Synthesis of struvite-enriched slow-release fertilizer using magnesium-modified biochar: Desorption and leaching mechanisms.

To improve the retention and slow-release abilities of nitrogen (N) and phosphorus (P), an 82 %-purity struvite fertilizer (MAP-BC) was synthesized using magnesium-modified biochar and a solution with a 2:1 concentration ratio of NH4+ to PO43- at a pH of 8. Batch microscopic characterizations and soil column leaching experiments were conducted to study the retention and slow-release mechanisms and desorption kinetics of MAP-BC. The slow-release mechanism revealed that the dissolution rate of high-purity struvite was the dominant factor of NP slow release. The re-adsorption of NH4+ and PO43- by biochar and unconsumed MgO prolonged slow release. Mg2+ ionized by MgO could react with PO43- released from struvite to form Mg3(PO4)2. The internal biochar exhibited electrostatic attraction and pore restriction towards NH4+, while magnesium modification and nutrient loading formed a physical antioxidant barrier that ensured long-term release. The water diffusion experiment showed a higher cumulative release rate for PO43- compared to NH4+, whereas in soil column leaching, the trend was reversed, suggesting that soil's competitive adsorption facilitated the desorption of NH4+ from MAP-BC. During soil leaching, cumulative release rates of NH4+ and PO43- from chemical fertilizers were 3.55-3.62 times faster than those from MAP-BC. The dynamic test data for NH4+ and PO43- in MAP-BC fitted the Ritger-Peppas model best, predicting release periods of 163 days and 166 days, respectively. The leaching performances showed that MAP-BC reduced leaching solution volume by 5.58 % and significantly increased soil large aggregates content larger than 0.25 mm by 24.25 %. The soil nutrients retention and pH regulation by MAP-BC reduced leaching concentrations of NP. Furthermore, MAP-BC significantly enhanced plant growth, and it is more suitable as a NP source for long-term crops. Therefore, MAP-BC is expected to function as a long-term and slow-release fertilizer with the potential to minimize NP nutrient loss and replace part of quick-acting fertilizer.

Adsorption of phosphate over a novel magnesium-loaded sludge-based biochar.

The production of sludge-based biochar to recover phosphorus (P) from wastewater and reuse the recovered phosphorus as agricultural fertilizer is a preferred process. This article mainly studied the removal of phosphate (PO4-P) from aqueous solution by synthesizing sludge-based biochar (MgSBC-0.1) from anaerobic fermentation sludge treated with magnesium (Mg)-loading-modification, and compared it with unmodified sludge-based biochar (SBC). The physicochemical properties, adsorption efficiency, and adsorption mechanism of MgSBC-0.1 were studied. The results showed that the surface area of MgSBC-0.1 synthesized increased by 5.57 times. The material surface contained MgO, Mg(OH)2, and CaO nanoparticles. MgSBC-0.1 can effectively remove phosphate in the initial solution pH range of 3.00-7.00, with a fitted maximum phosphorus adsorption capacity of 379.52 mg·g-1. The adsorption conforms to the pseudo second-order kinetics model and Langmuir isotherm adsorption curve. The characterization of the adsorbed composite material revealed the contribution of phosphorus crystal deposition and electrostatic attraction to phosphorus absorption.

Efficient Adsorption of Nitrogen and Phosphorus in Wastewater by Biochar.

Nitrogen and phosphorus play essential roles in ecosystems and organisms. However, with the development of industry and agriculture in recent years, excessive N and P have flowed into water bodies, leading to eutrophication, algal proliferation, and red tides, which are harmful to aquatic organisms. Biochar has a high specific surface area, abundant functional groups, and porous structure, which can effectively adsorb nitrogen and phosphorus in water, thus reducing environmental pollution, achieving the reusability of elements. This article provides an overview of the preparation of biochar, modification methods of biochar, advancements in the adsorption of nitrogen and phosphorus by biochar, factors influencing the adsorption of nitrogen and phosphorus in water by biochar, as well as reusability and adsorption mechanisms. Furthermore, the difficulties encountered and future research directions regarding the adsorption of nitrogen and phosphorus by biochar were proposed, providing references for the future application of biochar in nitrogen and phosphorus adsorption.

