Graphitic carbon nitride/biochar composite synthesized by a facile ball-milling method for the adsorption and photocatalytic degradation of enrofloxacin

In order to enhance the removal performance of graphitic carbon nitride (g-C₃N₄) on organic pollutant, a simultaneous process of adsorption and photocatalysis was achieved via the compounding of biochar and g-C₃N₄. In this study, g-C₃N₄ was obtained by a condensation reaction of melamine at 550°C. Then the g-C₃N₄/biochar composites were synthesized by ball milling biochar and g-C₃N₄ together, which was considered as a simple, economical, and green strategy. The characterization of resulting g-C₃N₄/biochar suggested that biochar and g-C₃N₄ achieved effective linkage. The adsorption and photocatalytic performance of the composites were evaluated with enrofloxacin (EFA) as a model pollutant. The result showed that all the g-C₃N₄/biochar composites displayed higher adsorption and photocatalytic performance to EFA than that of pure g-C₃N₄. The 50% g-C₃N₄/biochar performed best and removed 45.2% and 81.1% of EFA (10 mg/L) under darkness and light with a dosage of 1 mg/mL, while g-C₃N₄ were 19.0% and 27.3%, respectively. Besides, 50% g-C₃N₄/biochar showed the highest total organic carbon (TOC) removal efficiency (65.9%). Radical trapping experiments suggested that superoxide radical (?O₂^?) and hole (h⁺) were the main active species in the photocatalytic process. After 4 cycles, the composite still exhibited activity for catalytic removal of EFA.     

Simultaneous adsorption of As(Ⅲ) and Pb(Ⅱ) by the iron-sulfur codoped biochar composite:Competitive and synergistic effects

Simultaneous elimination of As(Ⅲ) and Pb(Ⅱ) from wastewater is still a great challenge.In this work,an iron-sulfur codoped biochar (Fe/S-BC) was successfully fabricated in a simplified way and was applied to the remediate the co-pollution of As(Ⅲ) and Pb(Ⅱ).The positive enthalpy indicated that the adsorption in As-Pb co-pollution was an endothermic reaction.The mechanism of As(Ⅲ) removal could be illustrated by surface complexation,oxidation and precipitation.In addition to precipitation and com...     

A critical review on the application of biochar in environmental pollution remediation: Role of persistent free radicals (PFRs)

Biochar as an emerging carbonaceous material has exhibited a great potential in environmental application for its perfect adsorption ability. However, there are abundant persistent free radicals (PFRs) in biochar, so the direct and indirect PFRs-mediated removal of organic and inorganic contaminants by biochar was widely reported. In order to comprehend deeply the formation of PFRs in biochar and their interactions with contaminants, this paper reviews the formation mechanisms of PFRs in biochar and the PFRs-mediated environmental applications of biochar in recent years. Finally, future challenges in this field are also proposed. This review provides a more comprehensive understanding on the emerging applications of biochar from the viewpoint of the catalytic role of PFRs.     

Responses of ammonia-oxidizing microorganisms to biochar and compost amendments of heavy metals-polluted soil

Heavy metal pollution affects soil ecological function. Biochar and compost can effectively remediate heavy metals and increase soil nutrients. The effects and mechanisms of biochar and compost amendments on soil nitrogen cycle function in heavy-metal contaminated soils are not fully understood. This study examined how biochar, compost, and their integrated use affected ammonia-oxidizing microorganisms in heavy metal polluted soil. Quantitative PCR was used to determine the abundance of ammonia-oxidizing archaea (AOA) and bacteria (AOB). Ammonia monooxygenase (AMO) activity was evaluated by the enzyme-linked immunosorbent assay. Results showed that compost rather than biochar improved nitrogen conversion in soil. Biochar, compost, or their integrated application significantly reduced the effective Zn and Cd speciation. Adding compost obviously increased As and Cu effective speciation, bacterial 16S rRNA abundance, and AMO activity. AOB, stimulated by compost addition, was significantly more abundant than AOA throughout remediation. Correlation analysis showed that AOB abundance positively correlated with NO₃^?-N (r = 0.830, P < 0.01), and that AMO activity had significant correlation with EC (r = -0.908, P < 0.01) and water-soluble carbon (r = -0.868, P < 0.01). Those seem to be the most vital factors affecting AOB community and their function in heavy metal-polluted soil remediated by biochar and compost.     

