Search Results (16)

Organic phosphorus (OP) constitutes an important and chemically diverse fraction of total phosphorus (TP) in aquatic environments, yet its removal mechanisms in substrate-based treatment systems remain insufficiently understood. In particular, the relative contributions of adsorption and microbial transformation to OP removal and their coupling effects are still unclear. To address this issue, gravel-, sludge-, and sludge biochar-based biofilters were operated under controlled phosphorus inputs with varying OP/inorganic phosphate (IP) compositions. Phosphorus removal performance, effluent phosphorus speciation, phosphatase activity, and microbial community characteristics were systematically analyzed to distinguish physicochemical and biological pathways. Results indicated that phosphorus removal was dominated by adsorption at early operational stages, with comparable performance across substrates. As the operation progressed, sludge-based substrates exhibited more stable removal than gravel, attributable to stronger Fe/Al-associated adsorption. Biologically active sludge biochar systems consistently maintained higher TP removal efficiencies (87.1–93.3%) than abiotic systems. Phosphatase-mediated OP mineralization governed phosphorus speciation transformation, while effective removal depended on subsequent immobilization of transformation products. Overall, the results demonstrate that efficient OP removal relies on a coupled bio–physicochemical mechanism, in which microbial transformation and substrate adsorption act synergistically. This insight offers guidance on optimizing phosphorus control in biofilters and constructed wetlands (CWs), especially for robust biofilters and CWs designed to treat OP-rich wastewaters. Full article

Phosphogypsum (PG) and phosphorus tailings (PT) are bulk solid wastes generated by the phosphorus chemical industry whose stockpiling poses significant environmental risks and represents a waste of resources. To achieve the goals of “treating waste with waste” and large-scale disposal, this study proposes a technical pathway involving the co-pyrolysis of phosphogypsum and phosphorus tailings to produce artificial soil-like materials. The effects of raw material ratio, pyrolysis temperature and duration, and biomass addition on the speciation transformation, leaching toxicity, and matrix characteristics of phosphorus (P) and fluorine (F) in the products were systematically investigated. Characterization techniques, including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM), were employed to elucidate the synergistic immobilization mechanism. The results indicate that under optimized conditions (PG:PT mass ratio of 6:4, pyrolysis temperature of 800 °C, duration of 2–3 h, and biomass addition of 20%–30%), the active forms of harmful elements in the product were significantly reduced. The proportion of water-soluble fluorine decreased from ~39% in raw phosphogypsum to less than 3%, with apatite phosphorus becoming the dominant form of phosphorus. Mechanistic studies reveal that the immobilization process follows a “multi-pathway synergy” mechanism: thermal activation promotes the in situ formation of thermodynamically stable fluorapatite through the reaction of Ca²⁺, PO₄³⁻, and F⁻ (chemical fixation); iron/aluminum oxides in phosphorus tailings and the biochar derived from added biomass provide adsorption sites for surface complexation (physicochemical fixation); and the melting of silicon–aluminum components forms an amorphous silicate network that physically encapsulates pollutant microcrystals. This study provides crucial theoretical foundations and process parameters for the synergistic disposal and soil-like resource utilization of phosphogypsum and phosphorus tailings, demonstrating significant environmental and economic benefits. Full article

Rising concentrations of organic carbon (OC), phosphorus, and nitrogen in liquid waste from urban, industrial, and agricultural sources pose persistent challenges for environmental protection and resource recovery. Despite extensive application of microfiltration (MF) and ultrafiltration (UF) in wastewater treatment, their role in selective organic carbon and nutrient fractionation remains insufficiently clear-cut and is often interpreted solely through nominal pore size. This review was guided by the hypothesis that the reported limitations of MF and UF for nutrient separation are not intrinsic to the technologies but arise from simplified interpretations of separation mechanisms. A unified analytical framework was developed by synthesizing recent studies, linking membrane surface charge, pore structure, solute speciation, fouling-induced secondary layers, and operating conditions to the observed separation behavior. The analysis shows that MF fractionates particulate OC and suspended solids, whereas UF extends separation to macromolecular OC and phosphorus mainly via indirect retention mechanisms. Dissolved nitrogen species largely permeate both membranes unless they are transformed into retainable forms. Performance differences between MF and UF are conditional and system-dependent, with enhanced selectivity emerging through process integration. MF and UF can thus be repositioned as strategic fractionation interfaces within integrated treatment systems supporting circular economy–oriented wastewater management. Full article