Response of tree growth to nutrient addition is size dependent in a subtropical forest.

Understanding how nutrient addition affects the tree growth is critical for assessing forest ecosystem function and processes, especially in the context of increased nitrogen (N) and phosphorus (P) deposition. Subtropical forests are often considered N-rich and P-poor ecosystems, but few existing studies follow the traditional "P limitation" paradigm, possibly due to differences in nutrient requirements among trees of different size classes. We conducted a three-year fertilization experiment with four treatments (Control, N-treatment, P-treatment, and NP-treatment). We measured soil nutrient availability, leaf stoichiometry, and relative growth rate (RGR) of trees across three size classes (small, medium and large) in 64 plots. We found that N and NP-treatments increased the RGR of large trees. P-treatment increased the RGR of small trees. RGR was mainly affected by N addition, the total effect of P addition was only 10 % of that of N addition. The effect of nutrient addition on RGR was mainly regulated by leaf stoichiometry. This study reveals that nutrient limitation is size dependent, indicating that continuous unbalanced N and P deposition will inhibit the growth of small trees and increase the instability of subtropical forest stand structure, but may improve the carbon sink function of large trees.

Structural design of La2(CO3)3 loaded magnetic biochar for selective removal of phosphorus from wastewater.

High levels of phosphorus released into the environment can cause eutrophication issues in wastewater, therefore discharge concentrations of such element are regulated in many countries. This study addresses the pressing need for effective phosphorus removal methods by developing a novel La2(CO3)3 and MnFe2O4 loaded biochar composite (LMB). A remarkable adsorption capacity towards the three forms of phosphorus from wastewater, including phosphate, phosphite, and etidronic acid monohydrate (as a representative of organic phosphorus), was exhibited by LMB (88.20, 16.35, and 15.95 mg g-1, respectively). The high saturation magnetization value (50.17 emu g-1) highlighted the easy separability and recyclability of the adsorbent. The adsorption process was well described by the Langmuir isotherm model and the pseudo-second-order kinetic model, which mainly involved chemisorption. Characterization results confirm the effective loading of La2(CO3)3 with ligand exchange and electrostatic attraction identified as the primary mechanisms. Importantly, the LMB demonstrated exceptional selectivity for phosphorus in wastewater samples containing various substances, exhibiting minimal interference from competing ions (Cl-, NO3-, SO42-, and CO32-). These findings enhance the understanding of LMB's application in efficient wastewater phosphorus removal. Holding significant promise in wastewater remediation, the LMB acts as an effective adsorbent, contributing substantially to the prevention and control of various types of phosphorus pollutants, thereby mitigating wastewater eutrophication.

Recent advances in ambient-stable black phosphorus materials for artificial catalytic nitrogen cycle in environment and energy.

Nitrogen cycle is crucial for the Earth's ecosystem and human-nature coexistence. However, excessive fertilizer use and industrial contamination disrupt this balance. Semiconductor-based artificial nitrogen cycle strategies are being actively researched to address this issue. Black phosphorus (BP) exhibits remarkable performance and significant potential in this area due to its unique physical and chemical properties. Nevertheless, its practical application is hindered by ambient instability. This review covers the synthesis methods of BP materials, analyzes their instability factors under environmental conditions, discusses stability improvement strategies, and provides an overview of the applications of ambient-stable BP materials in nitrogen cycle, including N2 fixation, NO3- reduction, NOx removal and nitrides sensing. The review concludes by summarizing the challenges and prospects of BP materials in the nitrogen cycle, offering valuable guidance to researchers.

Effects of redox on the phosphorus removal ability of iron-rich phosphorus sorption materials.

