Magnesium polypeptide combined with microbially induced calcite precipitation for remediation of lead contamination in phosphate mining wasteland soil.

Soil Pb contamination is inevitable, as a result of phosphate mining. It is essential to explore more effective Pb remediation approaches in phosphate mining wasteland soil to ensure their viability for a gradual return of soil quality for cultivation. In this study, a Pb-resistant urease-producing bacterium, Serratia marcescens W1Z1, was screened for remediation using microbially induced carbonate precipitation (MICP). Magnesium polypeptide (MP) was prepared from soybean meal residue, and the combined remediation of Pb contamination with MP and MICP in phosphate mining wasteland soil was studied. Remediation of Pb using a combination of MP with MICP strain W1Z1 (WM treatment) was the most effective, with the least exchangeable Pb at 30.37% and the most carbonate-bound Pb at 40.82%, compared to the other treatments, with a pH increase of 8.38. According to the community analysis, MP moderated the damage to microbial abundance and diversity caused by MICP. Total nitrogen (TN) was positively correlated with Firmicutes, pH, and carbonate-bound Pb. Serratia inoculated with strain W1Z1 were positively correlated with bacteria belonging to the Firmicutes phylum and negatively correlated with bacteria belonging to Proteobacteria. The available phosphate (AP) in the phosphate mining wasteland soil could encapsulate the precipitated Pb by ion exchange with carbonate, making it more stable. Combined MP-MICP remediation of Pb contamination in phosphate mining wasteland soil was effective and improved the soil microenvironment.

Combined use of biochar and phosphate rocks on phosphorus and heavy metal availability: A meta-analysis.

Biochar (BC) and phosphate rocks (PR) are alternative nutrient sources with multiple benefits for sustainable agriculture. The combination of these soil amendments serves two main purposes: to increase soil phosphorus (P) availability and to remediate heavy metal (HM) contamination. However, a further demonstration of the benefits and risks associated with the combined use of BC and PR (BC + PR) is needed, considering the specific characteristics of raw materials, soil types, experimental conditions, and climatic contexts. This meta-analysis is based on data from 28 selected studies, including 581 paired combinations evaluating effects on extraction and fractionation of cadmium (Cd) and lead (Pb), and 290 paired combinations for soil labile and non-labile P. The results reveal that BC, PR, and BC + PR significantly increase soil labile and non-labile P, with BC + PR showing a 150% greater increase compared to BC alone. In tropical regions, substantial increases in P levels were observed with BC, PR, and BC + PR exhibiting increments of 317, 798, and 288%, respectively. In contrast, temperate climate conditions showed lower increases, with BC, PR, and BC + PR indicating 54, 123, and 88% rises in soil P levels. Moreover, BC, PR, and BC + PR effectively reduce the bioavailability of Cd and Pb in soil, with BC + PR demonstrating the highest efficacy in immobilizing Cd. The synergistic effect of BC + PR highlights their potential for Cd remediation. BC + PR effectively reduces the exchangeable fraction of Cd and Pb in soil, leading to their immobilization in more stable forms, such as the residual fraction. This study provides valuable insights into the remediation potential and P management benefits of BC and PR, highlighting their importance for sustainable agriculture and soil remediation practices.

Effects of a novel Cd passivation approach on soil Cd availability, plant uptake, and microbial activity in weakly alkaline soils.

Heavy metal pollution, including that caused by cadmium (Cd), is a matter of increasing concern. Although in situ passivation remediation has been widely used to treat heavy metal-polluted soils, most studies have focused on acidic soils, while studies on alkaline soil conditions are scarce. In this study, the effects of biochar (BC), phosphate rock powder (PRP), and humic acid (HA) on Cd2+ adsorption were examined alone and in combination to choose an appropriate Cd passivation approach for weakly alkaline soils. Additionally, the combined impact of passivation on Cd availability, plant Cd absorption, plant physiology indexes, and soil microbial community was elucidated. BC had a higher Cd adsorption capacity and removal rate than those of PRP and HA. Moreover, HA and PRP enhanced the adsorption capacity of BC. A combination of biochar and humic acid (BHA), and biochar and phosphate rock powder (BPRP) significantly affected soil Cd passivation. BHA and BPRP decreased the plant Cd content and soil Cd-DTPA (diethylenetriaminepentaacetic acid) by 31.36 %, 20.80 %, 38.19 %, and 41.26 %, respectively; however, they increased the fresh weight by 65.64-71.48 % respectively, and dry weight by 62.41-71.35 %, respectively. Notably, only BPRP increased the node and root tip number in wheat. Total protein (TP) content increased in BHA and BPRP, with BHA showing lower TP than BPRP. BHA and BPRP showed a reduction in glutathione (GSH), malondialdehyde (MDA), H2O2, and peroxidase (POD); BHA showed a significantly lower GSH than BPRP. Additionally, BHA and BPRP increased soil sucrase, alkaline phosphatase, and urease activities, with BPRP showing considerably higher enzyme activity than BHA. Both BHA and BPRP increased the number of soil bacteria, altered the community composition, and critical metabolic pathways. The results demonstrated that BPRP could be used as a highly effective, novel passivation technique for the remediation of Cd-contaminated soil.

