Nano boron carbide effectively boost Fenton-like performance of hematite mediated systems: Roles of hematite exposed facets and synergistic catalysis between Fe and B.

The inherent properties of exposed facets of iron minerals played key roles in heterogeneous reactions at the mineral interface, and the addition of co-catalysts has been elucidated to further enhance the reactions for contaminants degradation. Here, synergistic Fenton-like catalytic reactivity of different hematite dominant exposed facets ({001}, {012}, {100}, and {113}) with nano boron carbide (B4C) was revealed. In 5 h, as compared with the cumulative •OH in the B4C/H2O2 system (96.9 µM), while that in the {001}/B4C/H2O2 system was decreased by 19.6%, those in the {012}/B4C/H2O2, {100}/B4C/H2O2, and {113}/B4C/H2O2 systems were increased by 53.8%, 75.9%, and 84.0%, respectively. Significantly, {113}/B4C/H2O2 system exhibited strong capability for degradation of a broad spectrum of organic pollutants, including typical phenol, endocrine disruptor (bisphenol A), antibiotic (sulfanilamide), dyes (Rhodamine B and methylene blue), and pesticide (atrazine). During the Fenton-like reactions, higher synergy factor, Fe(III)/Fe(II) cycling rate, and amount of Fe-O-B bond in the {113}/B4C/H2O2 system were shown than those in other systems, thus exhibiting its desirable catalytic performance for •OH production and pollutants oxidation. Iron species and X-ray photoelectron spectroscopy (XPS) analyses indicated that B-B bond and interfacial suboxide boron (e.g., B-O) could provide electrons to facilitate Fe(III) reduction for boosting the Fe(III)/Fe(II) cycling. Density functional theory (DFT) results demonstrated the formation of Fe-O-B bond on hematite {113}, {100}, and {012} facets, which were beneficial to the breakage of O-O bond of bound H2O2 molecule and thus improved the generation of •OH. This study emphasized the essential role of B4C in developing tailored hematite facets as a contaminant remediation substrate, and provided important insights into the design of efficient heterogeneous Fenton-like systems.

Nitrate and nitrite reduction by adsorbed Fe(II) generated from ligand-promoted dissolution of biogenic iron minerals in groundwater.

Chemical denitrification by redox-active Fe(II) species is pivotal in the coupled iron and nitrogen cycles. The reductive dissolution of ferric minerals by ligand can generate Fe(II)-ligand complexes, but their reducing capability for electrophilic pollutants like nitrate and nitrite remains uncertain. Here, biogenic secondary iron minerals (SIM) after dissimilatory iron reduction were reductively dissolved by oxalate and the siderophore desferrioxamine B, and subsequently the partially-dissolved SIM (SIMD) effectively removed NO2- from groundwater via reduction, while exhibiting much lower reactivity towards NO3-. The dissolution and removal processes were well-fitted with the Kabai model and the pseudo-second-order adsorption model, respectively. The equilibrium NO2- removal capacity (qe) of SIMD reached 0.146-0.223 mmol/g, accompanied with the rate constants as 0.433-0.810 g/(mmol·h). The emission of N2O and NO verified the occurrence of chemical denitrification during NO2- removal by SIMD. From the perspective of Fe(II) reactivity, SIMD exhibited higher densities of surface Fe(II) and more negative Eh values than SIM, and these two indicators showed linear correlations with the removal rates. Combined with microscopic, electrochemical and spectral analysis, our results indicated the redox reaction of adsorbed Fe(II)-complexes with NO2- on SIMD surface. The concurrent substance biochar was also considered, as it indirectly influenced dissolution and pollutant removal by shifting the iron mineral phase in SIM from magnetite to goethite. These findings highlight the significant role of reductive dissolution of iron mineral in N transformation, expand the electron pool available to support chemical denitrification, and have implications for Fe and N cycling coupling with pollutant reduction.

Biochar applications for efficient removal of energetic compound contaminants.

Military activities and the production or disposal of ammunition often lead to soil contamination with energetic compounds (ECs) such as dinitrotoluene, trinitrotoluene, and hexogen, posing significant threats to human health and the ecosystem. Biochar has emerged as a cost-effective and widely available solution for remediating contaminated sites characterized by its capacity for pollutant removal through adsorption and conversion process, along with minimal secondary pollution. This paper provides a comprehensive review of relevant literature on biochar's efficacy in eliminating ECs, including an analysis of the underlying mechanisms. The discussion addresses challenges and opportunities associated with biochar application in ECs remediation, offering insights for future research directions. In summary, the use of biochar for ECs removal presents a promising and eco-friendly approach, facilitating the remediation of contaminated sites while promoting soil function and ecosystem recovery.

