Activated ZnCl2 biochar and humic acid as additives in monoammonium phosphate fertilizer: Physicochemical characterization and agronomic effectiveness.

Activated zinc biochar (ZnBC) and humic acid (HA) were used as coating agents in a soluble monoammonium phosphate (MAP) to modify phosphorus (P) use efficiency by altering adsorption/desorption kinetics between the granule region and the soil. The coated treatments MAPZnBC and MAPHA were compared with MAP through P diffusivity, kinetics, and agronomic evaluation. Eucalyptus sawdust was used as biomass for biochar synthesis, and a pre-pyrolysis treatment with zinc chloride (ZnCl2) was applied. The P diffusivity was evaluated in the fertosphere zone. Adsorption and desorption potential of the ZnBC compared with control biochar (BC) was evaluated separately. Desorption kinetics of P from soil was assessed after incubation with MAPZnBC and MAPHA. The shoot dry matter yield (SDM), P uptake, and P use efficiency (PUE) were evaluated with a pot experiment in a clay Oxisol sown with maize and soybeans as successive plant trials, under glasshouse conditions. Surface area values of 940 and 305 m2 g-1 combined with adsorption capacities of 106 and 53 mg P g-1 for ZnBC and BC, respectively, confirm the increased capacity of activated biochar to adsorb P. Both MAPZnBC and MAPHA decreased P diffusivity compared to MAP after 20 days of incubation. Moreover, MAPZnBC and MAPHA presented 20% and 34% more water-soluble phosphorus recovery. MAPZnBC expressed an increase in SDM while MAPHA highlighted P uptake and PUE compared with MAP. Both kinetic studies and agronomic evaluations showed that ZnBC and HA are suitable as coatings for phosphate fertilizers in terms of increasing P efficiency in the fertosphere on high P-fixing soils.

Lead speciation and availability affected by plants in a contaminated soil.

Changes in lead (Pb) speciation in the rhizosphere may be plant species-dependent and dictate Pb fate and behavior in the soil-plant system. X-ray absorption near edge structure (XANES) spectroscopy can explain how these changes affect Pb availability in soils and its uptake by plants. We investigated the changes in Pb speciation and availability in the rhizosphere of eucalypt (Eucalyptus urophylla x Eucalyptus grandis), palisade grass (Urochloa brizantha cv. Marandu), and Indian mustard (Brassica juncea L.) using XANES spectroscopy. A greenhouse experiment was performed in a complete randomized design, with three plant species and a no plant control treatment. After three months, rhizosphere and bulk soil samples were collected, Pb speciation was assessed by Pb L3-edge XANES spectroscopy, and Pb concentration was determined in plant tissue. In bulk soil, we found Pb primarily as Pb-Il (Pb sorbed to illite; 48%) and lead monoxide (PbO; 36%). In the rhizosphere, Pb-Ka (Pb sorbed to kaolinite; 33-56%) and (CH3COO)2Pb (25-41%) were the main Pb forms, the latter suggesting Pb complexation by low molecular weight organic acids (LMWOAs). Palisade grass rhizospheric soil had a lower abundance of Pb-Ka and a higher abundance of (CH3COO)2Pb than eucalypt and mustard, which led to low Pb concentration in plant tissue. LMWOAs exudation followed by Pb2+ complexation is the apparent mechanism used by palisade grass to detoxify the rhizosphere and control Pb uptake. Given its low Pb uptake and potential to complex Pb in organic forms, palisade grass may be a promising species for Pb phytostabilization in contaminated soils.

Diffuse reflectance infrared Fourier transform spectroscopy for a qualitative evaluation of plant leaf pigment extraction.

The extraction and quantification of leaf pigments are easy, fast, and cheap procedures; on the other hand, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy associated with chemometrics tools could offer new insights into leaf biochemical composition. We aimed to boost the classic leaf pigment quantification, adding leaf biochemical information derived from DRIFT spectroscopy + principal component analysis, using the same leaf pigment extract produced by the classical quantification method. We performed a dose-response experiment using P as the limiting nutrient, and maize (Zea mays L.) as a plant-test. After 45 d of growth, we evaluated the effects of P fertilization in total maize shoot biomass, P shoot accumulation, leaf pigment quantification by UV-Vis, and the evaluation of biochemical variations by DRIFT spectroscopy analysis associated with a chemometric approach in the same leaf extract used for pigment quantification. P fertilization raised biomass accumulation (∼7.4×), P uptake (∼2.3×), and total chlorophyll a and b contents (∼2.1×). DRIFT spectroscopy analysis of extracted pigments revealed an elevated content of proteins and polysaccharides at high P availability. At low P availability, we found a low efficiency of N metabolism suggested by the accumulation of inorganic N forms. DRIFT spectroscopy applied together with the classic leaf pigment extraction and quantification method is a novel and promising tool for plant nutrition studies as a DRIFT spectroscopy metabolic profile protocol.