Improved efficiency of Sedum lineare (Crassulaceae) in remediation of arsenic-contaminated soil by phosphate-dissolving strain P-1 in association with phosphate rock.

The selection of appropriate plants and growth strategies is a key factor in improving the efficiency and universal applicability of phytoremediation. Sedum lineare grows rapidly and tolerates multiple adversities. The effects of inoculation of Acinetobacter sp. phosphate solubilizing bacteria P-1 and application of phosphate rock (PR) as additives on the remediation efficiency of As-contaminated soil by S. lineare were investigated. Compared with the control, both the single treatment and the combination of inoculation with strain P-1 and application of PR improved the biomass by 30.7-395.5%, chlorophyll content by 48.1-134.8%, total protein content by 12.5-92.4% and total As accumulation by 45.1-177.5%, and reduced the As-induced oxidative damage. Inoculation with strain P-1 increased the activities of superoxide dismutases and catalases of S. lineare under As stress, decreased the accumulation of reactive oxygen species in plant tissues and promoted the accumulation of As in roots. In contrast, simultaneous application of PR decreased As concentration in S. lineare tissues, attenuated As-induced lipid peroxidation and improved As transport to shoots. In addition, the combined application showed the best performance in improving resistance and biomass, which significantly increased root length by 149.1%, shoot length by 33%, fresh weight by 395.5% and total arsenic accumulation by 159.2%, but decreased the malondialdehyde content by 89.1%. Our results indicate that the combined application of strain P-1 and PR with S. lineare is a promising bioremediation strategy to accelerate phytoremediation of As-contaminated soils.

Bioleaching of rare-earth elements from phosphate rock using Acidithiobacillus ferrooxidans.

Phosphate rock containing rare-earth elements (REEs) is considered one of the most promising potential secondary sources of REEs, as evidenced by large tonnages of phosphate rock mined annually. The bioleaching of REEs from phosphate rock using Acidithiobacillus ferrooxidans was done for the first time in this study, and it was found to be greater than abiotic leaching and was more environmentally friendly. The result showed that the total leaching rate of REEs in phosphate rock was 28·46% under the condition of 1% pulp concentration and pH = 2, and the leaching rates of four key rare earths, Y, La, Ce and Nd, were 35·7, 37·03, 27·92 and 32·53% respectively. The bioleaching process was found to be accomplished by bacterial contact and Fe2+ oxidation. The blank control group which contained Fe2+ was able to leach some of the rare earths, indicating that the oxidation of Fe2+ may affect the leaching of rare earths. X-ray diffraction analysis showed that the minerals were significantly altered and the intensity of the diffraction peaks of dolomite and apatite decreased significantly after microbial action compared to the blank control, and it was observed that bacteria adhere to the mineral surface and the minerals become smooth and angular after bioleaching by scanning electron microscope, indicating that bacteria have a further effect on the rock based on Fe2+ oxidation. Finally, Fourier transform infrared spectroscopy and three-dimensional excitation-emission matrix fluorescence spectra analysis showed that extracellular polymeric substances participate in the bioleaching process.

Passive co-treatment of phosphorus-depleted municipal wastewater with acid mine drainage: Towards sustainable wastewater management systems.