Iron-rich phosphorus (P) sorption materials (PSMs) are often used in P removal structures, a best management practice able to sequester dissolved P from surface runoff, subsurface drainage, and wastewater. The use of bottom-upward flow in these structures is of great interest, but it creates an intrinsic complication: the presence of stagnant water between flow events may cause structures to develop anoxic conditions. It is unknown whether the redox sensitivity of iron (Fe), the predominant element in Fe-rich PSMs, will affect P binding under anoxic conditions. Understanding the potential impact of intermittent anoxic conditions on the solubility of previously adsorbed P is imperative for determining the feasibility of the bottom-up flow design. The objective of this research was to investigate the (1) development of anoxic conditions in the presence of Fe-rich PSM and tile drainage, (2) Fe-bound P mobilization and solubility, and (3) changes in P sorption capacity of Fe-rich PSMs after oxic conditions are restored. Three Fe-rich PSMs were tested in batch incubation studies: acid mine drainage residual, Fe-coated alumina, and steel metal shavings. Non-treated and P-treated PSM samples were incubated in biogeochemical reactors for as long as necessary to reach Eh = -200 mV. After incubation, dissolved P concentrations in P-treated samples and non-treated samples were similarly low, indicating stability of P retention of PSMs under anoxic conditions. The P removal ability of non-treated PSMs before and after undergoing incubation was not significantly altered, as determined in flow-through experiments. Potentially harmful trace metals were not detected in the incubated solutions. Our research shows that the development of anoxic conditions does not significantly impact PSMs Fe-bound P dissolution, and the P removal ability of PSMs persists after oxic conditions are reestablished.

The combined effects of lanthanum-modified bentonite and Vallisneria spiralis on phosphorus, dissolved organic matter, and heavy metal(loid)s.

The use of lanthanum-modified bentonite (LMB) combined with Vallisneria spiralis (V∙s) (LMB + V∙s) is a common method for controlling internal phosphorus (P) release from sediments. However, the behaviors of iron (Fe) and manganese (Mn) under LMB + V∙s treatments, as well as the associated coupling effect on P, dissolved organic matter (DOM), and heavy metal(loid)s (HMs), require further investigations. Therefore, we used in this study a microelectrode system and high-resolution dialysis technology (HR-Peeper) to study the combined effects of LMB and V∙s on P, DOM, and HMs through a 66-day incubation experiment. The LMB + V∙s treatment increased the sediment DO concentration, promoting in-situ formations of Fe (III)/Mn (IV) oxyhydroxides, which, in turn, adsorbed P, soluble tungsten (W), DOM, and HMs. The increase in the concentrations of HCl-P, amorphous and poorly crystalline (oxyhydr) oxides-bound W, and oxidizable HMs forms demonstrated the capacity of the LMB + V∙s treatment to transform mobile P, W, and other HMs forms into more stable forms. The significant positive correlations between SRP, soluble W, UV254, and soluble Fe (II)/Mn, and the increased concentrations of the oxidizable HMs forms suggested the crucial role of the Fe/Mn redox in controlling the release of SRP, DOM, and HMs from sediments. The LMB + V∙s treatment resulted in SRP, W, and DOM removal rates of 74.49, 78.58, and 54.78 %, which were higher than those observed in the control group (without LMB and V∙s applications). On the other hand, the single and combined uses of LMB and V·s influenced the relative abundances of the sediment microbial communities without exhibiting effects on microbial diversity. This study demonstrated the key role of combined LMB and V∙s applications in controlling the release of P, W, DOM, and HMs in eutrophic lakes.

Nutrient transport, shear strength and hydraulic characteristics of topsoils amended with mulch, compost and biosolids.

Anthropogenic disturbance of soils can disrupt soil structure, diminish fertility, alter soil chemical properties, and cause erosion. Current remediation practices involve amending degraded urban topsoils lacking in organic matter and nutrition with organic amendments (OA) to enhance vegetative growth. However, the impact of OAs on water quality and structural properties at rates that meet common topsoil organic matter specifications need to be studied and understood. This study tested three commonly available OAs: shredded wood mulch, leaf-based compost, and class A Exceptional Quality stabilized sewage sludge (or biosolids) for nutrient (nitrogen and phosphorus) water quality, soil shear strength, and hydraulic properties, through two greenhouse tub studies. Findings showed that nitrogen losses to leachate were greater in the biosolids amended topsoils compared to leaf-compost, mulch amended topsoils, and control treatments. Steady-state mean total nitrogen (N) concentrations from biosolids treatment exceeded typical highway stormwater concentrations by at least 25 times. Soil total N content combined with the carbon:nitrogen ratio were identified to be the governing properties of N leaching in soils. Study soils, irrespective of the type of amendment, reduced the applied (tap) water phosphorus (P) concentration of ∼0.3 mg-P/L throughout the experiment. Contrary to the effects on N leaching, P was successfully retained by the biosolids amendment, due to the presence of greater active iron contents. A breakthrough mechanism for P was observed in leaf compost amended soil, where the effluent concentrations of P continued to increase with each rainfall application, possibly due to an saturation of soil adsorption sites. The addition of OAs also improved the strength and hydraulic properties of soils. The effective interlocking mechanisms between the soil and OA surfaces could provide soil its required strength and stability, particularly on slopes. OAs also improved soil fertility to promote turf growth. Presence of vegetative root zones can further reinforce the soil and control erosion.