Preoperative versus postoperative nonsteroidal anti-inflammatory drugs in femoroacetabular impingement patients undergoing hip arthroscopy surgery: analgesic effect, joint function, patients' satisfaction, and quality of life.

BACKGROUND: Nonsteroidal anti-inflammatory drugs (NSAIDs) have analgesic effects on femoroacetabular impingement (FAI) patients undergoing hip arthroscopy surgery (HAS). However, the influence of medication time on the analgesic effect of NSAIDs is uncertain. This study aimed to compare the analgesic effect, joint function, quality of life (QoL), and patients' satisfaction between preoperative and postoperative NSAIDs in these patients. METHODS: In this prospective, observational study, 165 FAI patients undergoing HAS with NSAIDs (celecoxib, meloxicam, and nimesulide) for analgesia were divided into preoperative (PRE-A) and postoperative analgesia (POST-A) groups according to their actual medication. RESULTS: The visual analog scale (VAS) pain scores on the 1st (P < 0.001) and 3rd (D3) (P = 0.015) days after the operation were lower in the PRE-A group versus the POST-A group but not preoperatively (P = 0.262) or on the 7th day after the operation (D7) (P = 0.302). The proportion of patients receiving rescue analgesia decreased in the PRE-A group versus POST-A group (P = 0.041). However, the modified Harris hip score (mHHS), proportion of patients with an mHHS ≥ 70, and EuroQol-5-dimensional score at preoperative, 1st month (M1), and 3rd month (M3) after the operation were similar between the groups (all P > 0.050). The VAS score on D7 was greater in the PRE-A group compared to the POST-A group (P = 0.014), but the scores at M1 and M3 and the satisfaction and very satisfaction rates at D7, M1, and M3 did not differ between the groups (all P > 0.050). Subgroup analysis revealed that the type of NSAID did not affect most outcomes. CONCLUSION: Preoperative NSAIDs elevate analgesic effect and patients' satisfaction, but not joint function or QoL compared to postoperative NSAIDs in FAI patients undergoing HAS.

Biological Self-Assembled Transmembrane Electron Conduits for High-Efficiency Ammonia Production in Microbial Electrosynthesis.

Usually, CymA is irreplaceable as the electron transport hub in Shewanella oneidensis MR-1 bidirectional electron transfer. In this work, biologically self-assembled FeS nanoparticles construct an artificial electron transfer route and implement electron transfer from extracellular into periplasmic space without CymA involvement, which present similar properties to type IV pili. Bacteria are wired up into a network, and more electron transfer conduits are activated by self-assembled transmembrane FeS nanoparticles (electron conduits), thereby substantially enhancing the ammonia production. In this study, we achieved an average NH4+-N production rate of 391.8 µg·h-1·L reactor-1 with the selectivity of 98.0% and cathode efficiency of 65.4%. Additionally, the amide group in the protein-like substances located in the outer membrane was first found to be able to transfer electrons from extracellular into intracellular with c-type cytochromes. Our work provides a new viewpoint that contributes to a better understanding of the interconnections between semiconductor materials and bacteria and inspires the exploration of new electron transfer chain components.

Facile preparation of coprecipitates between iron oxides and dissolved organic matter for efficient Fenton-like degradation of norfloxacin.

As two important components of dissolved organic matter (DOM), dissolved black carbon (DBC) and humic acid (HA) possess different chemical and structural properties, which might influence their activities like metal complexation and mediating electron transfer. In this study, a series of coprecipitates of iron oxides (FeOx) and DOM (HA or DBC) having different C/Fe molar ratios (0.2-3.0) was prepared under ambient conditions, which exhibited excellent catalytic efficiencies upon Fenton-like degradation of norfloxacin (NOR). Pseudo-first-order rate constant of NOR oxidation catalyzed by DBC-FeOx (C/Fe=3.0, 1.13 h-1) was 30.5, 4.3-14.2, and 1.3-15.7 folds higher than those mediated by FeOx alone, HA-FeOx and DBC-FeOx coprecipitates having C/Fe molar ratios of 0.2 and 1.6, respectively. Due to the higher concentrations of surface-bound Fe(III)/Fe(II) in the DBC-FeOx mediated systems, improved Fe(III)/Fe(II) cycling rates, •OH accumulation and NOR degradation were observed as compared with those of counterpart systems mediated by HA-FeOx. Besides functioning in Fe-C complexation to accelerate FeOOH cleavage, carbonyl/carboxyl groups of the coprecipitates also serve as electron shuttles, both of which improved Fe(III)/Fe(II) cycling and •OH production. Our findings emphasized the influence of DOM source and compositions on Fe(III)/Fe(II) cycling and provided a facile approach of preparing Fe-C catalyst for contaminants elimination.