Industrial processes typically produce large wastewater volumes, which, if left untreated, greatly affect receiving ecosystems. However, wastewater treatment can be costly and energy-intensive, with the developing world particularly struggling with wastewater management. As such, simple and cost-effective solutions are urgently required with the passive (no energy or reagents) co-treatment of different wastewater matrices holding great promise. Here, wastewater from a phosphorus recovery system (chemical precipitation) was co-treated with acid mine drainage (AMD). Specifically, phosphorus-rich municipal wastewater was treated with hydrated lime, as to synthesize a wastewater-derived phosphorus product, i.e., calcium phosphate (Ca3(PO4)2), also producing a phosphorous-depleted alkaline effluent. The feasibility of valorising this effluent is examined here by using it for the passive co-treatment of real AMD. Different liquid-to-liquid (v/v) ratios were considered, with the optimum ratio (AMD to phosphate-depleted wastewater) being 1:9. The pH of the co-treated effluent was adjusted to 8.4 (from an initial value of 11.5 in the phosphorus-depleted wastewater and 2.2 in AMD), while metals (∼100% reduction of Fe, Mn, Ni, Cu, Pb, ≥99.5 for Al, Zn, and Mg, 80% for Cr, and 75% for As) and sulphate (89.26% reduction) contained in AMD were greatly removed. This was also the case for the remaining orthophosphate that was contained in the phosphorus-depleted wastewater (93.75% reduction). The electrical conductivity was also reduced in both the AMD (88.75%) and the phosphorus-depleted wastewater (69.21%), suggesting the removal of contaminants from both matrices. Results were underpinned by state-of-the-art analytical techniques, including FE-SEM/FIB/EDX, FTIR, and XRD, along with geochemical modelling (PHREEQC). Contaminants were removed through complexation, (co)adsorption, crystallization, and (co)precipitation. Overall, results suggest that the co-treatment of these wastewater matrices is feasible and could be directly scaled up (e.g., using waste stabilization ponds), while opportunities for the beneficiation of the produced sludge and for water reclamation (e.g., through membrane filtration) could also arise, further promoting the sustainably of this passive co-treatment method.

Effects of the joint application of phosphate rock, ferric nitrate and plant ash on the immobility of As, Pb and Cd in soils.

Phosphate rock (PR) and ferric salts have been frequently used to immobilize heavy metal(loid)s in soils, but in varied efficiencies referring to different metal(loid) pollutants. This study explored the effective application of plant ash (PA) to the previous formula of phosphate rock (PR) and ferric salts (Fe(NO3)3) (PR + Fe3++PA), compared to only PR, on the bioavailability and immobility of multi-metal(loid)s of selected arsenic (As), lead (Pb) and cadmium (Cd) in soils. Results from NaHCO3- extraction and toxicity characteristic leaching procedure (TCLP) implied the increase of the As mobility in soils by 7.0% and 2.6% using PR only, but the significant reduction of the As mobility by 24.2% and 82.4% jointly using PR + Fe3++PA. Meanwhile, the application of either PR alone or PR + Fe3++PA in soil significantly decreased Pb and Cd extracting in diethylene triamine pentacetate acid (DTPA) and TCLP, particularly, the immobilization effect of PR + Fe3++PA was better than that of PR. The leaching column test further confirmed the high durability of PR + Fe3++PA on the immobilization of As and Pb under the continuous acid exposure, but likely slightly increased the mobility of Cd (the accumulated concentration of Cd, 5.88 µg/L) compared to that (3.16 µg/L) in the untreated column (UN-column), which were both much lower than the level V (100 µg/L) of the Chinese National Quality Standard for Surface Water (GB 3838-2002). Therefore, PR + Fe3++PA exhibited the significant enhancement on the immobilization of As, Pb and Cd under simulated acid rain (SAR) leaching.

Oxalic acid activated phosphate rock and bone meal to immobilize Cu and Pb in mine soils.

The contamination of soil by copper (Cu) and lead (Pb) is a serious concern because of its high health risk via the food chain. Oxalic acid-activated phosphate rock (APR) and bone meal (BM) were applied to Cu and Pb co-contaminated soil to investigate their efficacy in the immobilization of Cu and Pb. APR and BM were applied into the contaminated soil (158.8 mg/kg total Pb and 573.2 mg/kg Cu) at four levels of dosages (0.1%, 0.5%, 2%, and 4%) and incubated for one year. The results demonstrated that the acid exchangeable Pb fraction in the soil treated with APR and BM decreased compared to the control, while there was no noticeable change in the acid-exchangeable Cu fraction in the soil treated with either APR or BM. Meanwhile, the application of BM and APR increased the fraction of residual Cu and Pb in the polluted soils. Moreover, the addition of either APR or BM at the dose of 4% decreased the concentrations of CaCl2-extractable Cu and Pb in the amended soil, and the percentages of that reduction in the APR amended soils were 56% and 91% and in BM amended soils were 67% and 64%, respectively. The immobilization of Cu and Pb by APR and BM might be induced by the increased soil pH and soluble P contents in the amended soils. In general, BM is more effective than APR on the immobilization of Cu in polluted soil, while APR had greater efficiency than BM on the immobilization of Pb when the levels of amendments were above 2%.

Agronomic efficiency of phosphate fertilizers produced by the re-use of a metallurgical acid residue.