Enhanced microbial reduction of aqueous hexavalent chromium by Shewanella oneidensis MR-1 with biochar as electron shuttle

Biochar, carbonaceous material produced from biomass pyrolysis, has been demonstrated to have electron transfer property(associated with redox active groups and multi condensed aromatic moiety), and to be also involved in biogeochemical redox reactions. In this study, the enhanced removal of Cr(VI) by Shewanella oneidensis MR-1(MR-1) in the presence of biochars with different pyrolysis temperatures(300 to 800 °C) was investigated to understand how biochar interacts with Cr(VI) reducing bacteria ...     

Preliminary study on the electrocatalytic performance of an iron biochar catalyst prepared from iron-enriched plants

Eichhornia crassipes is a hyperaccumulator of metals and has been widely used to remove metal pollutants from water, but disposal of contaminated plants is problematic.Biochar prepared from plants is commonly used to remediate soils and sequester carbon.Here, the catalytic activity of biochar prepared from plants enriched with iron was investigated as a potentially beneficial use of metal-contaminated plants.In a 30-day hydroponic experiment, E.crassipes was exposed to different concentrations of Fe(Ⅲ)(0, 4, 8, 16, 32 and 64 mg/L), and Fe-biochar(Fe-BC) was prepared by pyrolysis of the plant roots.The biochar was characterized using X-ray diffraction(XRD), scanning electron microscopy(SEM), energy dispersive X-ray spectrometry(EDS), Brunauer–Emmett–Teller(BET) analysis, X-ray photoelectron spectroscopy(XPS) and atomic absorption spectrometry(AAS).The original root morphology was visible and iron was present as γ-Fe_2O_3 and Fe_3O_4.The biochar enriched with Fe(Ⅲ) at 8 mg/L(8-Fe-BC) had the smallest specific surface area(SSA, 13.54 m~2/g) and the highest Fe content(27.9 mg/g).Fe-BC catalytic activity was tested in the electrocatalytic reduction of H_2O_2 using cyclic voltammetry(CV).The largest reduction current(1.82 mA/cm~2) was displayed by 8-Fe-BC, indicating the highest potential catalytic activity.We report here, for the first time, on the catalytic activity of biochar made from iron-enriched plants and demonstrate the potential for reusing metalcontaminated plants to produce a biochar catalyst.     

One-step preparation of a novel graphitic biochar/Cu0/Fe3O4 composite using CO2-ambiance pyrolysis to activate peroxydisulfate for dye degradation

Herein,a one-step co-pyrolysis protocol was adopted for the first time to prepare a novel pyrogenic carbon-Cu⁰/Fe₃O₄ heteroatoms (FCBC) in CO₂ ambiance to discern the roles of each component in PDS activation.During co-pyrolysis,CO₂ catalyzed formation of reducing gases by biomass which facilitated reductive transformation of Fe³⁺ and Cu²⁺ to Cu⁰ and Fe₃O₄,respectively.According to the a...     