Most of the phosphorus (P) input from feed ends up accumulating in the pond water or sediment, ultimately harming the environment. Rice demonstrates remarkable bioremediation potential. However, the mechanisms by which long-term rice impacts the sediment P cycle in aquaculture environments remain unclear. This study investigated the effects of a six-year rice–fish co-culture on sediment resuspension-driven P release, P speciation, and removal efficiency in intensive aquaculture. Our results indicated that the rice–fish co-culture (RF) system enhanced the P utilization efficiency by 128.36% while decreasing P residue in water and sediment by 77.42% and 34.62%, compared to the monoculture (F) system. The RF system reduced labile P pool (H₂O-IP, NaHCO₃-IP) contents, leading to a 74.89% and 82.20% reduction in sediment resuspension and P release rates, respectively. Concurrently, stable P pool (NaOH-IP, NaOH-OP) contents increased by 14.21% and 52.99%. Microbial mineralization in the 5–10 cm layer was enhanced, with acid phosphatase activity and relative abundance of functional gene phoC increasing by 19.69% and 327.61%. Our results showed that the six-year RF system enhanced sediment P cycling, reducing P release risk and improving P utilization. These findings inform eco-efficient aquaculture optimization, with future research needing isotope tracing and metagenomics to explore microbial roles. Full article

The influence of microplastics (MPs) on the availability of soil heavy metals (HMs) is a current research hotspot, but how MPs regulate HM availability via soil properties and the bacterial community remains unclear. This study investigated the effects of polyethylene (PE) MP concentrations on soil properties, bacterial communities, surface chemistry, and the speciation of cadmium (Cd) and lead (Pb) through soil incubation. Results indicated that as PE MP concentration increased, soil pH and cation exchange capacity declined, while organic carbon concentration increased. Available phosphorus and alkali–hydrolyzable nitrogen concentrations increased at 0.1% and 1% PE MPs, but decreased at 10% PE MPs. Bacterial community indices, including Simpson, ACE, and Chao1, increased at 0.1% and 1% PE MPs but decreased at 10% PE MPs. PE MPs (0.1% and 1%) reduced DTPA–Cd/Pb, promoting their transformation into stable forms and surface complexation with oxygen–containing groups. In contrast, 10% PE MPs disrupted the formation of PbO, PbCO₃, and Cd(OH)₂, producing the opposite effect. The random forest model revealed that soil organic carbon and available phosphorus were the primary factors influencing DTPA–Pb and DTPA–Cd, respectively. Partial least squares path modeling demonstrated that PE MPs altered the physicochemical characteristics of soil and structure of bacterial communities, ultimately impacting transformation of Cd and Pb speciation, with these changes being highly dependent on PE MP concentration. Full article

Existing studies have demonstrated the positive effects of nano-sized iron oxide on compost maturity, yet the impact of nano-sized iron oxide on phosphorus speciation and bacterial communities during the composting process remains unclear. In this study, pig manure and straw were used as raw materials, with biochar-supported nano-sized iron oxide (BC-Fe₃O₄NPs) as an additive and calcium peroxide (CaO₂) as a co-agent, to conduct an aerobic composting experiment with pig manure. Four treatments were tested: CK (control), F1 (1% BC-Fe₃O₄NPs), F2 (5% BC-Fe₃O₄NPs), and F3 (5% BC-Fe₃O₄NPs + 5% CaO₂). Key findings include the following. (1) BC-Fe₃O₄NPs increased compost temperatures, with F3 reaching 61℃; F1 showed optimal maturity (C/N ratio: 12.90). (2) BC-Fe₃O₄NPs promoted stable phosphorus forms; Residual-P proportions were higher in F1, F2, and F3 (25.81%, 51.16%, 51.68%) than CK (19.32%). (3) Bacterial phyla Firmicutes, Actinobacteria, and Proteobacteria dominated. BC-Fe₃O₄NPs altered community composition, especially on day 7. Firmicutes dominated CK, F1, and F3; Proteobacteria dominated F2. At the genus level, day 7 showed Corynebacterium (CK), Clostridum (F1, F3), and Caldibacillus (F2) as predominant. (4) Pearson correlation analysis revealed shifted correlations between phosphorus forms and bacterial phyla after BC-Fe₃O₄NPs addition. Firmicutes positively correlated with NaOH-OP in F1 during the thermophilic phase, facilitating phosphate release and adsorption by BC-Fe₃O₄NPs. The significance of correlations diminished with increasing additive concentration; in F3, all phyla positively correlated with various phosphorus forms. Full article