Biomechanical effect of Coflex and X-STOP spacers on the lumbar spine: a finite element analysis.

OBJECTIVE: To explore the biomechanical differences between Coflex and X-STOP devices by finite element analysis. METHODS: Based on the normal lumbar CT images from a healthy adult volunteer, four finite element models including the healthy lumbar segment model, the mild degenerated lumbar segment model, a Coflex fixed lumbar segment model and X-STOP fixed lumbar segment model were constructed. A simulation analysis under the conditions of flexion, extension, lateral bending, and rotation was performed to compare range of motion (ROM), intradiscal pressure, the facet joint force, the maximum Von Mises stress and the peak facet contact forces, between Coflex and X-STOP devices. RESULTS: Compared to the mild degenerated lumbar segment model at surgical level L4-L5, Coflex and X-STOP could reduce ROM in extension by 98.34% and 95.86%, respectively, decrease peak stress of intervertebral discs in extension by 59.4% and 66.17%, respectively, and release peak force of facet joint in extension by 97.09% and 95.42%, respectively. Both devices had no significant impact on adjacent levels. The maximum Von Mises stress in Coflex device was 637.56 Mpa in flexion, 528.86 Mpa in extension, while the maximum Von Mises stress in X-STOP device was 476.65 Mpa at extension position. The peak facet contact forces of Coflex and X-STOP devices appeared in extension and were 19.76 Mpa and 49.28 Mpa, respectively. CONCLUSIONS: Coflex and X-STOP devices can effectively decrease the ROM and intradiscal pressure in extension, without affecting the adjacent levels.

Graphene Oxide Nanoparticle-Loaded Ginsenoside Rg3 Improves Photodynamic Therapy in Inhibiting Malignant Progression and Stemness of Osteosarcoma.

Osteosarcoma serves as a prevalent bone cancer with a high metastasis and common drug resistance, resulting in poor prognosis and high mortality. Photodynamic therapy (PDT) is a patient-specific and non-invasive tumor therapy. Nanoparticles, like graphene oxide have been widely used in drug delivery and PDT. Ginsenoside Rg3 is a principal ginseng component and has presented significant anti-cancer activities. Here, we constructed the nanoparticles using GO linked with photosensitizer (PS) indocyanine green (ICG), folic acid, and polyethylene glycol (PEG), and loaded with Rg3 (PEG-GO-FA/ICG-Rg3). We aimed to explore the effect of PEG-GO-FA/ICG-Rg3 combined with PDT for the treatment of osteosarcoma. Significantly, we found that Rg3 repressed proliferation, invasion, and migration, and enhanced apoptosis and autophagy of osteosarcoma cells, while the PEG-GO-FA/ICG-Rg3 presented a higher activity, in which NIR laser co-treatment could remarkably increase the effect of PEG-GO-FA/ICG-Rg3. Meanwhile, stemness of osteosarcoma cell-derived cancer stem cells was inhibited by Rg3 and PEG-GO-FA/ICG-Rg3, and the combination of PEG-GO-FA/ICG-Rg3 with NIR laser further significantly attenuated this phenotype in the system. Moreover, NIR laser notably improved the inhibitor effect of PEG-GO-FA/ICG-Rg3 on the tumor growth of osteosarcoma cells in vivo. Consequently, we concluded that PEG-GO-FA/ICG-Rg3 improved PDT in inhibiting malignant progression and stemness of osteosarcoma cell. Our finding provides a promising and practical therapeutic strategy for the combined treatment of osteosarcoma.

Extracellular electron transfer influences the transport and retention of ferrihydrite nanoparticles in quartz sand coated with Shewanella oneidensis biofilm.