The production of fertilizers with industrial wastes reduces the environmental impacts of waste disposal and improves environmental sustainability by generating added-value products. Our objective with this study was to evaluate the agronomic performance and potential soil/plant contamination with heavy metals of alternative phosphate (P) fertilizers, obtained from the acidulation of phosphate rocks (PR) by a metallurgical acidic waste. Seven P fertilizers were evaluated: three PR (Araxá, Patos, and Bayóvar), their respective acidulated products (PAPR), and triple superphosphate fertilizer (TSP). A greenhouse trial was carried out to test the agronomic performances of fertilizers in a sequentially cultivated maize-soybean-white oat. The reaction of PR with acid waste was effective to increase their solubility and improve plant yield and P uptake compared to their natural PR. There was a cumulative recovery by plants of 1.4 and 8.1% of added P via PR and PAPR, respectively. No increase in heavy metal (Cd, Pb, Cr, and Ni) availability in soil or accumulation in shoots was observed, indicating that the PAPR were environmentally safe. The usage of acid waste to produce P fertilizers therefore represents a strategic way to employ marginal products for the production of fertilizers.

Igneous phosphate rock solubilization by biofilm-forming mycorrhizobacteria and hyphobacteria associated with Rhizoglomus irregulare DAOM 197198.

Biofilm formation on abiotic and biotic surfaces was studied with two hyphobacteria, strongly attached to the surface of the arbuscular mycorrhizal fungus (AMF) Rhizoglomus irregulare (Ri) DAOM 197198 and two mycorrhizobacteria, loosely attached to the roots of different mycorrhizal plants. When the sparingly soluble igneous phosphate rock (PR) from Quebec, or when the chemical hydroxyapatite were used as sole phosphorus (P) source, hyphobacteria Rhizobium miluonense Rm3 and Burkholderia anthina Ba8 produced significantly more biofilms than mycorrhizobacteria Rahnella sp. Rs11 and Burkholderia phenazinium Bph12, as indicated by the crystal violet assay or by quantifying biofilm exopolysaccharides. As previously observed with planktonic bacteria, biofilms mobilized P by lowering the pH and releasing gluconic acid. The high efficiency of P mobilization by the hyphobacteria Ba8 was linked to the presence of more viable cells in its biofilm as revealed by the hydrolysis of fluorescein diacetate. Scanning electron microscopy micrographs showed a high adherence of the best P-solubilizer hyphobacteria Ba8 on the surface of Quebec PR. Hydroxyapatite porous structure did not allow a good adherence of Ba8. Ba8 formed an important biofilm on the hyphae of Ri DAOM 197198 with low reactive Quebec PR while no biofilm was observed with the high reactive hydroxyapatite. Results confirm the possible presence of specificity between the Ri DAOM 197198 and the hyphobacteria and suggest that the interaction would be regulated by the availability of P.

Solubilization of phosphorus from phosphate rocks with Acidithiobacillus thiooxidans following a growing-then-recovery process.

Phosphorus is an essential nutrient for the synthesis of biomolecules and is particularly important in agriculture, as soils must be constantly supplemented with its inorganic form to ensure high yields and productivity. In this paper, we propose a process to solubilize phosphorus from phosphate rocks, where Acidithiobacillus thiooxidans cultures are pre-cultivated to foster the acidic conditions for bioleaching-two-step "growing-then-recovery"-. Our method solubilizes 100% of phosphorus, whereas the traditional process without pre-cultivation-single-step "growing-and-recovery"-results in a maximum of 56% solubilization. As a proof of principle, we demonstrate that even at low concentrations of the phosphate rock, 1% w/v, the bacterial culture is unviable and biological activity is not observed during the single-step process. On the other hand, in our method, the bacteria are grown without the rock, ensuring high acid production. Once pH levels are below 0.7, the mineral is added to the culture, resulting in high yields of biological solubilization. According to the Fourier Transform Infrared Spectroscopy spectrums, gypsum is the dominant phosphate phase after both the single- and two-step methods. However, calcite and fluorapatite, dominant in the un-treated rock, are still present after the single-step, highlighting the differences between the chemical and the biological methods. Our process opens new avenues for biotechnologies to recover phosphorus in tropical soils and in low-grade phosphate rock reservoirs.

[Combination of phosphorus solubilizing and mobilizing fungi with phosphate rocks and volcanic materials to promote plant growth of lettuce (Lactuca sativa L.)]. / Combinación de hongos movilizadores y solubilizadores de fósforo con rocas fosfóricas y materiales volcánicos para la promoción del crecimiento de plantas de lechuga (Lactuca sativa L.).

