and thus easily accessible via x rays or visible light that skims just above the plane of the gasket providing an enhanced aperture of radiation collection. We have demonstrated the utility of this method by obtaining Raman spectra of SnC2O4 and x-ray diffraction spectra of seleno-DL-cystine, all at high pressures.

Employing molecular dynamics simulations and DFT calculations to elucidate the energetic, structural, and spectroscopic attributes of (poly)valines in water solution

In this study, we explored how the growth of peptide chains containing valines impacts nuclear magnetic resonance (NMR) and optical absorption spectra. Results stem from equilibrated configurations in water, reflecting solvent influence and valine vibration. Utilizing fully atomistic molecular dynamics (MD), simulations, and density functional theory (DFT) including TD-DFT, we observe a notable shift in optical absorption towards longer wavelengths with increased valine count. Additionally, carbon atom magnetic signatures unveil distinct peptide bond characteristics. This work sheds light on the spectroscopic behavior of valine-rich peptide chains, crucial for understanding structural and functional properties, particularly in biomolecular contexts.

Synthesis and Characterization of Schiff Base Ligands and Their Palladium(II) Complexes

Abstract: This paper is concerned with the preparation and characterization of Schiff base ligands derived from the condensation of salicylaldehyde with three different diamines, namely, ethylenediamine, o-phenylenediamine, and trans-1,2-diaminocyclohexane. The Schiff base ligands were characterized by elemental analysis, melting point, FTIR, UV-Vis, 1H-NMR and 13C-NMR. The Schiff base ligands are reacted with palladium(II) ion via direct reaction or using a template method. Identical complexes were obtained from the two methods with the same percentage yields. The formulas obtained for the complexes are PdC16H16N2O2Cl2, [PdL1]Cl2; PdC16H16N2O2Br2, [PdL1]Br2; PdC16H16N2O2.(BF4)2, [PdL1](BF4)2; PdC20H16N2O2Cl2, [PdL2Cl]Cl; PdC20H16N2O2Br2, [PdL2]Br2; PdC20H15N2O2.BF4, [PdL2]BF4; PdC20H22N2O2Cl2, [PdL3]Cl2; PdC20H22N2O2Br2, [PdL3]Br2; PdC20H20N2O2.2H2O, [PdL3].2H2O. The isolated compounds were characterized based on their melting points, elemental analyses, conductivity measurements, nuclear magnetic resonance, FTIR and electronic absorption spectra.

Synthesis, separation, and characterization of spiro-fused cycloalkyl-embedded 5,15-porphodimethenes

The synthesis of cycloalkyl-fused porphodimethenes from a mixture of products was investigated. Each product was separated via silica gel column chromatography and characterized using nuclear magnetic resonance (NMR) and UV-visible absorption spectroscopies, and mass spectrometry. X-ray crystal structure analysis revealed their gable-like bent conformations bearing perpendicular cycloalkyl rings in which the dipyrrin pairs contacted closely so that the neighboring pyrrole rings formed circular hydrogen bonding networks, such as those in porphyrins. Such configurations also caused extreme downfield shifts of the methylene protons of the cycloalkyl rings in the 1H NMR spectra.

Structural and Spectroscopic Characterization of Copper(III) Complexes and Subsequent One-Electron Oxidation Reaction and Reactivity Studies.

The formation of Cu(III) species are often invoked as the key intermediate in Cu-catalyzed organic transformation reactions. In this study, we synthesized Cu(II) (1) and Cu(III) (3) complexes supported by a bisamidate-bisalkoxide ligand consisting of an ortho-phenylenediamine (o-PDA) scaffold and characterized them through an array of spectroscopic techniques, including UV-visible, electron paramagnetic resonance, X-ray crystallography, and 1H nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy. The Cu-N/O bond distances in 3 are ∼0.1 Å reduced compared to 1, implying a significant increase in 3's overall effective nuclear charge. Further, a Cu(III) complex (4) of a bisamidate-bisalkoxide ligand containing a trans-cyclohexane-1,2-diamine moiety exhibits nearly identical Cu-N/O bond distances to that of 3, inferring that the redox-active o-PDA backbone is not oxidized upon one-electron oxidation of the Cu(II) complex (1). In addition, a considerable difference in the 1s → 4p and 1s → 3d transition energy was observed in the X-ray absorption near-edge structure data of 3 vs 1, which is typical for the metal-centered oxidation process. Electrochemical measurements of the Cu(II) complex (1) in acetonitrile exhibited two consecutive redox couples at -0.9 and 0.4 V vs the Fc+/Fc reference electrode. One-electron oxidation reaction of 3 further resulted in the formation of a ligand-oxidized Cu complex (3a), which was characterized in depth. Reactivity studies of species 3 and 3a were explored toward the activation of the C-H/O-H bonds. A bond dissociation free energy (BDFE) value of ∼69 kcal/mol was estimated for the O-H bond of the Cu(II) complex formed upon transfer of hydrogen atom to 3. The study represents a thorough spectroscopic characterization of high-valent Cu complexes and sheds light on the PCET reactivity studies of Cu(III) complexes.

