The dynamic features and microbial mechanism of nitrogen transformation for hydrothermal aqueous phase as fertilizer in dryland soil.

Hydrothermal aqueous phase (HAP) contains abundant organics and nutrients, which have potential to partially replace chemical fertilizers for enhancing plant growth and soil quality. However, the underlying reasons for low available nitrogen (N) and high N loss in dryland soil remain unclear. A cultivation experiment was conducted using HAP or urea to supply 160 mg N kg-1 in dryland soil. The dynamic changes of soil organic matters (SOMs), pH, N forms, and N cycling genes were investigated. Results showed that SOMs from HAP stimulated urease activity and ureC, which enhanced ammonification in turn. The high-molecular-weight SOMs relatively increased during 5-30 d and then biodegraded during 30-90 d, which SUV254 changed from 0.51 to 1.47 to 0.29 L-1 m-1. This affected ureC that changed from 5.58 to 5.34 to 5.75 lg copies g-1. Relative to urea, addition HAP enhanced ON mineralization by 8.40 times during 30-90 d due to higher ureC. It decreased NO3-N by 65.35%-77.32% but increased AOB and AOA by 0.25 and 0.90 lg copies g-1 at 5 d and 90 d, respectively. It little affected nirK and increased nosZ by 0.41 lg copies g-1 at 90 d. It increased N loss by 4.59 times. The soil pH for HAP was higher than that for urea after 11 d. The comprehensive effects of high SOMs and pH, including ammonification enhancement and nitrification activity inhibition, were the primary causes of high N loss. The core idea for developing high-efficiency HAP fertilizer is to moderately inhibit ammonification and promote nitrification.

Structural, optical and photocatalytic properties of magnetic recoverable Mn0.6Zn0.4Fe2O4@Zn0.9Mn0.1O heterojunction prepared from waste Mn-Zn batteries.

Green, simple and high value-adding technology is crucial for realizing waste batteries recycling. In this work, the magnetically recyclable Mn0.6Zn0.4Fe2O4@Zn0.9Mn0.1O (MZFO@ZMO) heterojunctions are prepared from waste Mn-Zn batteries via a green bioleaching and sample co-precipitation method. The as-prepared catalysts with different Zn0.9Mn0.1O weight percentage (25%, 50% and 75%) have been comprehensively characterized in structure, optics, photoelectrochemistry and photocatalytic activity. Characterization results indicate that MZFO@ZMO heterojunctions with the core-shell structure, demonstrates excellent absorption intensity in the visible light region, outperforming that of individual ZnO and Zn0.9Mn0.1O. Especially, the staggered bandgap alignment of Mn0.6Zn0.4Fe2O4 and Zn0.9Mn0.1O greatly enhances electron transfer and charge separation in the binary heterojunction system. The optimized MZFO@50%-ZMO shows the highest photodegradation performance toward methylene blue (MB) under the visible light irradiation, with a 99.7% of photodegradation efficiency of 20 mg L-1 of MB within 90 min, and its reactive kinetic constants is about 7.2, 10.8 and 21.7 times higher than that of Zn0.9Mn0.1O, P25 TiO2 and Mn0.6Zn0.4Fe2O4, respectively. The MB photocatalytic mechanism is investigated in the scavenger and 5,5-dimethylpyrroline-N-oxide (DMPO) spin-trapping electron spin resonance (ESR) experiments, and h+ and *O2- are identified as the major active species for MB degradation. In addition, MZFO@50%-ZMO also exhibits a good reusability and high magnetic separation properties after six successive cycles. This new material indicates the advantages of low costs, simple reuse and great potential in application.

Effects of process water obtained from hydrothermal carbonization of poultry litter on soil microbial community, nitrogen transformation, and plant nitrogen uptake.