Migration and transformation of Sb are affected by Mn(III/IV) associated with lepidocrocite originating from Fe(II) oxidation

Antimony (Sb) is a recognized priority pollutant with toxicity that is influenced by its migration and transformation processes. Oxidation of Fe(II) to Fe(III) oxides, which is a common phenomenon in the environment, is often accompanied by the formation of Mn(III/IV) and might affect the fate of Sb. In this study, incorporated Mn(III) and sorbed/precipitated Mn(III/IV) associated with lepidocrocite were prepared by adding Mn(II) during and after Fe(II) oxidation, respectively, and the effects of these Mn species on Sb fate were investigated. Our results indicated that the association of these Mn species with lepidocrocite obviously enhanced Sb(III) oxidation to Sb(V), while concomitantly inhibiting Sb sorption due to the lower sorption capacity of lepidocrocite for Sb(V) than Sb(III). Additionally, Mn oxide equivalents increased in the presence of Sb, indicating that Sb oxidation by Mn(III/IV) associated with lepidocrocite was a continuous recycling process in which Mn(II) released from Mn(III/IV) reduction by Sb(III) could be oxidized to Mn(III/IV) again. This recycling process was favorable for effective Sb(III) oxidation. Moreover, Sb(V) generated from Sb(III) oxidation by Mn(III/IV) enhanced Mn(II) sorption at the beginning of the process, and thus favored Mn(III/IV) formation, which could further promote Sb(III) oxidation to Sb(V). Overall, this study elucidated the effects of Mn(III/IV) associated with lepidocrocite arisen from Fe(II) oxidation on Sb migration and transformation and revealed the underlying reaction mechanisms, contributing to a better understanding of the geochemical dynamics of Sb.     

Release and sedimentation behaviors of biochar colloids in soil solutions

The release of biochar colloids considerably affects the stability of biochar in environment. Currently, information on the release behavior and suspension stability of biochar colloids in real soil solutions is scarce. In this study, 20 soils were collected from different districts in China and the release behavior of biochar colloids and their suspension stability in soil solutions were systematically examined. The results showed that both pyrolysis temperature and biomass source had important effects on the formation of biochar colloids in soil solutions. The formation amount of biochar colloids from low pyrolysis temperatures (400 °C) (average amount of 9.33–16.41 mg/g) were significantly higher than those from high pyrolysis temperatures (700 °C) (average amount of less than 2 mg/g). The formation amount of wheat straw-derived biochar colloids were higher than those of rice straw-derived biochar colloids probably due to the higher O/C ratio in wheat-straw biochar. Further, biochar colloidal formation amount was negatively correlated with comprehensive effect of dissolved organic carbon, Fe and Al in soil solutions. The sedimentation curve of biochar colloids in soil solutions is well described by an exponential model and demonstrated high suspension stability. Around 40% of the biochar colloids were maintained in the suspension at the final sedimentation equilibrium. The settling efficiency of biochar colloids was positively correlated with comprehensive effect of the ionic strength and K, Ca, Na, and Mg contents in soil solutions. Our findings help promote a deeper understanding of biochar loss and stability in the soil-water environment.     

Influence of modified biochar supported sulfidation of nano-zero-valent-iron (S-nZVI/BC) on nitrate removal and greenhouse gas emission in constructed wetland

In this study, the biochar (BC) produced from sawdust, sludge, reed and walnut were used to support sulfidation of nano-zero-valent-iron (S-nZVI) to enhance nitrate (${\text{NO}}_3^{-}$-N) removal and investigate the impact on greenhouse gas emissions. Batch experiment results showed the S-nZVI/BC_{sawdust (2:1, 500)}, S-nZVI/BC_{sludge (2:1, 900)}, S-nZVI/BC_{reed (2:1, 700)}, and S-nZVI/BC _{walnut (2:1, 700)} respectively improved ${\text{NO}}_3^{-}$-N removal efficiencies by 22%, 20%, 3% and 0.1%, and the selectivity toward N₂ by 22%, 25%, 22% and 18%. S-nZVI uniformly loaded on BC provided electrons for the conversion of ${\text{NO}}_3^{-}$-N to N₂ through Fe⁰. At the same time, FeS_x layer was formed on the outer layer of ZVI in the sulfidation process to prevent iron oxidation, so as to improve the electrons utilization efficiency After adding four kinds of S-nZVI/BC into constructed wetlands (CWs), the ${\text{NO}}_3^{-}$-N removal efficiencies could reach 100% and the N₂O emission fluxes were reduced by 24.17%-36.63%. And the average removal efficiencies of TN, COD, TP were increased by 21.9%, -16.5%, 44.3%, repectively. The increasing relative abundances of denitrifying bacteria, such as Comamonas and Simplicispira, suggested that S-nZVI/BC could also improve the process of microbial denitrification. In addition, different S-nZVI/BC had different effects on denitrification functional genes (narG, nirk, nirS and nosZ genes), methanotrophs (pmoA) and methanogenesis (mcrA). This research provided an effective method to improve ${\text{NO}}_3^{-}$-N removal and reduce N₂O emission in CWs.     