Arbuscular mycorrhizal fungi (AMF) increase the uptake of soluble phosphates, while phosphorus solubilizing fungi (S) promote solubilization of insoluble phosphates complexes, favoring plant nutrition. Another alternative to maintaining crop productivity is to combine minerals and rocks that provide nutrients and other desirable properties. The aim of this work was to combine AMF and S with pyroclastic materials (ashes and pumices) from Puyehue volcano and phosphate rocks (PR) from Rio Chico Group (Chubut) - to formulate a substrate for the production of potted Lactuca sativa. A mixture of Terrafertil®:ashes was used as substrate. Penicillium thomii was the solubilizing fungus and Rhizophagus intraradices spores (AMF) was the P mobilizer (AEGIS® Irriga). The treatments were: 1) Substrate; 2) Substrate+AMF; 3) Substrate+S; 4) Substrate+AMF+S; 5) Substrate: PR; 6) Substrate: PR+AMF; 7) Substrate: PR+S and 8) Substrate: PR+AMF+S. Three replicates were performed per treatment. All parameters evaluated (total and assimilable P content in substrate, P in plant tissue and plant dry biomass) were significantly higher in plants grown in substrate containing PR and inoculas with S and AMF. This work confirms that the combination of S/AMF with Puyehue volcanic ashes, PR from the Río Chico Group and a commercial substrate promote the growth of L. sativa, thus increasing the added value of national geomaterials.

African crop yield reductions due to increasingly unbalanced Nitrogen and Phosphorus consumption.

The impact of soil nutrient depletion on crop production has been known for decades, but robust assessments of the impact of increasingly unbalanced nitrogen (N) and phosphorus (P) application rates on crop production are lacking. Here, we use crop response functions based on 741 FAO maize crop trials and EPIC crop modeling across Africa to examine maize yield deficits resulting from unbalanced N : P applications under low, medium, and high input scenarios, for past (1975), current, and future N : P mass ratios of respectively, 1 : 0.29, 1 : 0.15, and 1 : 0.05. At low N inputs (10 kg ha(-1)), current yield deficits amount to 10% but will increase up to 27% under the assumed future N : P ratio, while at medium N inputs (50 kg N ha(-1)), future yield losses could amount to over 40%. The EPIC crop model was then used to simulate maize yields across Africa. The model results showed relative median future yield reductions at low N inputs of 40%, and 50% at medium and high inputs, albeit with large spatial variability. Dominant low-quality soils such as Ferralsols, which are strongly adsorbing P, and Arenosols with a low nutrient retention capacity, are associated with a strong yield decline, although Arenosols show very variable crop yield losses at low inputs. Optimal N : P ratios, i.e. those where the lowest amount of applied P produces the highest yield (given N input) where calculated with EPIC to be as low as 1 : 0.5. Finally, we estimated the additional P required given current N inputs, and given N inputs that would allow Africa to close yield gaps (ca. 70%). At current N inputs, P consumption would have to increase 2.3-fold to be optimal, and to increase 11.7-fold to close yield gaps. The P demand to overcome these yield deficits would provide a significant additional pressure on current global extraction of P resources.

Assessing the influence of diverse phosphorus sources on bacterial communities and the abundance of phosphorus cycle genes in acidic paddy soils.

The impact of chemical fertilizers on soil microbial communities is well acknowledged. This study assesses the influence of various phosphorus sources on soil bacterial composition, abundance, and Phosphorus Cycle Gene Abundance. Three phosphorus sources (natural phosphate rock, triple super phosphate (TSP), and chemical fertilizer NPK) were field tested following two rice cultivation cycles. Soil samples were subsequently collected and analyzed for bacterial groups and phosphorus cycle genes. Results indicated that the bacterial community composition remained consistent, comprising five main phyla: Firmicutes, Actinobacteria, Proteobacteria, Halobacterota, and Chloroflexia, regardless of fertilizer type. NPK fertilizer significantly reduced the relative abundance of Chloroflexia by 19% and Firmicutes by 16.4%, while increasing Actinobacteria and Proteobacteria by 27.5 and 58.8%, respectively. TSP fertilizer increased Actinobacteria by 27.1% and Halobacterota by 24.8%, but reduced Chloroflexia by 8.6%, Firmicutes by 12.6%, and Proteobacteria by 0.6%. Phosphate rock application resulted in reductions of Chloroflexia by 27.1%, Halobacterota by 22.9%, and Firmicutes by 6.2%, alongside increases in Actinobacteria by 46.6% and Proteobacteria by 23.8%. Combined application of TSP, NPK, and phosphate rock led to increases in Proteobacteria (24-40%) and Actinobacteria (13-39%), and decreases in Chloroflexia (5.2-22%) and Firmicutes (6-12.3%) compared to the control (T0). While the different phosphorus sources did not alter the composition of phosphorus cycle genes, they did modulate their abundance. NPK fertilizer did not significantly affect ppK genes (57-59%) but reduced gcd (100 to 69%), 3-phytase (74 to 34%), appA (91 to 63%), and phoD (83 to 67%). Phosphate rock reduced appA and gcd by 27 and 15%, respectively, while increasing 3-phytase by 19%. TSP decreased ppK and phoD by 42 and 40%, respectively, and gcd and appA by 34 and 56%, respectively. Combined fertilizers reduced appA (49 to 34%), 3-phytase (10 to 0%), and gcd (27 to 6%), while increasing ppK (72 to 100%). Among tested phosphorus sources, natural phosphate rock was best, causing moderate changes in bacterial composition and phosphorus genes, supporting balanced soil microbial activity. These findings highlight the complex interactions between fertilizers and soil microbial communities, underscoring the need for tailored fertilization strategies to maintain soil health and optimize agricultural productivity.