Process water (PW) obtained from hydrothermal carbonization of nitrogen-rich (N-rich) biowaste is proposed to be a renewable resource utilized as a liquid N fertilizer. However, its effects on soil microbial community, N transformation, and plant N uptake are unclear or controversial. In this study, fertilizers were prepared with different percentages of PW (poultry litter, 220 °C 1 or 8 h, PW-S or -L) and urea to supply 160 mg kg-1 total N in a barren alkali soil. Results showed that the addition of PW relative to pure urea decreased organic N mineralization by low bio-accessibility, increased N loss by high soil pH, and decreased NO3--N by low nitrification substrate. It supported the lettuce in health but decreased plant N uptake by low NO3--N. It significantly increased the gram-positive bacteria that responded to resistant organic matter, changed the bacterial community to enhance decomposition, detoxification, ureolysis, and denitrification, and to decrease nitrification. Its inhibition effect on nitrification activity was stronger than that on nitrifiers growth. Different from PW-S, the addition of PW-L seriously and significantly decreased seed germination index and fungal biomass that responded to N retaining capacity, respectively. The best fertilizer was 50% urea +50% PW-S that supported the seed germination and seedling growth, and mildly affected microbial community.

Construction of a p-n heterojunction based on magnetic Mn0.6Zn0.4Fe2O4 and ZnIn2S4 to improve photocatalytic performance.

To improve the photocatalytic performance of Mn0.6Zn0.4Fe2O4 (MZFO) and ZnIn2S4 (ZIS) for organic pollutants, the p-n MZFO@ZIS heterojunctions with different weight percentage (10 ~ 40%) of MZFO are constructed from spent batteries and added indium ion via a green bioleaching and hydrothermal method. Structural, optical, and photocatalytic properties for the heterojunctions are investigated systematically by XRD, FT-IR, SEM-EDX, TEM, BET, VB-XPS, UV-vis DRS, PL, etc. The results confirm that p-n junction significantly improves the visible light adsorption and the separation efficiency of photogenerated carriers. Specifically, MZFO-25%@ZIS shows the highest photodegradation performance toward Congo red (CR), and its reactive kinetic constant is about 9.6, 7.8, and 7.0 times higher than that of P25 TiO2, MZFO, and ZIS, respectively, and MZFO-25%@ZIS still possesses a high reusability and simple magnetic separation after 5 cycles of reuse. The radical trapping experiments and electronic paramagnetic resonance (EPR) tests show that ·O2-, ·OH, and h+ are the most important active substance for degrading CR. The pathways for the CR degradation are further proposed based on the intermediate analysis. DFT + U calculations confirm that the high charge density of Zn-O, Fe-O, and Zn-S bonds in the MZFO and ZIS molecules provides the electrons for the sufficient production of free radicals. This work also provides a novel high value-added strategy for the green utilization of spent batteries.

Construction of magnetically recoverable MnZnFe2O4@Ag3PO4 Z-scheme photocatalyst for rapid visible-light-driven phenol degradation.

Visible-light-driven magnetic heterojunction as a promising photocatalysts has received much attention in environmental remediation. In this work, novel Z-scheme heterojunction MnZnFe2O4@Ag3PO4 (MZFO@APO) magnetic photocatalysts with excellent visible-light-driven photocatalytic activity are successfully constructed and characterized. The photocatalytic activity for phenol degradation is measured, and photodegradation mechanism is investigated with EPR, radical trapping experiments, and LC-MS. It turns out that the heterojunction introduced MZFO exhibits good adsorption effect on visible light and the direct Z-scheme bandgap alignment of MZFO and APO significantly improves charge separation and electron transfer, outperforming that of pure APO. MZFO@APO-40% with 40% APO content shows the rapid photodegradation performance, obtaining a 100% removal efficiency of phenol (25 mg L-1) after 12-min visible light irradiation, and its kinetic constants are approximately 25.3 and 4.9 times higher than that of P25 TiO2 and pure APO, respectively. Especially, MZFO@APO-40% also possesses a high magnetic separation property and can be efficiently reused for 5 cycles. Additionally, EPR and radical trapping experiments confirm that h+, O2-, and 1O2 are the main active species in the photocatalytic process. Hydroquinone and small molecular organic acids such as maleic acid and oxalic acid are detected by LC-MS, which further indicates that the pathway of phenol degradation involves hydroxylation, open-ring reactions, and mineralization reactions. The novel addition of MZFO in photocatalyst construction has the potential to promote its application in environmental remediation.

Green synthesis of magnetically recyclable Mn0.6Zn0.4Fe2O4@Zn1-xMnxS composites from spent batteries for visible light photocatalytic degradation of phenol.