Phosphorus (P) is an essential macronutrient for plants. The focus of this work is to recover P from biosolids and their derived biochar. The effect of three different pyrolysis temperatures (400 °C, 500 °C, and 600 °C) and two carrier gases (CO₂ and N₂) on P fractionation and the speciation of P on biochars produced from two biosolids were investigated. The Hedley chemical sequential extraction method and ³¹P liquid NMR were used for P characterization and quantification. Higher pyrolysis temperatures increased P fixation and decreased short-term P bioavailability. Carrier gas had also significant effects on P fractionation in the biochars. Biochar produced in a CO₂ environment had slightly higher water-soluble P, NaHCO₃-P_i, NaOH-P_i, and residual P than in biochar prepared in a N₂ environment, while HCl-P showed the opposite trend. Additionally, the predominant molecular configuration of P was present in the inorganic form identified by ³¹P liquid NMR spectra, while organic P transformed into inorganic P with increasing pyrolysis temperature. Full article

Arsenic (As) metabolism in freshwater algae at different growth phases has rarely been documented. To address this gap, this study was conducted to assess the intra- and extracellular As metabolism, along with speciation changes, in Microcystis aeruginosa across three growth phases. The treatment involved varying concentrations of As (0, 0.4, 0.6, 0.8 and 1 mg/L, in the form of arsenate, iAs^V) under three phosphorus levels (0.02 mg/L as low, 0.1 mg/L as medium, and 0.5 mg/L as high P in the form of phosphate). The findings revealed that extracellular iAs^V remained the dominant As species during the lag and exponential growth phases of M. aeruginosa in the growth media, while intracellular trivalent As (iAs^III) emerged as the pronounced species during the exponential growth phase, but also exhibited a significant negative correlation with the P levels. Moreover, elevated P levels had promoted the formation of intra- and extracellular dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) in the exponential growth phase. During the stationary growth phase, intracellular iAs^V was found to decrease with the increasing P levels. During the whole growth phases, P had consistently reduced algal As absorption levels. The significant promotion of algal As absorption in response to iAs^V was observed only during the lag growth phase. The As bioaccumulation exhibited a correlational relationship with the algal reproduction. Both low and high P levels (0.02 and 0.5 mg/L) decreased the accumulation of As in algae cells during the exponential and stationary growth phases. The transformation and release rate of As were concomitantly influenced by P, and exhibited the same trends within the growth phase. These trends differed between the exponential and stationary growth phases, with an inhibitory effect being present during the former, while a promotional effect was observed during the latter. This study provides insight into potential As hazards in freshwater lakes with algae bloom. Full article

Pig, cow, and sheep manure (PM, CM, and SM) are inevitable byproducts of agricultural economic development. Converting them into high add-on value biochar (PMB, CMB, and SMB) via pyrolysis is an efficient resource utilization measure. Phosphorus (P) speciation analyses help ensure the practical feasibility of the P reclamation of animal manure and their derived biochar and a reduction in environmental risk. This study conducted a modified extraction procedure to separate five inorganic P (IP) (soluble and loosely bound IP, aluminum-bound IP, Fe-bound IP, oxide-occluded IP, and Ca-bound IP) and organic P (OP) speciations, and combined X-ray diffraction (XRD) to investigate the major phosphate compound in the derived biochar after pyrolysis. Results revealed that more than 92% of P is concentrated in the derived biochar during pyrolysis processes carried out at 200–800 °C. The percentages of soluble and loosely bound IP, aluminum-bound IP, and OP in manure decreased significantly due to their transformation into more stable P fractions such as Ca-bound IP (79.01% in PMB, 800 °C) after pyrolysis. The Olsen-P percentages had a distinct reduction at 650 °C, indicating that pyrolysis at 650 °C was the optimal condition for the reduction in Olsen-P in manure. Full article