Adsorption effect and mechanism of Cd(II) by different phosphorus-enriched biochars.

The resource utilization of agricultural and forestry waste, especially the high-value transformation of low-grade phosphate rock and derivatives, is an important way to achieve sustainable development. This study focuses on the impregnation and co-pyrolysis of rice straw (RS) with fused calcium magnesium phosphate (FMP), FMP modified with citric acid (CA-FMP), and calcium dihydrogen phosphate (MCP) to produce three phosphorous-enriched biochars (PBC). The Cd(II) removal efficiency of biochars before and after phosphorus modification was investigated, along with the adsorption mechanism and contribution of biochars modified with different phosphorus sources to Cd(II) adsorption. The result indicated that CA-FMP and MCP could be more uniformly loaded onto biochar, effectively increasing the specific surface area (SSA) and total pore volume. The adsorption of Cd(II) onto PBC followed a mono-layer chemisorption process accompanied by intraparticle diffusion. The adsorption of Cd(II) by PBC involved ion exchange, mineral precipitation, complexation with oxygen-containing functional groups (OFGs), cation-π interaction, electrostatic interaction, and physical adsorption. Ion exchange was identified as the primary adsorption mechanism for Cd(II) by BC and FBC (51.53% and 53.15% respectively), while mineral precipitation played a major role in the adsorption of Cd(II) by CBC and MBC (51.10% and 47.98% respectively). Moreover, CBC and MBC significantly enhanced the adsorption capacity of Cd(II), with maximum adsorption amounts of 128.1 and 111.5 mg g-1 respectively.

Quality of Phosphate Rocks from Various Deposits Used in Wet Phosphoric Acid and P-Fertilizer Production.

Phosphate rocks (PRs) play a crucial role in ensuring the availability of phosphorous for the world's food needs. PRs are used to manufacture phosphoric acid in the wet process as well as P-fertilizers. The chemical and mineralogical compositions of PRs from Djebel Onk (Algeria), Khneifiss (Syria), Negev (Israel), Bou Craa (Morocco), and Khouribga (Morocco) are discussed in this study. PRs were characterized by inductively coupled plasma optical emission spectrometry (ICP-OES), cold vapor atomic absorption spectrometry (CVAAS), ion chromatography (IC), and X-ray diffraction (XRD), as well as gravimetric and potentiometric methods. All PRs were mainly composed of CaO, P2O5, SiO2, F, SO3, Na2O, MgO, Al2O3, Fe2O3, SrO, and K2O at the level of wt.%. The P2O5 content accounted for 28.7-31.2%, which indicates that these are beneficial rocks to a marketable product. The degree of PR purity expressed by the minor elements ratio index (MER index) varied from 2.46% to 10.4%, and the CaO/P2O5 weight ratio from 1.6 to 1.9. In addition, the occurrence of trace elements such as As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, Ti, V, U, and Zn, as well as Cr(VI) and Cl ions at the level of mg∙kg-1 was found. Since PRs will be used to produce P-fertilizers, their composition was compared with the regulatory parameters set up by EU Regulation 2019/1009 related to the heavy metals (As, Cd, Pb, Ni, Hg, Cu, Zn) and Cr(VI) contents in inorganic fertilizers. The heavy metals and Cr(VI) content in all PRs did not exceed the limit values. XRD analysis revealed that fluorapatite, hydroxyapatite, carbonate fluorapatite, and carbonate hydroxyapatite were the dominant minerals. The accuracy and precision of the used methods were evaluated by analysis of standard reference materials (SRM) for Western Phosphate Rock (NIST 694). The recovery was 85.3% for U and 109% for K2O, and the RSD ranged from 0.67% to 12.8%.