Magnetic binary heterojunctions are a kind of promising photocatalysts due to their high catalytic activity and easy magnetic separation; however, their synthesis may involve high costs or secondary environmental impacts. In this work, the magnetically recyclable Mn0.6Zn0.4Fe2O4@Zn1-xMnxS (MZFO@Zn1-xMnxS, x = 0.00-0.07) photocatalysts are synthesized from spent batteries via a green biocheaching and egg white-assisted hydrothermal method. The as-synthesized photocatalysts have been comprehensively characterized in phase, morphology, texture, optics, photoelectrochemistry and photocatalytic activity. Characterization results indicate that the desired core-shell structure MZFO@Zn1-xMnxS composites are successfully synthesized, theirs absorption intensity in the visible light region is greatly enhanced compared to Zn1-xMnxS. In addition, doped Mn2+ in ZnS host lattice and the staggered bandgap alignment of MZFO and Zn1-xMnxS greatly enhances electron transfer and charge separation in the binary heterojunction system. The optimized MZFO@Zn0.95Mn0.05S shows the highest photodegradation performance toward phenol under the visible light irradiation, with a complete degradation of 25 mg L-1 of phenol within 120 min, and its reactive kinetic constants is about 5.2 and 13.3 times higher than that of pure Zn0.95Mn0.05S and MZFO, respectively. Furthermore, the mechanism and pathways for the degradation of phenol are proposed. In addition, MZFO@Zn0.95Mn0.05S also exhibits a good reusability and high magnetic separation properties after 5 successive cycles. This new material has the advantages of low costs, simple reuse and great potential in application.

Phytotoxicity and nutrition behavior of process water obtained from the hydrothermal carbonization of poultry litter and its effect on lettuce germination and growth.

Nine hydrothermal carbonization process waters (PWs) of poultry litter were prepared at 180, 220, and 260 °C for 1, 4, and 8 h, respectively. They were characterized with pH, EC (electric conductivity), DOC (dissolved organic carbon), TN (total nitrogen), NH4+-N, NO3--N, etc. After diluted according to TN, the PWs were supplied as liquid nitrogen fertilizers and their phytotoxic and nutrition effects on lettuce germination and growth were studied. The results showed that the PWs from short time (1 h) were with low DOC/TN and DOC/NH4+-N and high NH4+-N/TN. Compared with the PWs from long time 4 and 8 h, they provided more NH4+-N and less DOC and resulted in lettuce with relatively high germination index (GI), dry biomass, and low antioxidant enzyme activities. Especially, the PW from 220 °C and 1 h significantly enhanced the dry weight by 196.3% relative to negative control of nitrogen deficiency. However, all the PWs led lettuce to an unhealthy condition, which decreased GI and the chlorophyll content and increased antioxidant enzyme activities. Furthermore, it was confirmed by linear regression that the ratios of DOC/TN, NH4+-N/TN, and DOC/NH4+-N were the determining indexes for evaluating the phytotoxicity and nutrition behavior of the PWs as liquid nitrogen fertilizers.

Thermal oxidation activation of hydrochar for tetracycline adsorption: the role of oxygen concentration and temperature.

Poplar hydrochar (RHC) was activated by thermal oxidation (TA-O) in air at 300 °C (O300) and in air + N2 (0.5% O2) at 500 and 700 °C (O500 and O700), respectively, and in N2 at 300-700 °C (N300-N700) as control. Samples characterized by various methods were used to analyze their effect on tetracycline adsorption. The results showed that TA-O greatly increased adsorption capacity qe, 100 (mg·g-1, C0 = 100 mg·L-1) from 6.29 for RHC to 33.32, 96.23 and 60.90 for O300, O500 and O700, respectively. The O300 increased carboxyl and aromaticity whereas little influenced on porosity. The O500, with the highest SBET and Smicro, enhanced adsorption probably by micropore filling and π-π interactions. The O700 fused micropore into mesopore but decreased the SBET, Smicro and qe, 100. Thus, thermal oxidation at 500 °C and 0.5% O2 is recommended for hydrochar activation to absorb tetracycline.

Green synthesis of a novel Mn-Zn ferrite/biochar composite from waste batteries and pine sawdust for Pb2+ removal.