Utilizing waste eggshells as a calcium precursor for contact precipitation of phosphorus from digested sludge centrate.

Phosphorus (P) recovery from wastewater is an essential component of the global P cycle. A contact precipitation process using chicken eggshells as a calcium (Ca) precursor was used to recover P from synthetic wastewater and real digested sludge centrate. Up to 96.4 % of P could be recovered from the digested sludge centrate after three repeated cycles of the contact precipitation process. In addition, 36.1 % of total chemical oxygen demand and 37.6 % of total ammonia nitrogen were removed from the centrate. Finally, most of the precipitates could be collected by a simple washing step. Scanning electron microscopy-energy dispersive spectroscopy and x-ray diffraction results indicated that the eggshells played three roles in this process: Ca source, precipitation substrate, and filter medium. Precipitates were mainly brushite. This research provides a new perspective on P recovery from wastewater using waste eggshells, and if further optimized, has a potential for practical future applications.

Efficient removal of phosphorus and nitrogen from aquatic environment using sepiolite-MgO nanocomposites: preparation, characterization, removal performance, and mechanism.

Excessive phosphorus will lead to eutrophication in aquatic environment; the efficient removal of phosphorus is crucial for wastewater engineering and surface water management. This study aimed to fabricate a nanorod-like sepiolite-supported MgO (S-MgO) nanocomposite with high specific surface area for efficient phosphate removal using a facile microwave-assisted method and calcining processes. The impact of solution pH, adsorbent dosage, contact time, initial phosphate concentrations, Ca2+ addition, and N/P ratio on the phosphate removal was extensively examined by the batch experiments. The findings demonstrated that the S-MgO nanocomposite exhibited effective removal performance for low-level phosphate (0 ~ 2.0 mM) within the pH range of 3.0 ~ 10.0. Additionally, the nanocomposite can synchronously remove phosphate and ammonium in high-level nutrient conditions (> 2.0 mM), with the maximum removal capacities of 188.49 mg P/g and 89.78 mg N/g. Quantitative and qualitative analyses confirmed the successful harvesting of struvite in effluent with high-phosphate concentrations, with the mechanisms involved attributed to a synergistic combination of sorption and struvite crystallization. Due to its proficient phosphate removal efficiency, cost-effectiveness, and substantial removal capacity, the developed S-MgO nanocomposite exhibits promising potential for application in phosphorus removal from aquatic environments.

Lignite-steel slag constructed wetland with multi-functionality and effluent reuse.

Constructed wetlands (CWs) are widely used to treat wastewater, while innovative studies are needed to support resource conservation, enhance multi-functionality, and improve the effectiveness of effluent usage. This study assessed the potential of CW's multiple functions by combining low-rank coal (lignite) and industrial waste (steel slag) in different configurations as CW substrates. The results of scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and metagenomic sequencing showed that the experimental treatment with lignite and steel slag mixtures had the highest multi-functionality, including efficient nutrient removal and carbon sequestration, as well as hydroponic crop production. Lignite and steel slag were mixed to form lignite-steel slag particle clusters, where Ca2+ dissolved on the surface of steel slag was combined with PO43- in wastewater to form Ca3(PO4)2 precipitation for phosphorus removal. A biofilm grew on the surface of lignite in this cluster, and OH- released from steel slag promoted lignite to release fulvic acid, which provided a carbon source for heterotrophic microorganisms and promoted denitrification. Moreover, fulvic acid enhanced carbon sequestration in CWs by increasing the biomass of Phragmites australis. The effluent from lignite-steel slag CW increased cherry tomato yield and quality while saving N and P applications. These results provide new ideas for the "green" and economic development of CW technology.