Uranium in phosphate rocks and mineral fertilizers applied to agricultural soils in East Africa.

Phosphate rock, pre-concentrated phosphate ore, is the primary raw material for the production of mineral phosphate fertilizer. Phosphate rock is among the fifth most mined materials on earth, and it is also mined and processed to fertilizers in East Africa. Phosphate ore can contain relevant heavy metal impurities such as toxic cadmium and radiotoxic uranium. Prolonged use of phosphate rock powder as a fertilizer and application of mineral fertilizers derived from phosphate rock on agricultural soils can lead to an accumulation of heavy metals that can then pose an environmental risk. This work assesses the uranium concentrations in four major phosphate rocks originating from East Africa and four mineral phosphate fertilizers commonly used in the region. The concentration measurements were performed using energy-dispersive X-ray fluorescence spectrometry. The results showed that the uranium concentration in phosphate rock ranged from as low as 10.7 mg kg-1 (Mrima Hill deposit, Kenya) to as high as 631.6 mg kg-1 (Matongo deposit, Burundi), while the concentrations in phosphate fertilizers ranged from 107.9 for an imported fertilizer to 281.0 mg kg-1 for a local fertilizer produced from Minjingu phosphate rock in Tanzania. In this context, it is noteworthy that the naturally occurring concentration of uranium in the earth crust is between 1.4 and 2.7 mg kg-1 and uranium mines in Namibia commercially process ores with uranium concentrations as low as 100-400 mg kg-1. This study thus confirms that East African phosphate rock, and as a result the phosphate fertilizer produced from it can contain relatively high uranium concentrations. Options to recover this uranium are discussed, and it is recommended that public-private partnerships are established that could develop economically competitive technologies to recover uranium during phosphate rock processing at the deposits with the highest uranium concentrations.

Effects of Low-Phosphorus Diets Supplemented with Phytase on the Production Performance, Phosphorus-Calcium Metabolism, and Bone Metabolism of Aged Hy-Line Brown Laying Hens.

This study was conducted to evaluate the effects of phytase supplementation in low-phosphorus diets on the production performance, phosphorus-calcium metabolism, and bone metabolism in laying hens from 69 to 78 weeks of age. Hy-Line Brown laying hens (n = 1350) were assigned randomly to six treatments with five replicates of 45 birds. A corn-soybean meal-based diet with no inorganic phosphates was formulated to contain 0.12% non-phytate phosphorus (NPP) and 1470 FTU/kg phytase (Released phytate phosphorus content ≥ 0.1%). Inorganic phosphorus (dicalcium phosphate) was supplemented into the basal diet to construct five test diets (level of NPP supplementation = 0.10%, 0.15%, 0.20%, 0.25%, and 0.30%). The level of calcium carbonate was adjusted to ensure that all six experimental diets contained the same calcium percentage (3.81%). The feeding trial lasted 10 weeks (hens from 69 to 78 weeks of age). Upon supplementation with phytase (1470 FTU/kg), supplemental inorganic phosphates (dicalcium phosphate) had no significant effects (p > 0.05) on the production performance or egg quality. Significant differences in serum levels of calcium, phosphorus, copper, iron, zinc, or manganese were not detected across treatments (p > 0.05). Hens fed NPP (0.15%, 0.20%, 0.25%, and 0.30%) had higher levels (p < 0.0001) of tibial ash, calcium, and phosphorus than those not fed inorganic phosphates. The tibial breaking strength of the group without inorganic phosphates was significantly lower than that of the other groups (p < 0.01). Dietary supplementation with inorganic phosphates had no effect (p > 0.05) on serum levels of calcitonin (CT) and 1,25-dihydroxy-vitamin D3 (1,25-(OH)2D3). Hens that did not receive supplementation with inorganic phosphates had higher serum levels of parathyroid hormone (PTH), osteoprotegerin (OPG), type-I collagen c-telopeptide (CTX-I), and tartrate-resistant acid phosphatase 5b (TRACP-5b) compared with those in the other groups (p < 0.01). Serum levels of CTX-I and TRACP-5b were significantly lower in the NPP-supplementation groups of 0.25% and 0.30% than in the 0.10% NPP-supplementation group (p < 0.01). Dietary supplementation with inorganic phosphates had no effect (p > 0.05) on serum levels of bone-alkaline phosphatase (BAP), osteocalcin (OCN), or osteopontin (OPN). Hens not fed inorganic phosphate had the highest renal expression of phosphorus transporter type IIa Na/Pi cotransporter (NaPi-Ⅱa). Renal expression of NaPi-Ⅱa was increased significantly in NPP-supplementation groups of 0.10-0.20% compared with that in NPP-supplementation groups of 0.25% and 0.30% (p < 0.0001). The results indicated that a reduction in NPP supplementation to 0.15% (dietary NPP level = 0.27%) with phytase inclusion did not have an adverse effect on the production performance or bone health of laying hens from 69 to 78 weeks of age, which might be attributed to renal phosphorus reabsorption and bone resorption. These findings could support the application of low-phosphorus diets in the poultry industry.