Magnetic ferrite/biochar composites are a kind of promising adsorbents due to their high adsorption efficiency and facile magnetic separation; however, their synthesis is associated with high cost and secondary environmental impacts. In this study, a novel Mn-Zn ferrite/biochar composite (MZF-BC) is synthesized via a green two-step biocheaching and hydrothermal method using waste batteries and pine sawdust. Characterization results indicate that the introduced Mn-Zn ferrite particles are successfully embedded and coated on biochar (BC), and synthesized MZF-BC50 with 50% BC content exhibits best performance with a specific surface area of 138.5 m2 g-1, the saturation magnetization of 27.5 emu g-1 and CEC value of 53.2 mmol 100 g-1. The maximum adsorption capacity of Pb2+ is 99.5 mg g-1 based on the Langmuir sorption isotherm study at 298 K, and pseudo-second-order model accurately describes the adsorption process. Regeneration test suggests that MZF-BC50 can be efficiently reused for 6 cycles. In addition, it exhibits a good selective Pb2+ and Cd2+ removal performance in lead-acid battery wastewater. The results illustrate that this newly developed material has low cost and rapid remediation of Pb2+ as good application potential.

Interactions between electrokinetics and rhizoremediation on the remediation of crude oil-contaminated soil.

An electrokinetics (EK)-enhanced phytoremediation system with ryegrass was constructed to remediate crude oil-polluted soil. The four treatments employed in this study included (1) without EK or ryegrass (CK-NR), (2) EK only (EK-NR), (3) ryegrass only (CK-R), and (4) EK and ryegrass (EK-R). After 30d of ryegrass growth, EK at 1.0 V·cm-1 with polarity reversal (PR-EK) was supplied for another 30 d. The electric current was recorded during remediation. The pH, electrical conductivity, total petroleum hydrocarbon content (TPH), 16S rDNA, functional genes of AlkB, Nah, and Phe, DGGE, and dehydrogenase activity in soil were measured. The physical-chemical indexes of the plant included the length, dry mass, and chlorophyll contents of the ryegrass. Results showed that EK-R removed 18.53 ±â€¯0.53% of TPH, which was higher than that of other treatments (13.34-14.31%). Meanwhile, the values of 16S rDNA, AlkB, Nah, Phe, and dehydrogenase activity in the bulk soil of EK-R all increased. Further clustering analysis with numbers of genes and DGGE demonstrated that EK-R was similar to the ryegrass rhizosphere soils in both EK-R and CK-R, while the EK treatment of EK-NR was similar to that of CK-NR without EK and ryegrass. These results indicate that the PR-EK treatment used in this experiment successfully enlarged the existing scale of the rhizosphere microorganisms, improved microbial activity and enhanced degradation of TPH.

Synthesis of novel waste batteries-sawdust-based adsorbent via a two-stage activation method for Pb2+ removal.

The novel waste alkaline battery-sawdust-based adsorbents (WABAs) are prepared by a two-stage activation method with the negative electrode materials as activator and different doping ratio of the positive electrode materials and pine sawdust as raw materials. The characteristics of the WABAs are analyzed by SEM, XRD, FT-IR, and specific surface determination (SBET). The Pb2+ adsorption properties of the WABAs are studied by changing the pH of solution, contact time, initial concentration, and temperature. It turns out that when the doping mass ratio is 1:4, the optimum performance of the WABAs is obtained, and comparing with the samples prepared by pure biomass, the iodine adsorption value, total acid groups, and cation exchange capacity (CEC) separately increased by 13, 106, and 22%, respectively. Kinetic studies show that the pseudo-second-order model is more suitable for describing the Pb2+ adsorption process and the Langmuir isotherm provides better fitting to the equilibrium data. The thermodynamic parameters indicate the adsorption process would be spontaneous and endothermic. Besides, the prepared WABAs could be reused for 5 cycles with high removal efficiency. This study provides an alternative route for waste alkaline battery treatment. Graphical abstract The schematic diagram of synthesis of waste batteries-sawdust-based adsorbent via a two-stage activation method for Pb2+ removal.

A study of biochemical route on construction of waste battery ferrite applying for nickel removal.