Migration of phosphorus in pig manure during pyrolysis process and slow-release mechanism of biochar in hydroponic application.

Pyrolysis is an effective method for treating of livestock and poultry manure developed in recent years. It can completely decompose pathogens and antibiotics, stabilize heavy metals, and enrich phosphorus (P) in biochar. To elucidate the P migration mechanism under different pig manure pyrolysis temperatures, sequential fractionation, solution 31P nuclear magnetic resonance, X-ray photoelectron spectroscopy, X-ray diffraction, and K-edge X-ray absorption near-edge structure techniques were used to analyze the P species in pig manure biochar (PMB). The results indicated that most of the organic P in the pig manure was converted to inorganic P during pyrolysis. Moreover, the transformation to different P groups pathways was clarified. The phase transition from amorphous to crystalline calcium phosphate was promoted when the temperature was above 600 °C. The content of P extracted by hydrochloric acid, which was the long-term available P for plant uptake, increased significantly. PMB pyrolyzed at 600 °C can be used as a highly effective substitute for P source. It provides the necessary P species (e.g. water-soluble P.) and metal elements for the growth of water spinach plants, and which are slow-release comparing with the Hogland nutrient solution.

The impact of the distribution method for struvite (Crystal Green) on the chemical composition of soybean and their utility in animal nutrition.

One of the main factors considered in assessing the nutritional value of feed is its chemical composition, which can be modified by fertilization. Faced with reducing P resources, alternative sources of this element are being sought. Phosphorus is an essential nutrient in soybean cultivation. The aim of the study was to use an alternative source of phosphorus fertilizer and compare its impact on the chemical composition of soybean seeds with that of a traditional fertilizer (Super FOS DAR). The study investigated a range of factors in animal nutrition as well as the basic content of macro- and microelements. A pot experiment with the Abelina soybean variety was conducted at the Experimental Station of the Wroclaw University of Environmental and Life Sciences. The experiment considered two factors against the control: phosphorus fertilizer placement (band, broadcast) and different phosphorus fertilization (Super FOS DAR, Crystal Green). Use of struvite (Crystal Green)) caused positive changes in selected amino acids content and in the nutritional value of protein in soybean seeds; this can enhance the value of soybean seeds as well as increase certain macroelements and microelements. Phosphorus fertilizer significantly increased the content of lysine, leucine, valine, phenyloalanine and tyrosine. Band fertilization with struvite caused a significant increase in amino acids (lysine, leucine, valine, phenyloalanine and tyrosine) as well as in the nutritional value of protein (as measured by the essential amino acid index, protein efficiency ratio and biological value of the protein). Favorable changes under the influence of the application of struvite were recorded in the content of calcium, as well as phosphorus, iron, and manganese. The value of the struvite in the case of its use as phosphorus fertilizer is promising; however, it needs further study.

Staged purification of phosphogypsum using pH-dependent separation process.

Phosphogypsum (PG) is an industrial by-product of the transformation of phosphate rocks. For decades, PG has been a source of environmental concern due to the massive amount produced thus far, i.e., 7 billion tons, with a current production rate of 200-280 million tons per year. Phosphate minerals contain various impurities that precipitate and concentrate within PG. These impurities hinder PG usability in various sectors. This paper aims to purify PG using an innovative process based on staged valorization of PG. Initially, PG dissociation by ethylenediaminetetraacetic acid (EDTA) was optimized. After screening of different parameters and monitoring the ionic conductivity of solutions, it was disclosed that a pH-dependent solubilization process in the presence of EDTA resulted in high solubility of PG, up to 11.82 g/100 mL at pH > 11. Subsequently, a recovery of the purified PG by selective precipitation of calcium sulfate dihydrate (CSD) from obtained filtrate through pH adjustment to 3.5 were investigated. An abatement of 99.34% Cr, 97.15% Cd, 95.73% P2O5, 92.75% Cu, 92.38% Al2O3, 91.16% Ni, 74.58% Zn, 72.75% F, 61.43% MgO, 58.8% Fe2O3, 56.97% K2O, and 55.41% Ba was achieved. The process relied on the variation of EDTA chelation properties towards monovalent, divalent, and trivalent cations at different pHs. According to the findings of this study, a staged purification process in the presence of EDTA is an effective method for removing impurities from the industrial PG.