Characterization and application of magnetic biochar for the removal of phosphorus from water.

Activated biochars were prepared from residues of medium density fiberboard (MDF) produced by the furniture industry. Biomass residue was pre-treated with FeCl3 in two different FeCl3:biomass ratios (0.5:1 and 1:1, w/w) aiming to produce a matrix embedded with iron oxide. The pyrolysis process produced maghemite on the biochar surface and its magnetic properties were confirmed by its attraction to a hand magnet and its magnetic susceptibility. Samples were also characterized using scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS), surface area by BET-N2, Fourier transform infrared (FTIR), X-ray diffraction, magnetic susceptibility, and cation exchange capacity (CEC). Magnetic biochar exhibited up to twelve-fold higher surface area than the non-magnetic biochar, which varies according the maghemite particles content. Iron oxide on biochar surface also contributed for increasing CEC around ten-fold compared to non-magnetic biochars. Phosphorus adsorption isotherms showed that these magnetic biochars have high capacity to sorb oxyanions like phosphate, especially at lower pH. Thus, these magnetic biochars could be used to clean water bodies contaminated with oxyanions in acidic conditions.

Biochar as composite of phosphate fertilizer: Characterization and agronomic effectiveness.

Organomineral phosphate fertilizers (OMP) may reduce phosphate release rate and its direct contact to the soil solid phase, increasing the effectiveness of phosphorus (P) fertilization. This study aimed to evaluate the effect of granulating biochar (BC) with triple superphosphate (TSP) in two forms (blend or coated) and three proportions (5, 15 and 25%, w/w) on the P release kinetics and plant growth. A successive plant trial using two soils of contrasting P buffering capacities and five P doses (0, 20, 40, 80 and 120 mg kg-1) was set to investigate the agronomic effectiveness of OMP that presented the slowest P release kinetic. The kinetic test showed that within the first 1.5 h, TSP, OMP blend and OMP coated fertilizers released 92, 82 and 36% of total P, respectively. Thereby, BC addition to TSP reduced the P release rate, mainly due to coating. The fertilizers coated with 15% and 25% BC (C15 and C25, respectively) presented the slowest P release rate. For the plant trial, C15 was chosen because it requires less BC when compared with C25 fertilizer. In the first crop, C15 provided more P to plants, especially in the soil with high P buffering capacity, which increased by 10% and 20% the P uptake and the P recovered by the plant when compared with TSP, respectively. In the sandy soil, fertilizers C15 and TSP showed the same performances regarding yield, P uptake and P recovery rate. At consecutive cultivation, regardless of the soil type, P sources (C15 and TSP) did not differ in yield, P uptake and P recovery. Therefore, biochar-based organomineral phosphate fertilizer can enhance P use efficiency in high P-fixing tropical soils, increasing P recovery and uptake when compared with TSP.

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.

Nitrogen release from urea with different coatings.

BACKGROUND: Coatings or urease inhibitors are designed to reduce losses of ammonia [NH3(g) ] from urea fertilizers. However, nitrogen (N) release and its effects on soil solution have not previously been evaluated under standardized conditions in soils. In this study, the urea fertilizers were incubated in chambers filled with sandy loam soil, adapted for the collection of NH3(g) and soil solution by centrifugation. RESULTS: In the fast-release N fertilizers, around 93% and 100% of urea-N applied was recovered within the first hours of incubation. In contrast, in the slow-release N fertilizers, less than 40% of urea-N applied, was recovered at 19 days of incubation. The maximum N release from the fertilizers followed the order: UP1 (106%) ≈ UNBPT (102%) ≈ urea (93%) > USP2 (57%) ≈ USP3 (57%) > USP4 (31%) ≈ USP5 (18%). NH3(g) volatilization accounted for only 3% of the applied N in the slow-release fertilizers, which corresponded to about 88% less than the NH3(g) loss from prilled urea. CONCLUSION: This study demonstrated distinct N release patterns, which changed the N dynamics in the soil. Some coatings effectively delayed urea release from granules and reduced NH3(g) gas losses, while other were not efficient. © 2017 Society of Chemical Industry.