Microbial biofilm has been found to impact the mobility of nanoparticles in saturated porous media by altering physicochemical properties of collector surface. However, little is known about the influence of biofilm's biological activity on nanoparticle transport and retention. Here, the transport of ferrihydrite nanoparticles (FhNPs) was studied in quartz sands coated with biofilm of Shewanella oneidensis MR-1 that is capable of reducing Fe(III) through extracellular electron transfer (EET). It was found that MR-1 biofilm coating enhanced FhNPs' deposition under different pH/ionic strength conditions and humic acid concentrations. More importantly, when the influent electron donor (glucose) concentration was increased to promote biofilm's EET activity, the breakthrough of FhNPs in biofilm-coated sands was inhibited. A lack of continuous and stable supply of electron donor, on the contrary, led to remobilization and release of the originally retained FhNPs. Column experiments with biofilm of EET-deficient MR-1 mutants (ΔomcA/ΔmtrC and ΔcymA) further indicated that the impairment of EET activity decreased the retention of FhNPs. It is proposed that the effective surface binding and adhesion of FhNPs that is required by direct EET cannot be neglected when evaluating the transport of FhNPs in sands coated with electroactive biofilm.

Construction and validation of nomogram to predict distant metastasis in osteosarcoma: a retrospective study.

BACKGROUND: Osteosarcoma is most common malignant bone tumors. OS patients with metastasis have a poor prognosis. There are few tools to assess metastasis; we want to establish a nomogram to evaluate metastasis of osteosarcoma. METHODS: Data from the Surveillance, Epidemiology, and End Results (SEER) database of patients with osteosarcoma were retrieved for retrospective analysis. We identify risk factors through univariate logistic regression and multivariate logistic regression analysis. Based on the results of multivariate analysis, we established a nomogram to predict metastasis of patients with osteosarcoma and used the concordance index (C-index) and calibration curves to test models. RESULTS: One thousand fifteen cases were obtained from the SEER database. In the univariate and multivariate logistic regression analysis, age, primary site, grade, T stage, and surgery are risk factors. The nomogram for metastasis was constructed based on these factors. The C-index of the training and validation cohort was 0.754 and 0.716. This means that the nomogram predictions of patients with metastasis are correct, and the calibration plots also show the good prediction performance of the nomogram. CONCLUSION: We successfully develop the nomogram which can reliably predict metastasis in different patients with osteosarcoma and it only required basic information of patients. The nomogram that we developed can help clinicians better predict the metastasis with OS and determine postoperative treatment strategies.

Synergistic catalytic Fenton-like degradation of sulfanilamide by biosynthesized goethite-reduced graphene oxide composite.

A series of goethite (Gt)-graphene (rGO) composites (Gt-rGO) having different rGO contents (2%-10%) was biologically prepared under mild conditions with Acidovorax sp. BoFeN1 and exhibited comparable or even higher catalytic efficiencies upon sulfonamides degradation than most known chemically synthesized catalysts. Pseudo-first-order rate constant of sulfanilamide degradation (60 µM, 0.971 h-1) in the system mediated by Gt-rGO with the optimal rGO content of 6% was 6.7, 15.4 and 168.1 folds higher than those in the control rGO/H2O2, Gt/H2O2 and H2O2 systems, respectively. Excellent synergistic catalytic effects between Gt and rGO in Gt-rGO were identified in four continuous cycles. The Gt-rGO systems exhibited more efficient •OH generation, H2O2 decomposition and Fe(II) accumulation rates than the control Gt or rGO systems. Fast Fe(III)/Fe(II) cycling was obtained in the Gt-rGO systems, which might be due to the strong Fe-C coordination and the decrease of rGO aggregation and Gt particle sizes. Additionally, Gt particles in Gt-rGO exposed more defects as active sites for H2O2 activation. High-performance liquid chromatography-mass spectrometer analysis suggested that sulfanilamide was gradually degraded through hydroxylation, C-N cleavage and benzene ring opening. The results provided a new approach for the tailored design of eco-friendly, cost-effective and efficient iron (oxyhydr)oxides-graphene catalysts for contaminants elimination.

Energy Taxis toward Redox-Active Surfaces Decreases the Transport of Electroactive Bacteria in Saturated Porous Media.

