Treatment of distiller grain with wet-process phosphoric acid leads to biochar for the sustained release of nutrients and adsorption of Cr(VI).

Soil amendment products, such as biochar, with both sustained nutrient release and heavy metal retention properties are of great need in agricultural and environmental industries. Herein, we successfully prepared a new biochar material with multinutrient sustained-release characteristics and chromium removal potential derived from distiller grain by wet-process phosphoric acid (WPPA) modification without washing. SEM, TEM TG-IR, in situ DRIFTS and XRD characterization indicated that biochar and polyphosphate formed simultaneously and were tightly intertwined by one-step pyrolysis. The optimal product (PKBC-400) had the most stable carbon structure and an adequate P-O-P structure with less P loss. Batch experiments illustrated that 92.83% P (ortho-P), 85.94% K, 41.49% Fe, 78.42% Al and 65.60% Mg were continuously released in water from PKBC-400 within 63 days, and the maximum Cr removal rate reached 83.57% (50 mg/L K2Cr2O7, pH=3.0) with an increased BET surface area (304.0557 m2/g) after nutrient release. SEM, IC and 31P NMR analyses revealed that the dissolution and hydrolysis of polyphosphates not only realized the sustained release of multiple nutrients but also significantly improved the sustained release performance. The proposed resource utilization strategy provided new ideas for Cr hazard control, biomass waste utilization and fertilizer development.

Selective adsorption of various phosphorus species coexistence in water-soluble ammonium polyphosphate on goethite: Experimental investigation and molecular dynamics simulation.

The geochemical processes of polyphosphates (poly-Ps) are important for phosphorus (P) management and environmental protection. Water-soluble ammonium polyphosphate (APP) containing various P species has been increasingly used as an alternative P-fertilizer. The various P species coexistence and the chelation of poly-Ps with mental would trigger the P's competitive adsorption and affect the APP's adsorption intensity on goethite, compared to single orthophosphate (P1). P adsorption behaviors of APP1 with two P species and APP2 with seven P species on goethite were investigated via batch experiments in comparison to the traditional P-fertilizer of mono-ammonium phosphate (MAP). Coadsorption of P1 and pyrophosphate (P2) on goethite was investigated by molecular dynamics (MD) simulation. The more Fe3+ dissolved from goethite as a bridge due to the chelation of poly-Ps in APP and contributed to the stronger APP adsorption on goethite compared with MAP. Ion chromatography and spectral analysis showed P1 and P2 in APP were mainly adsorbed by goethite via mainly forming bidentate complexes. The goethite preferentially adsorbed P1 at lower APP concentration but increased the poly-Ps' adsorption at higher APP concentration. MD simulation showed that electrostatic interaction and hydrogen bonds played a key role in water-phosphates-goethite systems. The P1 pre-adsorbed on goethite could be replaced by P2 at high P2 concentration. The results develop new insights regarding the selective adsorption of various P species coexistence in goethite-rich environments.

Differences in main processes to transform phosphorus influenced by ammonium nitrogen in flooded intensive agricultural and steppe soils.

Exogenous ammonium nitrogen (AN) fertilization/deposition and the subsequently induced soil acidification, might exacerbate soil phosphorus (P) transformation and mobility, whereas poor understanding in abiotic and biotic processes still existed between intensively cultivated soil with high proportion of legacy inorganic P (Pi) in comparison to natural steppe soil with high proportion of organic P (Po). Column batch flooded experiment using vegetable (VEG) and steppe (STE) soils was conducted to investigate the P transformation and mobility influenced by 60-day intermittent elution with an (1500 mg N kg-1) solution or an acid sulfate (107 mmol H+ kg-1) solution. The results showed that AN elution significantly decreased the contents of all Pi fractions and strengthened Pi leaching, whereas acid elution increased the contents of Al-Pi, Fe-Pi, and reductant-soluble Pi and reduced P leaching in VEG soil. In contrast, AN elution increased the contents of soluble-Po and Al-(Pi + Po) and decreased Ca-P and Fe-Pi, no effects on P leaching, whereas acid elution increased the contents of soluble-(Pi + Po), Al-(Pi + Po), Fe-(Pi + Po) and reduced P leaching in STE soil. Variances analysis showed that pH and microbial biomass carbon were the most important factors to predict the P composition of the VEG and the STE soil, respectively. This indicated that AN elution released the soil mineral-bound phosphate with ammonia oxidation coupled with Fe(III) reduction, besides the same chemical influences on Fe/Al oxides as acid elution in VEG soil; while predominantly affected biochemical/biological processes of soil P by changing microbial biomass and enzyme activities in STE soil.

Manure and nitrogen application enhances soil phosphorus mobility in calcareous soil in greenhouses.

Over many years, high phosphorus (P) loading for intensive vegetable cropping in greenhouses of North China has contributed to excessive P accumulation, resulting in environmental risk. In this study, the influences of manure and nitrogen (N) application on the transformation and transport of soil P were investigated after nine years in a greenhouse tomato double cropping system (winter-spring and autumn-winter seasons). High loading of manure significantly increased the soil inorganic P (Pi), inositol hexakisphosphate (IHP), mobile P and P saturation ratio (PSR, >0.7 in 0-30 cm depth soil; PSR was estimated from P/(Fe + Al) in an oxalate extract of the soil). The high rate of N fertilizer application to the studied calcareous soil with heavy loading of manure increased the following: (i) mobile organic P (Po) and Pi fractions, as evidenced by the decrease in the ratio of monoesters to diesters and the proportion of stable Pi (i.e., HCl-Pi) in total P (Pt) in 0-30 cm depth soil; (ii) relative distribution of Po in the subsoil layer; and (iii) P leaching to soil depths below 90 cm and the proportion of Po in Pt in the leachate. More acidic soil due to excessive N application increased P mobility and leaching. The increase in Ox-Al (oxalate-extractable Al) and the proportion of microbe-associated Po related to N application at soil depths of 0-30 cm suggested decrease in the net Po mineralization, which may contribute to downward transport of Po in the soil profile.

Phosphorus in China's Intensive Vegetable Production Systems: Overfertilization, Soil Enrichment, and Environmental Implications.

China's vegetable production has experienced a rapid growth in recent years. Total production amounted to 522.7 million Mg (1 Mg = 10 g) in 2009, which was more than nine times that in 1980 and represented >50% of the world production. Meanwhile, excessive use of animal manures and chemical fertilizers in vegetable fields has brought various production and environmental challenges, including excessive accumulation of nutrients in soils and accelerated water pollution problems. In this study, we have evaluated the current status of phosphorus (P) in China's intensive vegetable production systems based on data summarized from nearly 100 publications plus results from our recent experiments. Gross overfertilization occurred in greenhouse (571 kg P ha) and open-field (117 kg P ha) vegetable systems compared with P removal in harvested crops (44 and 25 kg P ha) per season. Excess P input led to soil enrichment of labile P, measured as Olsen-P, averaging 179 (greenhouses) and 100 mg P kg (open fields) in the 0- to 20-cm soil depth, and in some cases led to P leaching, as evidenced by increases in Olsen-P and CaCl-P at the 40- to 60-cm soil depth. The vast majority of vegetable soils had Olsen-P exceeding the critical level (46.0-58.0 mg P kg) for optimum vegetable yield. Innovative policies and strategies are urgently needed to implement science-based nutrient management practices to attain sustainable vegetable production while protecting natural and environmental resources.