Assessment of phosphorus status in a calcareous soil receiving long-term application of chemical fertilizer and different forms of swine manures.

The continuous use of organic inputs in crop production calls for an improved understanding of how these inputs might alter soil phosphorus (P). This study assessed how the continuous application of different forms of swine manure influences the mechanism of P transformation and release potential. Soil samples were collected from a clay loam soil receiving no P or 100 kg P ha-1 applied as either chemical fertilizer (CHEM), swine liquid manure (SWL), composted swine manure (SWC), or solid swine manure (SWS) every other year for 16 years in a corn-soybean rotation. Available P increased in soils treated with the chemical and organic fertilizers. The greatest increase was found in the SWC and SWS and was closely related to a 1% increase in the organic C content, and 1.3- and 1.2-unit increase in the soil pH for SWC and SWS treatment, respectively. Nonlabile HCl-P form was also higher in SWC- and SWS-treated soils. Despite the similarities between SWS and SWC, SWS significantly had a lower maximum P sorption (Qmax ) and higher equilibrium P concentration at zero net sorption (EPCO) probably related to the higher organic NaOH-P. Similarly, higher organic NaOH-P together with lower cation exchange capacity, aluminum, and calcium explained the lower Qmax in SWL. This suggests that increase in organic NaOH-P forms limits the soil potential to retain P. Overall, the SWL treatment presents a unique effect on changes in soil property and P chemistry that warrants further investigation.

Contrasting fertilization response of soil phosphorus forms and functional bacteria in two newly reclaimed vegetable soils.

Fertilization is a pervasive approach to agricultural production enhancing vegetable nutrients such as phosphorus (P) absorption. However, unreasonable fertilization strategies result in high levels of residual P in vegetable planting systems. To better understand the mechanisms of soil phosphorus dynamics responding to inorganic/organic fertilization, we conducted a 3-year field experiment in two newly reclaimed vegetable fields in southern China. The results revealed that soil Olsen-P in CF (mineral fertilization) and OF (Combined application of organic and inorganic fertilizers) increased by approximately 210.6 % and 183.6 %, respectively, while stable P proportion decreased by approximately 9.2 % and 18.1 %, respectively, compared with CK. Combined application of organic and inorganic fertilizer increased the proportion of moderately labile P (NaOH-P) by 1-6 % in comparison with chemical fertilizer and facilitated the conversion from diester-P to monoester-P, indicating that applying pig manure enhanced the potential soil P bioavailability. Besides, organic-inorganic fertilization shaped a bacterial community with more connectivity and stability and changed keystone taxa related to the P transformation of the network. Phenylobacterium, Solirubrobacter, and Modestobacter were regarded as core genera for mobilizing soil phosphorus. However, residual P content in newly reclaimed soils under fertilization, especially for chemical fertilizer, remained non-negligible and may cause potential environmental risks. The partial least squares path modeling results demonstrated that fertilization management had both direct and indirect positive effects on P fraction through the improvement of soil nutrients e.g. total N and soil organic carbon, and bacterial community, while soil properties mainly determined the variation of soil P species. Our results provide comprehensive insights into the current status of legacy P forms and the vital role of fertilizer, key soil properties and bacteria in P dynamics in newly reclaimed vegetable field.

Urbanization increases the risk of phosphorus loss in sandy soils of tropical ecosystems.