The fate and transport of bacteria in porous media are essential for bioremediation and water quality control. However, the influence of biological activities like extracellular electron transfer (EET) and swimming motility toward granular media on cell transport remains unknown. Here, electroactive bacteria with higher Fe(III) reduction abilities were found to demonstrate greater retention in ferrihydrite-coated sand. Increasing the concentrations of the electron donor (1-10 mM lactate), shuttle (0-50 µM anthraquinone-2,6-disulfonate), and acceptor (ferrihydrite, MnO2, or biochar) under flow conditions significantly reduced Shewanella oneidensis MR-1's mobility through redox-active porous media. The deficiency of EET ability or flagellar motion and inhibition of intracellular proton motive force, all of which are essential for energy taxis, enhanced MR-1's transport. It was proposed that EET could facilitate MR-1 to sense, tactically move toward, and attach on redox-active media surface, eventually improving its retention. Positive linear correlations were established among parameters describing MR-1's energy taxis ability (relative taxis index), cell transport behavior (dispersion coefficient and relative change of effluent percentage), and redox activity of media surface (reduction potential or electron-accepting rate), providing novel insights into the critical impacts of bacterial microscale motility on macroscale cell transport through porous media.

Improving waste activated sludge dewaterability with sodium periodate pre-oxidation on extracellular polymeric substances.

The efficiency of sludge dewatering is affected by the structure and composition of hydrated extracellular polymeric substances (EPS). Degrading EPS can improve the sludge dewatering performance. As an oxidizing agent, sodium periodate (NaIO4 ) has ability to oxidize organics, which is expected to decompose the protein and polysaccharide in EPS and improve the efficiency of sludge dewaterability. This study adopted NaIO4 , for the first time, as an advanced oxidation agent to regulate EPS of waste activated sludge and was combined with anionic polyacrylamide (APAM) as a flocculant to subsequently enhance sludge dewatering. Response surface methodology (RSM) was used to determine the optimal conditions of pH, NaIO4 , and APAM. The results showed that the composite conditioner's specific resistance of filtration (SRF) and the water content of the vacuum-filtered cake (Wc) were highly enhanced compared with those of the raw sludge (RS) under pH 6.5, a NaIO4 concentration of 50 mg/g dry solids (DS), and an APAM concentration of 5 mg/g DS. Owing to the pre-oxidation achieved by NaIO4 under a mildly acid environment, sludge flocs were broken. Subsequently, chemical coagulation (APAM) agglomerated the smaller particles into larger flocs of sludge by adsorption and bridging, thus improving sludge dewaterability. PRACTITIONER POINTS: A novel conditioner, pH/NaIO4 /APAM, was explored for sludge dewatering. IO3 • and HO• oxidized extracellular polymeric substances (EPS). Degradation of the protein content of EPS released bound water. Highly enhanced sludge dewaterability was achieved under optimal conditions.

Interaction between hexavalent chromium and biologically formed iron mineral-biochar composites: Kinetics, products and mechanisms.

Biogenic Fe(II) is a dominant natural reductant to convert carcinogenic Cr(VI) to less toxic Cr(III). Field-applied biochar could promote microbial production of Fe(II) and form iron-biochar composites. Although there have been mounting research on the interactions of biochar or Fe(II) with Cr(VI), their coupling effects on Cr(VI) immobilization have been largely neglected. Here, iron mineral-biochar composite (IMBC) was prepared via biochar-mediated dissimilatory reduction of ferrihydrite or goethite by Shewanella oneidensis MR-1, and its reaction with Cr(VI) was investigated. IMBC was able to effectively remove aqueous Cr(VI) via reductive transformation by adsorbed Fe(II). The removal process nicely followed pseudo-second-order kinetics and Langmuir isotherm model. The removal ability of IMBC decreased with increasing pH (5.5-8.0) but was independent of ionic strength changes (0-100 mM). After reaction, the Fe-Cr coprecipitates formed on IMBC exhibited slightly higher Fe/Cr ratios (0.93-0.96) than those on corresponding iron mineral controls (0.88-0.94). For IMBC, while the presence of biochar decreased the reactivity of adsorbed Fe(II), their removal capacities were ~30% higher than those of iron minerals alone, due to the enhanced yields of adsorbed Fe(II). These findings improved our knowledge of interactions among biochar, iron mineral and iron-reducing bacteria and their contribution to chromium immobilization.

Goethite-humic acid coprecipitate mediated Fenton-like degradation of sulfanilamide: The role of coprecipitated humic acid in accelerating Fe(III)/Fe(II) cycle and degradation efficiency.