Co-substituted Ca–La magnetoplumbite ferrite microwave absorbers at 100 GHz

Millimeter wave absorption exceeding 70 GHz has been performed in a Co-substituted Ca–La magnetoplumbite (M-type) ferrite. A polymerized complex method was used to increase the substitution of La and Co ions in the M-type ferrite. The increase in the magnetic anisotropy field combined with the remaining significant saturation magnetization results in good magnetic resonance absorption in the millimeter range of 70–100 GHz. Above 70 GHz, good millimeter wave absorption of more than −20 dB was achieved in 0.25 mm thickness plates of Ca0.46La0.54Fe11Co0.28O19-η and Ca0.42La0.58Fe11Co0.58O19-η. Highly Co-substituted Ca–La M-type ferrites may, thus, be promising candidates for magnetic absorption materials operating in frequencies of up to 100 GHz.

Degradation Mechanism of Metal–Organic Framework Drug Nanocarriers Studied by Solid-State Nuclear Magnetic Resonance and X-ray Absorption Near-Edge Structure Spectroscopy

Degradation Mechanism of Metal–Organic Framework Drug Nanocarriers Studied by Solid-State Nuclear Magnetic Resonance and X-ray Absorption Near-Edge Structure Spectroscopy

The nanomechanical properties of non-crosslinked calcium aluminosilicate hydrate: The influences of tetrahedral Al and curing age

Calcium aluminosilicate hydrate (C-A-S-H) is the binding phase of both blended cement-based and alkali-activated materials. The intrinsic mechanical properties of non-cross-linked C-A-S-H are important while experimentally unvalidated. Here, the properties are for the first time measured using high-pressure X-ray diffraction. The incompressibility and bulk modulus K0 of C-A-S-Hs are correlated to their nanostructure and stability using nuclear magnetic resonance and X-ray absorption spectroscopies. Al coordination in stable C-A-S-H (Al/Si = 0.1) cured for 546 days is purely tetrahedral (AlIV), while in metastable C-A-S-H (Al/Si = 0.05) cured for only 182 days is both AlIV and pentahedral (AlV). The stable C-A-S-H is stiffer along the a,b,c-axis with higher K0 relative to C-S-H. Short-curing-induced metastable C-A-S-H (Al/Si = 0.05) shows expanded interlayer and softer c-axis, thus lower K0 than C-S-H and the stable C-A-S-H. Our results highlight the stiffening effect of AlIV incorporation and the negative influences of insufficient curing on the nanomechanical properties of non-cross-linked C-A-S-H at Ca/Si = 1.

Relationship between chloride migration coefficient and pore structures of long-term water curing concrete

The chloride migration coefficient is a useful index for quality control and durability design of reinforced concrete. This paper explored the relationship between chloride migration coefficient and pore structures of long-term water curing concrete. Low-field nuclear magnetic resonance (NMR) and water absorption were used to probe the total porosity and pore sizes distribution. An appropriate dosage of supplementary cementitious materials reduced the total porosity and increased the proportion of capillary pores in the concrete. Fly ash, slag and silica fume effectively increased the capillary pores in the concrete. The capillary pores of 0.35 water to cement ratio concrete with 25% slag was 20% higher than that of the 0.35 water to cement ratio plain concrete at 415 days. The capillary pores of 0.45 water to cement ratio concrete with 25% slag was 32% higher than that of the 0.45 water to cement ratio plain concrete at 415 days. The big pores in the concrete were significantly reduced. According to our analysis, pores were divided into four parts: 0 ∼ R12, R12 ∼ R23, R23 ∼ 50 μm, ≥ 50 μm. R12 and R23 were the sequential minimum distribution frequency pore sizes in the pore size distribution figures tested by the Low-field NMR method. The chloride migration coefficient was dependent on the porosity which included the pore size over R23 and the pore radius R3. R3 was the biggest pore size among several peak frequency pore sizes in the figure of pore size distribution. Their relationship was non-linear. This meant the controlling factors of chloride migration in the concrete were larger capillary pores, voids and the porosity made up of these large capillary pores and voids. The persistent evolution of pores determined the permeability of concrete in late age.