The aim of this study was to assess the total concentration and speciation variation of heavy metals (Pb, Cd, Cu and Zn) during composting and vermicomposting of industrial sludge with different addition rations of rice husk biochar. Results indicated that pH, EC, total phosphorus (TP) and total potassium (TK) were increased and total organic carbon (TOC) and total nitrogen (TN) were decreased during the composting of industrial sludge with biochar compared with the control (sludge without biochar). The addition of earthworm to the biochar-amended sludge further decreased pH and TOC but highly enhanced the EC, TN, TP and TK. Comparatively lower concentrations of total and DTPA-extractable heavy metals were observed in biochar-amended sludge treatments mixed with earthworm in comparison with the biochar-amended sludge treatments without earthworm or the control. Sequential extraction methods demonstrated that vermicomposting of sludge with biochar converted more metals bound with exchangeable, carbonate and organic matter into the residual fraction in comparison with those composting treatments of sludge with biochar. As a result, the combination of rice husk biochar and earthworm accelerated the passivation of heavy metals in industrial sludge during vermicomposting. Rice husk biochar and earthworm can play a positive role in sequestering the metals during the treatment of industrial sludge. This research proposed a potential method to dispose the heavy metals in industrial sludge to transform waste into resource utilization. Full article

Repeated applications of phosphorus (P) fertilizers result in the buildup of P in soil (commonly known as legacy P), a large fraction of which is not immediately available for plant use. Long-term applications and accumulations of soil P is an inefficient use of dwindling P supplies and can result in nutrient runoff, often leading to eutrophication of water bodies. Although soil legacy P is problematic in some regards, it conversely may serve as a source of P for crop use and could potentially decrease dependence on external P fertilizer inputs. This paper reviews the (1) current knowledge on the occurrence and bioaccessibility of different chemical forms of P in soil, (2) legacy P transformations with mineral and organic fertilizer applications in relation to their potential bioaccessibility, and (3) approaches and associated challenges for accessing native soil P that could be used to harness soil legacy P for crop production. We highlight how the occurrence and potential bioaccessibility of different forms of soil inorganic and organic P vary depending on soil properties, such as soil pH and organic matter content. We also found that accumulation of inorganic legacy P forms changes more than organic P species with fertilizer applications and cessations. We also discuss progress and challenges with current approaches for accessing native soil P that could be used for accessing legacy P, including natural and genetically modified plant-based strategies, the use of P-solubilizing microorganisms, and immobilized organic P-hydrolyzing enzymes. It is foreseeable that accessing legacy P will require multidisciplinary approaches to address these limitations. Full article

Cadmium presence in soil is considered a significant threat to human health. Biochar is recognized as an effective method to immobilize Cd ions in different soils. However, obtaining effective and viable biochar to remove elevated Cd from postmining soil remains a challenge. More modifiers need to be explored to improve biochar remediation capacity. In this investigation, pot experiments were conducted to study the effects of poplar-bark biochar (PBC600) and thiourea-modified poplar-bark biochar (TPBC600) on Cd speciation and availability, as well as on soil properties. Our results showed that the addition of biochar had a significant influence on soil properties. In the presence of TPBC600, the acid-soluble and reducible Cd fractions were transformed into oxidizable and residual Cd fractions. This process effectively reduced Cd bioavailability in the soil system. Compared to PBC600, TPBC600 was more effective in improving soil pH, electrical conductivity (EC), organic matter (SOM), total nitrogen (TN), ammonium nitrogen (${\mathrm{NH}}_4^{+}-\mathrm{N}$), nitrate nitrogen (${\mathrm{NO}}_3^{-}-\mathrm{N}$), available potassium (AK), available phosphorus (AP), and available sulfur (AS). However, this improvement diminished as incubation time increased. Results of Pearson correlation analysis, multivariate linear regression analysis, and principal component analysis showed that soil pH and available phosphorus played key roles in reducing the available cadmium in soil. Therefore, TPBC600 was shown to be an effective modifier that could be used in the remediation of soil polluted with Cd. Full article