While extensive studies found that dissociative and iron mineral-adsorbed humic acid (HA) could either stimulate or inhibit Fenton-like processes, little was known about the influence of iron mineral-coprecipitated HA on Fenton-like reactions. Here, goethite and HA (Gt-HA) coprecipitates having different C:Fe molar ratios (C:Fe = 0.16-0.99) were biologically prepared, and for the first time, investigated for their abilities of H2O2 activation and catalytic degradation of sulfanilamide. For system containing Gt-HA with the optimal C:Fe ratio of 0.30, over 91.1% of sulfanilamide (10 mg/L) was removed in 2 h, which was 46.2% higher than that of the control Gt system. Additionally, H2O2 decomposition, •OH production, and organic carbon removal in Gt-HA systems were all more efficient than those in Gt system. Higher carbon moieties stability and lower micropore surface area of Gt-HA decreased the competition for •OH and H2O2, thus helped to improve degradation efficiency. Electrochemical analysis, quenching experiments, and Fe species detection showed that the coprecipitated HA could serve as electron shuttle and complex with Fe(III) mainly via carboxyl groups at octahedral sites to improve Fe(III)/Fe(II) transformation. This study improved our understanding of Fe(III)/Fe(II) cycling in Fe‒C coprecipitates and demonstrated the potential of developing Fe‒C coprecipitates as efficient catalysts in Fenton-like processes.

Acceleration of goethite-catalyzed Fenton-like oxidation of ofloxacin by biochar.

While carbon materials have been well studied to stimulate the homogeneous Fenton-like processes, little was known about their impacts on iron mineral-catalyzed heterogeneous Fenton-like reactions. Here, it was found that biochar prepared at 300 °C or 600 °C (BC300 or BC600) greatly stimulated the degradation of ofloxacin (OFX) in a goethite (Gt)-mediated Fenton-like system. In 4 h, while only 38.4 % and 48.4 % OFX were removed in Gt/H2O2 and BC600/H2O2 systems, the removal efficiency reached over 94.0 % in Gt/BC600/H2O2 system. And the pseudo-first-order rate constant of Gt/H2O2, BC600/H2O2 and Gt/BC600/H2O2 systems were 0.12, 0.16 and 0.72 h-1, respectively, indicating the occurrence of synergistically catalytic degradation. •OH was identified as the major oxidant. Both the •OH yield and the H2O2 utilization efficiency of Gt/BC600/H2O2 system were higher than those of Gt/H2O2 and BC600/H2O2 systems. BC600 showed better stimulation effects than BC300. The persistent free radicals (PFRs) of BC could activate H2O2 and partly contribute to •OH production in the Gt/BC/H2O2 system. While BC could not directly reduce Fe(III) in Gt, it improved the cycling of Fe(III)/Fe(II) through complexing Fe(III) with its carboxyl group. Potential pathways were proposed for OFX degradation in the Gt/BC/H2O2 system.

Roles of molecular weight-fractionated extracellular polymeric substance in transformation of Au(III) to Au nanoparticles in aqueous environments.

Extracellular polymeric substance (EPS) is widely distributed in natural environments and plays important roles in the biogeochemical cycling of heavy metal. Earlier works reported that EPS could reduce metal ions such as Au(III) and Ag(I) to corresponding metal nanoparticles (NPs). EPS is a complex mixture of microbiogenic polymers with wide molecular weight (MW) distribution, and the specific components of EPS responsible for Au(III) reduction and AuNPs stabilization are still not well understood. In this study, the EPS of Shewanella oneidensis MR-1 was divided into six fractions with MW of <3, 3-10, 10-30, 30-50, 50-100, and >100 kDa, respectively through the ultrafiltration method and the roles of MW-fractionated EPS in the reduction of Au(III) to AuNPs were investigated. It was found that the low MW (<3 kDa) EPS was the major reducing agent in EPS but the fraction itself could not convert high concentration (>25 mg/L) of Au(III) to stable AuNPs due to its inferior AuNPs-stabilizing capacity. The high MW (>50 kDa) EPS could act as coating reagents to increase the stability of the formed AuNPs with sizes of 20-50 nm, but had low Au(III)-reducing activity. The carboxyl-containing substances in EPS may play crucial roles in stabilizing AuNPs. This finding is important for a better understanding of the differential roles of MW-fractionated EPS in the transformation and fate of Au(III) and AuNPs, as well as other metal ions and metal NPs in natural environments.