Quinoline based thiosemicarbazones as colorimetric chemosensors for fluoride and cyanide ions and DFT studies

High toxicity and extensive accessibility of fluoride and cyanide ions in diverse environmental media encouraged attention for scheming well-organized probes for their detection. Keeping in mind we have designed and synthesized thiosemicarbazone-based chemosensors RB-1, RB-2 and RB-3 for the detection of fluoride and cyanide ions. The structural elucidation of the synthesized chemosensors is done by employing different analytical techniques including nuclear magnetic resonance and electronic absorption specrtoscopies. Admirable detection limit, binding constant and fast response time (2 s) to F− and CN− ions enlarged the applications of these chemosensors. Additional confirmation of the sensing ability of these chemosensors is derived from DFT and TDDFT calculations with M06/6-311G(d,p) method by performing FMO, UV–Vis, QTAIM and global reactivity parameters elucidation. Overall results point out that investigated chemosensors are suitable candidates for sensing the F− ions. These chemosensors were successfully applied to detect F− ions in a commercial toothpaste sample.

Cu2+ and Cu3+ acceptors in β-Ga2O3 crystals: A magnetic resonance and optical absorption study

Electron paramagnetic resonance (EPR) and optical absorption are used to characterize Cu2+ (3d9) and Cu3+ (3d8) ions in Cu-doped β-Ga2O3. These Cu ions are singly ionized acceptors and neutral acceptors, respectively (in semiconductor notation, they are Cu− and Cu0 acceptors). Two distinct Cu2+ EPR spectra are observed in the as-grown crystals. We refer to them as Cu2+(A) and Cu2+(B). Spin-Hamiltonian parameters (a g matrix and a 63,65Cu hyperfine matrix) are obtained from the angular dependence of each spectrum. Additional electron-nuclear double resonance (ENDOR) experiments on Cu2+(A) ions give refined 63Cu and 65Cu hyperfine matrices and provide information about the nuclear electric quadrupole interactions. Our EPR results show that the Cu2+(A) ions occupy octahedral Ga sites with no nearby defect. The Cu2+(B) ions, also at octahedral Ga sites, have an adjacent defect, possibly an OH− ion, an oxygen vacancy, or an H− ion trapped within an oxygen vacancy. Exposing the crystals at room temperature to 275 nm light produces Cu3+ ions and reduces the number of Cu2+(A) and Cu2+(B) ions. The Cu3+ ions have an S = 1 EPR spectrum and are responsible for broad optical absorption bands peaking near 365, 422, 486, 599, and 696 nm. An analysis of loops observed in the Cu3+ EPR angular dependence gives 2.086 for the g value and 22.18, 3.31, and −25.49 GHz for the principal values of D (the fine-structure matrix). Thermal anneal studies above room temperature show that the Cu3+ ions decay and the Cu2+ ions recover between 75 and 375 °C.

An Atomistic Model Describing the Structure and Morphology of Cu-Doped C-S-H Hardening Accelerator Nanoparticles.

Calcium silicate hydrate (C-S-H) is the main binding phase in Portland cement. The addition of C-S-H nanoparticles as nucleation seeds has successfully been used to accelerate the hydration process and the precipitation of binding phases either in conventional Portland cement or in alternative binders. Indeed, the modulation of the hydration kinetics during the early-stage dissolution-precipitation reactions, by acting on the nucleation and growth of binding phases, improves the early strength development. The fine-tuning of concrete properties in terms of compressive strength and durability by designed structural modifications can be achieved through the detailed description of the reaction products at the atomic scale. The nano-sized, chemically complex and structurally disordered nature of these phases hamper their thorough structural characterization. To this aim, we implement a novel multi-scale approach by combining forefront small-angle X-ray scattering (SAXS) and synchrotron wide-angle X-ray total scattering (WAXTS) analyses for the characterization of Cu-doped C-S-H nanoparticles dispersed in a colloidal suspension, used as hardening accelerator. SAXS and WAXTS data were analyzed under a unified modeling approach by developing suitable atomistic models for C-S-H nanoparticles to be used to simulate the experimental X-ray scattering pattern through the Debye scattering equation. The optimization of atomistic models against the experimental pattern, together with complementary information on the structural local order from 29Si solid-state nuclear magnetic resonance and X-ray absorption spectroscopy, provided a comprehensive description of the structure, size and morphology of C-S-H nanoparticles from the atomic to the nanometer scale. C-S-H nanoparticles were modeled as an assembly of layers composed of 7-fold coordinated Ca atoms and decorated by silicate dimers and chains. The structural layers are a few tens of nanometers in length and width, with a crystal structure resembling that of a defective tobermorite, but lacking any ordering between stacking layers.