Remediation of arsenic-contaminated paddy field by a new iron oxidizing strain (Ochrobactrum sp.) and iron-modified biochar

Iron-oxidizing strain (FeOB) and iron modified biochars have been shown arsenic (As) remediation ability in the environment. However, due to the complicated soil environment, few field experiment has been conducted. The study was conducted to investigate the potential of iron modified biochar (BC-FeOS) and biomineralization by a new found FeOB to remediate As-contaminated paddy field. Compared with the control, the As contents of G_B (BC-FeOS), G_F (FeOB), G_FN (FeOB and nitrogen fertilizer), G_BF (BC-FeOS and FeOB) and G_BFN (BC-FeOS, FeOB and nitrogen fertilizer) treatments in pore water decreased by 36.53%–80.03% and the microbial richness of iron-oxidizing bacteria in these treatments increased in soils at the rice maturation stage. The concentrations of available As of G_B, G_F, G_FN, G_BF and G_BFN at the tillering stage were significantly decreased by 10.78%–55.48%. The concentrations of nonspecifically absorbed and specifically absorbed As fractions of G_B, G_F, G_FN, G_BF and G_BFN in soils were decreased and the amorphous and poorly crystalline hydrated Fe and Al oxide-bound fraction was increased. Moreover, the As contents of G_B, G_F, G_FN, G_BF and G_BFN in rice grains were significantly decreased (*P < 0.05) and the total As contents of G_FN, G_BF and G_BFN were lower than the standard limit of the National Standard for Food Safety (GB 2762-2017). Compared with the other treatments, G_BFN showed the greatest potential for the effective remediation of As-contaminated paddy fields.     

Enhanced removal of high-As(Ⅲ) from Cl(-Ⅰ)-diluted SO4(-Ⅱ)-rich wastewater at pH 2.3 via mixed tooeleite and(Cl(-Ⅰ)-free) ferric arsenite hydroxychloride formation

An advanced cost-saving method of removal of high-As(Ⅲ) from SO₄(-Ⅱ)-rich metallurgi cal wastewater has been developed by diluting the SO₄(-Ⅱ) content with As(Ⅲ)-Cl(-Ⅰ)-rich metallurgical wastewater and then by the direct precipitation of As(Ⅲ) with Fe(Ⅲ) at pH2.3.As(Ⅲ) removal at various SO₄(-Ⅱ)/Cl(-Ⅰ) molar ratios and temperatures was investigated The results showed that 65.2–98.2%of As(III) immobilization into solids occurred at the SO₄(Ⅱ)/Cl(-Ⅰ) mo...     

Enzymatic preparation of hydrophobic biomass with one-pot synthesis and the oil removal performance

Oil pollution is causing deleterious damage to aquatic ecosystems and human health. The utilization of agricultural waste such as corn stalk (CS) to produce biosorbents has been considered an ecofriendly and efficient approach for removing oil. However, most previous studies focused on the modification of the whole CS, which is inefficient due to the heterogeneity of CS. In this study, corn stalk pith (CP), which has excellent amphipathic characteristics, was selected to prepare a high-efficienc...     