Increasing Soluble Phosphate Species by Treatment of Phosphate Rocks with Acidic Waste.

The development of efficient fertilizers with a diminished environmental footprint will help meet the increasing demand for food and nutrients by a growing global population. Our objective was to evaluate whether an acidic mine waste (AMW) could be used beneficially by reacting it with sparingly soluble phosphate rocks (PRs) to produce more soluble P fertilizer materials. Three PRs from Brazil and Peru were reacted with different concentrations of AMW. Changes in mineralogy and P species were determined using a combination of X-ray diffraction and phosphorus K-edge XANES spectroscopy, in addition to extractable P concentrations. Increasing the AMW concentration typically increased extractable P. X-ray diffraction data showed transformation of apatite to other species when PRs were reacted with AMW at ≥50% (v/v) in water, with gypsum or anhydrite forming at AMW concentrations as low as 12.5%. Linear combination fitting analysis of X-ray absorption near edge structure spectra also indicated a progressive transformation of apatite to noncrystalline Fe(III)-phosphate and more soluble Ca-phosphates with increasing AMW concentration. Because this AMW is costly to dispose of, reacting it with PR to produce a higher-grade phosphate fertilizer material could decrease the environmental impacts of the AMW and diminish the consumption of pure acids in conventional P fertilizer production.

Soluble phosphate fertilizer production using acid effluent from metallurgical industry.

Preventive and effective waste management requires cleaner production strategies and technologies for recycling and reuse. Metallurgical industries produce a great amount of acid effluent that must be discarded in a responsible manner, protecting the environment. The focus of this study was to examine the use of this effluent to increase reactivity of some phosphate rocks, thus enabling soluble phosphate fertilizer production. The effluent was diluted in deionized water with the following concentrations 0; 12.5; 25; 50; 75% (v v(-1)), which were added to four natural phosphate rocks: Araxá, Patos, Bayovar and Catalão and then left to react for 1 h and 24 h. There was an increase in water (PW), neutral ammonium citrate (PNAC) and citric acid (PCA) soluble phosphorus fractions. Such increases were dependent of rock type while the reaction time had no significant effect (p < 0.05) on the chemical and mineralogical phosphate characteristics. Phosphate fertilizers with low toxic metal concentrations and a high level of micronutrients were produced compared to the original natural rocks. The minimum amount of total P2O5, PNAC and PW, required for national legislation for phosphate partially acidulated fertilizer, were met when using Catalão and the effluent at the concentration of 55% (v v(-1)). Fertilizer similar to partially acidulated phosphate was obtained when Bayovar with effluent at 37.5% (v v(-1)) was used. Even though fertilizers obtained from Araxá and Patos did not contain the minimum levels of total P2O5 required by legislation, they can be used as a nutrient source and for acid effluent recycling and reuse.

Long-term manure application effects on phosphorus speciation, kinetics and distribution in highly weathered agricultural soils.

Phosphorus (P) K-edge XANES and Fe K-edge EXAFS spectroscopies along with sequential P chemical fractionation and desorption kinetics experiments, were employed to provide micro- and macro-scale information on the long-term fate of manure application on the solid-state speciation, kinetics and distribution of P in highly weathered agricultural soils of southern Brazil. Soil test P values ranged from 7.3 up to 16.5 times as much higher than the reference soil. A sharp increase in amorphous Fe and Al amounts were observed as an effect of the consecutive application of manures. Whereas our results showed that the P sorption capacity of some manured soils was not significantly affected, P risk assessment indices indicated that P losses should be expected, likely due to the excessive manure rates applied to the soils. The much higher contents of amorphous Fe and Al (hydr)oxides (55% and 80% increase with respect to the reference soil, respectively) in manured soils seem to have counterbalanced the inhibiting effect of soil organic matter on P sorption by creating additional P sorption sites. Accordingly, the newly created P sorbing surfaces were important to prevent an even larger P loss potential. Phosphorus K-edge XANES lent complimentary hints on the loss of crystallinity and transformation of originally present Fe-P minerals into poorly crystalline ones as an effect of manuring, whereas Fe K-edge EXAFS provided insights into the structural changes underwent in the soils upon manure application and soil management.