Mobilization, transformation, and bioavailability of fluvial suspended sediment-associated particulate phosphorus (PP) plays a key role in governing the surface water quality of agricultural catchment streams. Knowledge on the molecular P speciation of suspended sediment is valuable in understanding in-stream PP cycling processes. Such information enables the design of appropriate catchment management strategies in order to protect surface water quality and mitigate eutrophication. In this study, we investigated P speciation associated with fluvial suspended sediments from two geologically contrasting agricultural catchments. Sequential chemical P extractions revealed the operationally defined P fractions for the fluvial suspended sediments, with Tintern Abbey (TA) dominated by redox-sensitive P (P_CBD), Al, and Fe oxyhydroxides P (P_NaOH) and organic P (P_Org) while Ballyboughal (BB) primarily composed of acid soluble P (P_Detr), redox-sensitive P (P_CBD), and loosely sorbed P (P_NH4Cl). The dominant calcareous (Ca) elemental characteristic of BB suspended sediment with some concurrent iron (Fe) influences was confirmed by XRF which is consistent with the catchment soil types. Ca-P sedimentary compounds were not detected using bulk P K-edge XANES, and only P K-edge µ-XANES could confirm their presence in BB sediment. Bulk P K-edge XANES is only capable of probing the average speciation and unable to resolve Ca-P as BB spectra is dominated by organic P, which may suggest the underestimation of this P fraction by sequential chemical P extractions. Notably, µ-XANES of Ca K-edge showed consistent results with P K-edge and soil geochemical characteristics of both catchments where Ca-P bonds were detected, together with calcite in BB, while in TA, Ca-P bonds were detected but mostly as organic complexed Ca. For the TA site, Fe-P is detected using bulk P K-edge, which corresponds with its soil geochemical characteristics and sequential chemical P extraction data. Overall, P concentrations were generally lower in TA, which led to difficulties in Fe-P compound detection using µ-XANES of TA. Overall, our study showed that coupling sequential chemical P extractions with progressively more advanced spectroscopic techniques provided more detailed information on P speciation, which can play a role in mobilization, transformation, and bioavailability of fluvial sediment-associated P. Full article

Previous studies, conducted at the inception of rewetting degraded peatlands, reported that rewetting increased phosphorus (P) mobilization but long-term effects of rewetting on the soil P status are unknown. The objectives of this study were to (i) characterize P in the surface and subsurface horizons of long-term drained and rewetted percolation mires, forest, and coastal peatlands and (ii) examine the influence of drainage and rewetting on P speciation and distributions using wet-chemical and advanced spectroscopic analyses. The total P was significantly (p < 0.05) different at the surface horizons. The total concentration of P ranged from 1022 to 2320 mg kg−1 in the surface horizons and decreased by a factor of two to five to the deepest horizons. Results of the chemical, solution 31P nuclear magnetic resonance (NMR), and P K-edge X-ray absorption near-edge structure (XANES) indicated that the major proportions of total P were organic P (Po). In the same peatland types, the relative proportions of Po and stable P fractions were lower in the drained than in the rewetted peatland. The results indicate that long-term rewetting not only locks P in organic matter but also transforms labile P to stable P fractions at the surface horizons of the different peatland types. Full article

This study investigated the speciation, transformation, and availability of P during indigenous vegetable production by employing a combination of chemical and spectroscopic techniques. The study focused on sites in two ecozones of SSA, the dry savanna (lna, Republic of Benin) and rainforest (Ilesha, Nigeria). Both sites were cultivated with two indigenous vegetable species: local amaranth (Amaranthus cruentus (AC)) and African eggplant (Solanum macrocarpon (SM)). The soils were treated with 5 t/ha poultry manure and urea fertilizer at the rates of 0, 20, 40, 60, and 80 kg N/ha. Soil samples were collected before planting and after harvest. Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was used to determine P speciation in these soils. Quantitative analysis showed that adsorbed and organic P were the two dominant P species in the manure amended dry savanna (DS) soils before planting and after harvest in soils cultivated with both AC and SM, with the addition of urea (40 kg N/ha) causing an increase in the organic P form in dry savanna soils cultivated with AC. Soils of the rainforest (RF) cultivated with AC initially had large amounts of apatite P in the manure amended soils prior to planting, which was transformed to adsorbed and organic P after harvest. Urea addition to the rainforest soils shifted the dominant P species from organic P to adsorbed and apatite P, which was likely to limit P availability. Soils cultivated with SM had similar proportions of both organic and adsorbed P forms, with 40 kg N/ha addition slightly increasing the proportion of adsorbed P. Full article