Remediation performance and mechanisms of Cu and Cd contaminated water and soil using Mn/Al-layered double oxide-loaded biochar

The combined pollution of heavy metals is ubiquitous worldwide. Mn/Al-layered double oxide-loaded crab shells biochar (LDO/BC) was prepared, so as to remediate the combined pollution of Cd and Cu in soil and water. The pristine and used LDO/BC were characterized and the results revealed that the layered double oxide was successfully loaded on crab shells biochar (BC) and metal element Ca in crab shells was beneficial to the formation of more regular layered and flake structure. The maximal adsorption capacity (Q_m) of LDO/BC for aqueous Cu²⁺ and Cd²⁺ was 66.23 and 73.47 mg/g, respectively. LDO/BC and BC were used to remediate e-waste-contaminated soil for the first time and exhibited highly efficient performance. The extraction amount of Cu and Cd in the contaminated soil by diethylene triamine penta-acetic acid (DTPA) after treating with 5% LDO/BC was significantly reduced from 819.84 to 205.95 mg/kg (with passivation rate 74.8%) and 8.46 to 4.16 mg/kg (with passivation rate 50.8%), respectively, inferring that the bioavailability of heavy metals declined remarkably. The experimental result also suggested that after remediation by LDO/BC the exchangeable and weak acid soluble Cu and Cd in soil translated to reducible, residual and oxidizable fraction which are more stable state. Precipitation, complexation and ion exchange were proposed as the possible mechanisms for Cd and Cu removal. In general, these experiment results indicate that LDO/BC can be a potentially effective reagent for remediation of heavy metal contaminated water and soil.     

Adsorption and recovery of phosphate from water by amine fiber, effects of co-existing ions and column filtration

A weak-base adsorption fiber,acrylic amine fiber(AAF),was prepared for removal and recovery of phosphate from water.The adsorption properties of the AAF for phosphate and effects of co-existing ions were investigated using batch and column filtration experiments,scanning electron microscope,and Fourier transform infrared techniques.Experimental results showed that AAF had a high phosphate adsorption capacity of 119 mg/g at pH 7.0.The effects of calcium,sulfate,carbonate,nitrate,and fluoride show...     

An investigation of changes in water quality throughout the drinking water production/distribution chain using toxicological and fluorescence analyses

Changes in water quality from source water to finished water and tap water at two conventional drinking water treatment plants(DWTPs) were monitored.Beside the routine water quality testing,Caenorhabditis elegans-based toxicity assays and the fluorescence excitation–emission matrices technique were also applied.Both DWTPs supplied drinking water that met government standards.Under current test conditions,both the investigated finished water and tap water samples exhibited stronger lethal,genotox...     

Physiological and biochemical responses of Microcystis aeruginosa to phosphine (PH3) under elevated CO2

Phosphine(PH₃) is an important factor driving the outbreak of cyanobacterial blooms that produce toxic microcystin threating human health.To clarify the physiological and biochemical responses of cyanobacteria to PH₃ under elevated CO₂ concentration,Microcystis aeruginosa was used in the coupling treatment of 1000 ppmv CO₂ and PH₃ at different concentrations respectively.The chlorophyll a(Chl-a),carotenoid,net photosynthetic rate and total p...     

Remediation of Cu and As contaminated water and soil utilizing biochar supported layered double hydroxide: Mechanisms and soil environment altering

Preparing materials for simultaneous remediation of anionic and cationic heavy metals contamination has always been the focus of research. Herein a biochar supported FeMnMg layered double hydroxide (LDH) composites (LB) for simultaneous remediation of copper and arsenic contamination in water and soil has been assembled by a facile co-precipitation approach. Both adsorption isotherm and kinetics studies of heavy metals removal by LB were applied to look into the adsorption performance of adsorbents in water. Moreover, the adsorption mechanisms of Cu and As by LB were investigated, showing that Cu in aqueous solution was removed by the isomorphic substitution, precipitation and electrostatic adsorption while As was removed by complexation. In addition, the availability of Cu and As in the soil incubation experiments was reduced by 35.54%–63.00% and 8.39%–29.04%, respectively by using LB. Meanwhile, the addition of LB increased the activities of urease and sucrase by 93.78%–374.35% and 84.35%–520.04%, respectively, of which 1% of the dosage was the best. A phenomenon was found that the richness and structure of microbial community became vigorous within 1% dosage of LB, which indirectly enhanced the passivation and stabilization of heavy metals. These results indicated that the soil environment was significantly improved by LB. This research demonstrates that LB would be an imaginably forceful material for the remediation of anionic and cationic heavy metals in contaminated water and soil.     