Structure and Magnetism of Few-Layer Nanographene Clusters in Carbon Microspheres

The solid-phase pyrolysis method was used to synthesize carbon microspheres, consisting of clusters of few-layer nanographene and amorphous carbon. Powders of metal-free phthalocyanine and polyethylene served as precursors of the synthesized carbon microspheres. The pyrolysis products of metal-free phthalocyanine samples SPc(700) and SPc(900) contained 4 and 1 atom % nitrogen, respectively, replacing carbon in the graphene lattice in pyrrolic and pyridinic coordination. There are no impurity nitrogen atoms in the products of the pyrolysis of polyethylene. The SPc(700) sample showed strong paramagnetism with a concentration of paramagnetic centers of ∼5 × 1019 spin g–1 and a temperature-independent diamagnetism susceptibility of χDia = −1 × 10–6 emu g–1 Oe–1. In a temperature range of 5–300 K, ferromagnetism was also revealed with a temperature dependence similar to that of ferromagnetic cluster spin glasses, with maximum saturation magnetization, MSFM = 3 × 10–2 emu g–1, and coercive force, Hc = 400 Oe, at Tsg = 25 K. It was shown that the ferromagnetism in the SPc(700) sample is due to π(p)-electrons of zigzag-type edge states as well as nitrogen impurity atoms. The experimental results are interpreted based on the temperature dependence of the spin correlation length. It was revealed that the temperature dependence of the integral of the magnetic resonance absorption intensity closely resembles the temperature behavior of the saturation magnetization of the ferromagnetic component.

Enhanced light harvesting and charge separation of carbon and oxygen co-doped carbon nitride as excellent photocatalyst for hydrogen evolution reaction

Solar-driven water splitting has been regarded as a promising strategy for renewable hydrogen production. Among many semiconductor photocatalysts, graphitic carbon nitride (g-C3N4) has received tremendous attention due to its two-dimensional structure, appropriate band gap and decent photocatalytic activity. However, it suffers severe charge recombination problems, affecting its practical performance. In this work, we demonstrated that dual heteroatoms (C and O) doped g-C3N4 can exhibit about 3 times higher catalytic performance for hydrogen evolution than that of the normal g-C3N4 with a hydrogen evolution rate reaching 2595.4 umol g−1h−1 and an apparent quantum efficiency at 420 nm of 16.6%. The heteroatoms (C and O) doped g-C3N4 photocatalyst also exhibited superior removal performance when removing Rhodamine B (RhB) . X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (ssNMR) and X-ray absorption near-edge structure (XANES) spectroscopy reveal that the carbon and oxygen dopants replace the sp2 nitrogen and bridging N atom, respectively. DFT calculations demonstrate the codoping of carbon and oxygen- induced the generation of mid-gap state, leading to the improvement of light harvesting and charge separation.

"In-water" Dehydration Reaction of an Aromatic Diol on an Inorganic Surface.

The effect of a synthetic saponite surface on the "in-water" dehydration reaction of diol was examined using 4-formyl-1-methylquinolinium salt (MQu+) as a substrate. The equilibrium between aldehyde (MQu+-Aldehyde) and diol (MQu+-Diol) was affected by the surrounding environment. The equilibrium behavior was observed by 1H nuclear magnetic resonance (NMR) and UV-vis absorption measurements. Although MQu+ was completely in the form of MQu+-Diol in water, the equilibrium almost shifted to the MQu+-Aldehyde side when MQu+ was adsorbed on the saponite surface in water. In addition, the MQu+-Aldehyde ratio depended on the negative charge density of saponite. The factors that determine MQu+-Aldehyde: MQu+-Diol ratio were discussed from the thermodynamic analysis of the system. These data indicate that the electrostatic interaction between the charged saponite surface and MQu+ stabilized the aldehyde side enthalpically and destabilized it entropically. The major reason for these results is considered to be the difference in adsorption stabilization between MQu+-Aldehyde and MQu+-Diol on saponite surfaces.

Recent advances of the ionic chiral selectors for chiral resolution by chromatography, spectroscopy and electrochemistry.