Mn-Zn ferrite (Mn1 - xZnxFe2O4, x = 0.2, 0.4, 0.6, and 0.8) nanomaterials were prepared by bioleaching and hydrothermal synthesis from waste Zn-Mn batteries. The materials were characterized by XRD, SEM, BET, VSM, CEC, and isoelectric point. It turned out when x = 0.4, synthesized Mn-Zn ferrite had best performance which was nanoferrite crystal structure with a specific surface area that reached 37.77 m2/g, the saturation magnetization was 62.85 emu/g, and isoelectric point and the CEC value were 7.33 and 43.51 mmol/100 g, respectively. In addition, the adsorption characteristics on Ni2+ were explored. The results of experiment suggested that data was more in line with the Freundlich model compared with Langmuir and Dubinin-Radushkevich isotherm models. Kinetics studies showed that pseudo-second-order kinetics was more suitable for describing the Ni2+ adsorption process where the maximum theoretical adsorption quantity was 52.99 mg/g. Thermodynamic parameters indicated the adsorption process can be spontaneous as an endothermic reaction, and warming was advantageous to adsorption. Besides, the adsorbent could be reused for six cycles with high removal efficiency. The magnetic and adsorptive properties of the adsorbent were promising, which had a high application value. Graphical abstract Fabrication process of nanometer ferrite by biological technology and hydrothermal synthesis for removal of Ni2.

Metallic ions catalysis for improving bioleaching yield of Zn and Mn from spent Zn-Mn batteries at high pulp density of 10.

Bioleaching of spent batteries was often conducted at pulp density of 1.0% or lower. In this work, metallic ions catalytic bioleaching was used for release Zn and Mn from spent ZMBs at 10% of pulp density. The results showed only Cu(2+) improved mobilization of Zn and Mn from the spent batteries among tested four metallic ions. When Cu(2+) content increased from 0 to 0.8 g/L, the maximum release efficiency elevated from 47.7% to 62.5% for Zn and from 30.9% to 62.4% for Mn, respectively. The Cu(2+) catalysis boosted bioleaching of resistant hetaerolite through forming a possible intermediate CuMn2O4 which was subject to be attacked by Fe(3+) based on a cycle of Fe(3+)/Fe(2+). However, poor growth of cells, formation of KFe3(SO4)2(OH)6 and its possible blockage between cells and energy matters destroyed the cycle of Fe(3+)/Fe(2+), stopping bioleaching of hetaerolite. The chemical reaction controlled model fitted best for describing Cu(2+) catalytic bioleaching of spent ZMBs.

Process controls for improving bioleaching performance of both Li and Co from spent lithium ion batteries at high pulp density and its thermodynamics and kinetics exploration.

Release of Co and Li from spent lithium ion batteries (LIBs) by bioleaching has attracted growing attentions. However, the pulp density was only 1% or lower, meaning that a huge quantity of media was required for bioleaching. In this work, bioleaching behavior of the spent LIBs at pulp densities ranging from 1% to 4% was investigated and process controls to improve bioleaching performance at pulp density of 2% were explored. The results showed that the pulp density exerted a considerable influence on leaching performance of Co and Li. The bioleaching efficiency decreased respectively from 52% to 10% for Co and from 80% to 37% for Li when pulp density rose from 1% to 4%. However, the maximum extraction efficiency of 89% for Li and 72% for Co was obtained at pulp density of 2% by process controls. Bioleaching of the spent LIBs has much greater potential to occur than traditional chemical leaching based on thermodynamics analysis. The product layer diffusion model described best bioleaching behavior of Co and Li.

[Determination of patulin in juice by ultra performance liquid chromatography-tandem mass spectrometry].

A method was developed for the simultaneous determination of patulin in juice by solid phase extraction (SPE)-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS). The cloudy juice was hydrolyzed by enzyme and extracted by ethyl acetate. The extract of cloudy juice was then enriched and purified by an HLB SPE cartridge. If the juice was clear it was directly treated by the cartridge as above. The separation was performed on a C18 column with the gradient elution of acetonitrile and water. The patulin was detected by MS with electrospray negative ionization (ESI-) in the mode of multiple reaction monitoring (MRM). The good linearity was observed in the range of 1.0 - 500 microg/L with the correlation coefficient of 0. 999 and the limit of quantitation of 5.0 microg/kg. The recoveries were in the range of 80. 6% -91. 8% at three spiked levels of 5.0, 25.0 and 100.0 microg/kg with the relative standard deviations of 1.5% -7.3%. It was proved to be a simple, reliable and accurate method which can fully meet the requirements of patulin detection in juice samples according to most domestic and international legislations.