High phosphate removal using La(OH)3 loaded chitosan based composites and mechanistic study

Our present study was to prepare a biomass-supported adsorbents with high adsorptive capacity and high selectivity to prevent the accelerated eutrophication in water body. To this end, different metal hydroxide (La, Zr and Fe) first was successfully loaded on chitosan microspheres. Then the quaternary ammonium group with different content was introduced into the adsorbent by polymerization. By comparison of adsorption properties, chitosan-La(OH)₃-quaternary ammonium-20% (CS-La-N-20%) has strong adsorption to phosphate (160 mg/g) by immobilizing nano-sized La(OH)₃ within a quaternary-aminated chitosan and it maintain high adsorption in the presence of salt ions. The pH results indicated that the CS-La-N-20% would effectively sequestrate phosphate over a wide pH range between 3 and 7 without significant La³⁺ leaching. What's more, adsorption capacity on the introduce of positively charged quanternary-aminated groups was significantly higher than that of the unmodified adsorbents at alkaline conditions. The column adsorption capacity reached 1300 bed volumes (BV) when phosphate concentration decreased until 0.5 mg/L at 6 BV/hr. The column adsorption/desorption reveals that no significant capacity loss is observed, indicating excellent stability and repeated use property. Characterizations revealed that phosphate adsorption on CS-La-N-20% through ligand exchange (impregnated nano-La(OH)₃) and electrostatic attraction (positively charged quanternary-aminated groups). All the results suggested that CS-La-N-20% can serve as a promising adsorbent for preferable phosphate removal in realistic application.     

Evaluating the biotoxicity of surface water in a grassy lake in North China

The biological toxicity of aquatic ecosystems should be considered when assessing the effects of toxicity on the water environment. The aim of this study was to identify the main pollutants in the Baiyangdian (BYD) and the factors that contribute to biological toxicity. We determined various physical and chemical indicators in the surface water of the BYD, including nutrients and heavy metals, and the biological toxicity. We also explored the sources of the main pollutants and how the pollutants contributed to toxicity in the lake, using correlation analysis and an index of the biological toxicity. The results showed that total nitrogen (TN), ammoniacal nitrogen (NH₄⁺-N), chromium (Cr), and zinc (Zn) were the main pollutants in the BYD surface water. The average concentration of Cr was 2.3 times greater than the Class V threshold, and the concentrations at about 65% of the sampling points, mainly those in the southern part of the BYD, exceeded the threshold standard. The average concentration of Zn was 1.25 times higher than the Class V threshold, with the concentrations of about 35% of the samples greater than the threshold concentration. The integrated toxicity of the surface water to luminescent bacteria ranged from 0.51% to 58%, and averaged 24.07%, which was within the range of moderate toxicity. The inhibition rates were high near Diantou (59%) and Duan (51.6%). The pollutant levels in the BYD tend to be related to the population density, with pollution mainly caused by sewage and domestic garbage, with little influence from local industries. Cr and TN were strongly correlated, but the biological toxicity was not correlated with any of the individual environmental indicators, which suggests that the toxicity in the surface water of the BYD reflected the combined effects of the environmental factors, rather than a single factor. The information from this study, about the main pollutants and the relationships between the physical and chemical properties of the surface water in the BYD, can be used to support plans for restoring the BYD.