Ionic chiral selectors have been received much attention in the field of asymmetric catalysis, chiral recognition, and preparative separation. It has been shown that the addition of ionic chiral selectors can enhance the recognition efficiency dramatically due to the presence of multiple intermolecular interactions, including hydrogen bond, π-π interaction, van der Waals force, electrostatic ion-pairing interaction, and ionic-hydrogen bond. In the initial research stage of the ionic chiral selectors, most of work center on the application in chromatographic separation (capillary electrophoresis, high-performance liquid chromatography, and gas chromatography). Differently, more and more attention has been paid on the spectroscopy (nuclear magnetic resonance, fluorescence, ultraviolet and visible absorption spectrum, and circular dichroism spectrum) and electrochemistry in recent years. In this tutorial review as regards the ionic chiral selectors, we discuss in detail the structural features, properties, and their application in chromatography, spectroscopy, and electrochemistry.

Relative proportions of organic carbon functional groups in biochars as influenced by spectral data collection and processing

Solid-state 13C Nuclear Magnetic Resonance (NMR) and synchrotron-based X-ray Absorption Near-Edge Structure (XANES) have applications for determining the relative proportions of organic C functional groups in materials. Spectral data obtained by NMR is typically processed using integration (INTEG) whereas XANES spectral data is typically processed using deconvolution (DECONV). The objective of this study was to examine the impact of spectral data collection and processing on the estimated relative proportions of organic C functional groups in biochars. Biochars showed large variations in aromatic C (45–97%), alkyl C (0–23%), O-alkyl C (1–41%), phenolic C (0–20%) and carboxylic C (0–20%). NMR had a better ability than XANES to differentiate % aromatic C across biochars, and the mean % aromatic C was always greater for NMR-INTEG and NMR-DECONV than for XANES-INTEG or XANES-DECONV. NMR-INTEG showed significant associations with NMR-DECONV and XANES-INTEG for % aromatic C and alkyl C, but there were no significant associations between NMR and XANES for % O-alkyl C, phenolic C and carboxylic C. As well, there was no association between NMR-INTEG and XANES-DECONV for any organic C functional group, and in some cases, spectral data collection and processing influenced the quantification of organic C functional groups in a given biochar to the extent that the differences observed were as large as differences observed between biochars when analyzed using the same spectral data collection and processing technique. We conclude that great caution must be taken when comparing studies that determined organic C functional groups in materials using NMR-INTEG versus XANES-DECONV.

Subsoils\u2014a sink for excess fertilizer P but a minor contribution to P plant nutrition: evidence from long-term fertilization trials

BackgroundThe phosphorus (P) stocks of arable subsoils not only influence crop production but also fertilizer P sequestration. However, the extent of this influence is largely unknown. This study aimed to (i) determine the extent of P sequestration with soil depth, (ii) analyze P speciation after long-term P fertilization, and (iii) compare soil P tests in predicting crop yields. We analyzed four long-term fertilizer trials in Germany to a depth of 90 cm. Treatments received either mineral or organic P, or a combination of both, for 16 to 113 years. We determined inorganic and organic P pools using sequential extraction, and P speciation using 31P nuclear magnetic resonance (NMR) and X-ray absorption near edge structure (XANES) spectroscopy. In addition, we applied three P soil tests, double-lactate (DL), calcium acetate lactate (CAL), and diffusive gradients in thin films (DGT).ResultsThe results suggested that plants are capable of mobilizing P from deeper soil layers when there is a negative P budget of the topsoil. However, fertilization mostly only showed insignificant effects on P pools, which were most pronounced in the topsoil, with a 1.6- to 4.4-fold increase in labile inorganic P (Pi; resin-P, NaHCO3–Pi) after mineral fertilization and a 0- to 1.9-fold increase of organic P (Po; NaHCO3–Po, NaOH–Po) after organic P fertilization. The differences in Po and Pi speciation were mainly controlled by site-specific factors, e.g., soil properties or soil management practice rather than by fertilization. When modeling crop yield response using the Mitscherlich equation, we obtained the highest R2 (R2 = 0.61, P < 0.001) among the soil P tests when using topsoil PDGT. However, the fit became less pronounced when incorporating the subsoil.ConclusionWe conclude that if the soil has a good P supply, the majority of P taken up by plants originates from the topsoil and that the DGT method is a mechanistic surrogate of P plant uptake. Thus, DGT is a basis for optimization of P fertilizer recommendation to add as much P fertilizer as required to sustain crop yields but as low as necessary to prevent harmful P leaching of excess fertilizer P.