Phosphorus (P) is naturally present in soils. However, urbanization can promote additional inputs of P into the soil that lead to saturation of the binding sites exceeding the maximum sorption capacity. Soils saturated with P act as important diffuse sources of pollution of water resources. The flow of P from the soil to aquatic ecosystems is an aggravating factor for water scarcity, especially in the semiarid region. Knowing phosphorus dynamics in the soil is essential to protect water quality and ensure its multiple uses. In this paper, a total of fifty soil samples, twenty-five from natural soils and twenty-five from urban soils, were evaluated for the effect of urbanization on P sorption characteristics and their relationship with the physical and chemical attributes of the soil. The soil samples were characterized physically and chemically, and the P sorption characteristics were obtained from the adjustment of Langmuir and Freundlich equations by nonlinear regression. Urbanization results in increased soil P saturation and reduced P sorption capacity. Our results show that the sandy texture of the soils studied had a standardizing effect on the soil's physical properties, maintaining, even after urbanization, the physical quality similar to natural soil. In contrast, pH (in water and KCl), base saturation, sodium saturation, potential acidity, exchangeable Al3+, exchangeable Mg2+, available P, and P-rem are valuable indicators in the segregation between natural and urban soils. The reduction of P sorption capacity in urban soils increases the risks related to P loads in aquatic ecosystems that experience urban expansion worldwide. These data serve as a basis for decision-making regarding the appropriate soil monitoring and management of urban expansion areas in watersheds to control P flow to aquatic systems.

Co-precipitation of iron and silicon: Reaction kinetics, elemental ratios and the influence of phosphorus.

A sufficient supply of dissolved silicon (DSi) relative to dissolved phosphorus (DP) may decrease the likelihood of harmful algal blooms in eutrophic waters. Oxidative precipitation of Fe(II) at oxic-anoxic interfaces may contribute to the immobilization of DSi, thereby exerting control over the DSi availability in the overlying water. Nevertheless, the efficacy of DSi immobilization in this context remains to be precisely determined. To investigate the behavior of DSi during Fe(II) oxidation, anoxic solutions containing mixtures of aqueous Fe(II), DSi, and dissolved phosphorus (DP) were exposed to dissolved oxygen (DO) in the batch system. The experimental data, combined with kinetic reaction modeling, indicate that DSi removal during Fe(II) oxidation occurs via two pathways. At the beginning of the experiments, the oxidation of Fe(II)-DSi complexes induces the fast removal of DSi. Upon complete oxidation of Fe(II), further DSi removal is due to adsorption to surface sites of the Fe(III) oxyhydroxides. The presence of DP effectively competes with DSi via both of these pathways during the initial and later stages of the experiments, with as a result more limited removal of DSi during Fe(II) oxidation. Overall, we conclude that at near neutral pH the oxidation of Fe(II) has considerable capacity to immobilize DSi, where the rapid homogeneous oxidation of Fe(II)-DSi results in greater DSi removal compared to surface adsorption. Elevated DP concentration, however, effectively outcompetes DSi in co-precipitation interactions, potentially contributing to enhanced DSi availability within aquatic systems.

Mapping Phosphorus Availability in Soil at a Large Scale and High Resolution Using Novel Diffusive Gradients in Thin Films Designed for X-ray Fluorescence Microscopy.

A novel binding layer (BL) as part of the diffusive gradients in thin films (DGT) technique was developed for the two-dimensional visualization and quantification of labile phosphorus (P) in soils. This BL was designed for P detection by synchrotron-based X-ray fluorescence microscopy (XFM). It differs from the conventional DGT BL as the hydrogel is eliminated to overcome the issue that the fluorescent X-rays of P are detected mainly from shallow sample depths. Instead, the novel design is based on a polyimide film (Kapton) onto which finely powdered titanium dioxide-based P binding agent (Metsorb) was applied, resulting in superficial P binding only. The BL was successfully used for quantitative visualization of P diffusion from three conventional P fertilizers applied to two soils. On a selection of samples, XFM analysis was confirmed by quantitative laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The XFM method detected significant differences in labile P concentrations and P diffusion zone radii with the P fertilizer incubation, which were explained by soil and fertilizer properties. This development paves the way for fast XFM analysis of P on large DGT BLs to investigate in situ diffusion of labile P from fertilizers and to visualize large-scale P cycling processes at high spatial resolution.