Facilitated bioreduction of nitrobenzene by lignite acting as low-cost and efficient electron shuttle.

The searching for efficient and economical redox mediators to promote the treatment of wastewater containing recalcitrant organic compounds is greatly needed. In this study, the redox mediator activities of four different lignite samples to facilitate the bioreduction of nitrobenzene by Shewanella oneidensis MR-1 were tested for the first time. The initial nitrobenzene reduction rate was increased by 40.4%-90.3% in the presence of 50 mg/L of different lignite samples. Lignite collected from Xinjiang (XJL) having more oxygenated groups performed better in enhancing nitrobenzene bioreduction. The stimulating effects increased with the increase of lignite dosage (0-200 mg/L) and the decrease of lignite particle size (150-0.1 µm). However, the pristine XJL samples with assorted sizes of particles exhibited better stimulating effects than size-fractionated ones, implying that different-sized XJL particles might have synergetic effects on the bioreduction process. When humic acid or iron was removed from XJL, its promoting effects were decreased, demonstrating the crucial roles of both components in lignite-enhanced nitrobenzene bioreduction. Nitric acid treatment could form more oxygenated moieties on lignite surface, which played vital roles in promoting nitrobenzene bioreduction. The initial nitrobenzene bioreduction rate in the presence of HNO3-treated XJL was 80.8% higher than that obtained with pristine XJL. This study proposed an effective and readily available redox mediator that could be applied to promote the bioreduction of recalcitrant electrophilic pollutants.

Transformation of silver ions to silver nanoparticles mediated by humic acid under dark conditions at ambient temperature.

The conversion of silver materials in environments would impact their toxicity and risk. Previous studies have reported that silver ions (Ag+) could be reduced to silver nanoparticles (AgNPs) by natural organic matters (NOM) under sunlight or heating conditions. However, whether such reaction could occur in darkness at ambient temperature and the transformation mechanism were unclear. This study found that Ag+ at environmentally relevant concentrations (as low as 1 µg/L) could be reduced to AgNPs by Suwannee River humic acid (SRHA) in darkness at 30 °C. The reaction mechanism probed by X-ray absorption fine structure spectroscopy revealed that Ag+ was first bound to the carboxylic groups of SRHA to form Ag+-SRHA ligands, which were then reduced to metallic Ag. The increase of pH (6-9) and the coexistence of formate, acetate, carbonate, and sulfate promoted the formation of AgNPs. Besides, the formed AgNPs would coalesce to large aggregates under acidic conditions or in the presence of sulfate. These results suggest that the dark transformation of Ag+ to AgNPs mediated by NOM could occur in environments and are important for the better understanding of the natural origin of AgNPs.

Effect on sludge disintegration by EDTA-enhanced thermal-alkaline treatment.

Sludge disintegration is an effective pretreatment to enhance the biodegradability of sludge. At present, the thermal-alkaline is one of the most commonly used methods, but it has a massive consumption of energy and chemical reagents. EDTA-enhanced thermal-alkaline treatment was used to strengthen the dewatered sludge disintegration at mid-low temperature in this study. Results showed that the dissolving-out quantity of soluble chemical oxygen demand and the volatile solid (VS) in residual sludge in the EDTA-added group were 14.7% higher and 7% lower than those in control system without EDTA, respectively, indicating that EDTA addition improved the performance of sludge disintegration. The addition of EDTA loosened the floc structure and enhanced the hydrolyzability of dissolved organic matters (DOM) with a narrower distribution of the relative molecular weight. The membrane damage of microbial cells in EDTA-added group reached 73.3% after 120 min, which was much higher than that in the control group (31.9%). EDTA contains a large number of hydrogen bond acceptors and could form hydrogen bonds with alcohols and phenols in solubilization products and DOM. It was speculated that the mechanism of EDTA-enhanced sludge disintegration was related to the formation of hydrogen bonds between EDTA and organic matter inside and outside the cell. PRACTITIONER POINTS: The addition of EDTA facilitated the thermal-alkali cracking of dewatered sludge. EDTA increased the particle size of sludge and enhanced the hydrolysis of DOM. The strengthening effect mainly occurred at the beginning of TB-EPS dissolving slowly. Hydrogen bond played important roles in the enhanced disintegration of sludge by EDTA.