Effect of phosphate rock acid insoluble residue on hydration process and mechanical properties of α-hemihydrate gypsum.

The application of α-hemihydrate gypsum (α-HH) is limited by several factors, such as a rapid hydration rate, short setting time, poor water resistance, and high cost. Especially because of the high production cost, although α-HH has excellent mechanical strength, it is rarely used in the field of building materials. In this study, based on the composition characteristics of new industrial solid waste (phosphate-rock acid-insoluble residue, PAIR) and to meet the needs of resource utilization, gypsum matrix composites were prepared by adding PAIR to α-HH to solve the problems of short setting time and poor water resistance of gypsum matrix composites and improve the comprehensive properties of α-HH products. The results show that when the different types of pores formed during the hydration of α-HH were filled with inert substances, such as silicon dioxide, insoluble phosphate, and calcium fluoride from PAIR, the proportion of mesopores in the composite products increased, whereas that of harmful macropores decreased. The compressive and flexural softening coefficients of the PAIR/α-HH system with 23% PAIR were the highest at 57.25 and 60.125%, respectively, and the water resistance of the system was improved; when the content of PAIR reaches 35%, the strength of the composite products decreased from 58.125 to 43.8 MPa. The HPO42- in PAIR partially replaces the SO42- ion in the dihydrate gypsum (DH) lattice to form a Ca(SO4, HPO4)•2H2O double salt, leading to the production of eutectic phosphorus. Soluble F-, Al3+, Mg2+, and phosphorus-containing substances in PAIR form a variety of complex ions in PAIR/α-HH aqueous solution, which are adsorbed onto the surface of the new DH phase; the crystal morphology changed from thick, long columns to clusters, thin rods, and plates, inhibiting the nucleation and growth of DH and changing its crystal growth rate and crystallization behavior. Therefore, the setting time of gypsum is prolonged; when 35% PAIR was added, the induced nucleation period of the PAIR/α-HH system was prolonged from 40 to 265 min, and the final setting time was from 12 to 360 min. By mixing solid waste PAIR, while the setting time of α-HH is prolonged, its water resistance is improved, and its mechanical strength is not significantly reduced, reducing the cost. From the perspective of economy and environmental protection, this study is a way to α-HH is widely used in the field of building materials.

The Synergistic Effect of Biochar-Combined Activated Phosphate Rock Treatments in Typical Vegetables in Tropical Sandy Soil: Results from Nutrition Supply and the Immobilization of Toxic Metals.

Sandy soils in tropical areas are more vulnerable to potential toxic elements as a result of their low nutrition. The composite addition of biochar and phosphate material is considered a promising method of immobilizing toxic metals in sandy soils, but the synergistic effects of this process still need to be further explored, especially in typical tropical vegetables. In this study, a pot experiment was conducted to evaluate the agronomic and toxic metal-immobilization effects of single amendments (phosphate rock, activated phosphate rock, and biochar) and combined amendments, including biochar mixed with phosphate rock (BCPR) and biochar mixed with activated phosphate rock (BCAPR), on vegetables grown in tropical sandy soil. Among these amendments, the composite amendment BCAPR was the most effective for increasing Ca, Mg, and P uptake based on water spinach (Ipomoea aquatica L.) and pepper (Capsicum annuum L.), showing increased ratios of 22.5%, 146.0%, and 136.0%, respectively. The SEM-EDS and FTIR analysis verified that the activation process induced by humic acid resulted in the complexation and chelation of the elements P, Ca, and Mg into bioavailable forms. Furthermore, the retention of available nutrition elements was enhanced due to the strong adsorption capacity of the biochar. In terms of cadmium (Cd) and lead (Pb) passivation, the formation of insoluble mineral precipitates reduced the mobility of these metals within the BCAPR treatments, with the maximum level of extractable Cd (86.6%) and Pb (39.2%) reduction being observed in the tropical sandy soil. These results explore the use of sustainable novel cost-effective and highly efficient bi-functional mineral-based soil amendments for metal passivation and plant protection.