How does the biochar-supported sulfidized nanoscale zero-valent iron affect the soil environment and microorganisms while remediating cadmium contaminated paddy soil?

In previous studies, iron-based nanomaterials, especially biochar (BC)-supported sulfidized nanoscale zero-valent iron (S-nZVI/BC), have been widely used for the remediation of soil contaminants. However, its potential risks to the soil ecological environment are still unknown. This study aims to explore the effects of 3% added S-nZVI/BC on soil environment and microorganisms during the remediation of Cd contaminated yellow-brown soil of paddy field. The results showed that after 49 d of incubation, S-nZVI/BC significantly reduced physiologically based extraction test (PBET) extractable Cd concentration (P < 0.05), and increased the immobilization efficiency of Cd by 16.51% and 17.43% compared with S-nZVI and nZVI/BC alone, respectively. Meanwhile, the application of S-nZVI/BC significantly increased soil urease and sucrase activities by 0.153 and 0.446 times, respectively (P < 0.05), improving the soil environmental quality and promoting the soil nitrogen cycle and carbon cycle. The results from the analysis of the 16S rRNA genes indicated that S-nZVI/BC treatment had a minimal effect on the bacterial community and did not appreciably alter the species of the original dominant bacterial phylum. Importantly, compared to other iron-based nanomaterials, incorporating S-nZVI/BC significantly increased the soil organic carbon (OC) content and decreased the excessive release of iron (P < 0.05). This study also found a significant negative correlation between OC content and Fe(II) content (P < 0.05). It might originate from the reducing effect of Fe-reducing bacteria, which consumed OC to promote the reduction of Fe(III). Accompanying this process, the redistribution of Cd and Fe mineral phases in the soil as well as the generation of secondary Fe(II) minerals facilitated Cd immobilization. Overall, S-nZVI/BC could effectively reduce the bioavailability of Cd, increase soil nutrients and enzyme activities, with less toxic impacts on the soil microorganisms.

High performance self-assembled sulfidized nanoscale zero-valent iron for the immobilization of cadmium in contaminated sediments: Optimization, microbial response, and mechanisms.

Sulfidized nanoscale zero-valent iron (S-nZVI) showed excellent removal capacity for cadmium (Cd) in aqueous phase. However, the remediation effects of S-nZVI on Cd-contaminated sediment and its interactions with microorganisms in relation to Cd fate remain unclear. The complexity of the external environment posed a challenge for Cd remediation. This study synthesized S-nZVI with different S and Fe precursors to investigate the effect of precursors and applied the optimal material to immobilize Cd in sediments. Characterization analysis revealed that the precursor affected the morphology, Fe0 crystallinity, and the degree of oxidation of the material. Incubation experiments demonstrated that the immobilization efficiency of Cd using S-nZVIFe3++S2- (S/Fe = 0.14) reached the peak value of 99.54%. 1% and 5% dosages of S-nZVI significantly reduced Cd concentration in the overlying water, DTPA-extractable Cd content, and exchangeable (EX) Cd speciation (P < 0.05). Cd leaching in sediment and total iron in the overlying water remained at low levels during 90 d of incubation. Notably, each treatment maintained a high Cd immobilization efficiency under different pH, water/sediment ratio, organic acid, and coexisting ion conditions. Sediment physicochemical properties, functional bacteria, and a range of adsorption, complexation and precipitation of CdS effects dominated Cd immobilization.

Affecting factors and mechanism of removing antibiotics and antibiotic resistance genes by nano zero-valent iron (nZVI) and modified nZVI: A critical review.

Antibiotics and antibiotic resistance genetic pollution have become a global environmental and health concern recently, with frequent detection in various environmental media. Therefore, finding ways to control antibiotics and antibiotic resistance genes (ARGs) is urgently needed. Nano zero-valent iron (nZVI) has shown a positive effect on antibiotics degradation and restraining ARGs, making it a promising solution for controlling antibiotics and ARGs. However, given the current increasingly fragmented research focus and results, a comprehensive review is still lacking. In this work, we first introduce the origin and transmission of antibiotics and ARGs in various environmental media, and then discuss the affecting factors during the degradation of antibiotics and the control of ARGs by nZVI and modified nZVI, including pH, nZVI dose, and oxidant concentration, etc. Then, the mechanisms of antibiotic and ARGs removal promoted by nZVI are also summarized. In general, the mechanism of antibiotic degradation by nZVI mainly includes adsorption and reduction, while promoting the biodegradation of antibiotics by affecting the microbial community. nZVI can also be combined with persulfates to degrade antibiotics through advanced oxidation processes. For the control of ARGs, nZVI not only changes the microbial community structure, but also affects the proliferation of ARGs through affecting the fate of mobile genetic elements (MGEs). Finally, some new ideas on the application of nZVI in the treatment of antibiotic resistance are proposed. This paper provides a reference for research and application in this field.

Activation of persulfate by biochar-supported sulfidized nanoscale zero-valent iron for degradation of ciprofloxacin in aqueous solution: process optimization and degradation pathway.

The pollution of antibiotics, specifically ciprofloxacin (CIP), has emerged as a significant issue in the aquatic environment. Advanced oxidation processes (AOPs) are capable of achieving stable and efficient removal of antibiotics from wastewater. In this work, biochar-supported sulfidized nanoscale zero-valent iron (S-nZVI/BC) was adopted to activate persulfate (PS) for the degradation of CIP. The impacts of different influencing factors such as S/Fe molar ratios, BC/S-nZVI mass ratios, PS concentration, S-nZVI/BC dosage, CIP concentration, initial pH, coexisting anions, and humic acid on CIP degradation efficiency were explored by batch experiments. The results demonstrated that the highest degradation ability of S-nZVI/BC was achieved when the S/Fe molar ratio was 0.07 and the BC/S-nZVI mass ratio was 1:1. Under the experimental conditions with 0.6 g/L S-nZVI/BC, 2 mmol/L PS, and 10 mg/L CIP, the degradation rate reached 97.45% after 90 min. The S-nZVI/BC + PS system showed significant degradation in the pH range from 3 to 9. The coexisting anions affected the CIP degradation efficiency in the following order: CO32- > NO3- > SO42- > Cl-. The radical quenching experiments and electron paramagnetic resonance (EPR) revealed that oxidative species, including SO4•-, HO•, •O2-, and 1O2, all contribute to the degradation of CIP, in which •O2- plays a particularly prominent role. Furthermore, the probable degradation pathway of CIP was explored according to the 12 degradation intermediates identified by LC-MS. This study provides a new idea for the activation method of PS and presents a new approach for the treatment of aqueous antibiotics with highly catalytic active nanomaterials.

Immobilization of cadmium in river sediments by different modified nanoscale zero-valent iron: performance, mechanisms, and Fe dissolution.

Modified nanoscale zero-valent iron (NZVI) exhibited great potential for the remediation of heavy metal contaminated river sediments, but its mechanisms and environmental risks are still unclear. This study systematically discussed the performance and the mechanisms of modified NZVI materials, i.e., sodium alginate-coated NZVI (SNZVI), rhamnolipid-coated NZVI (RNZVI), and graphene oxide-loaded NZVI (GNZVI), for the stabilization of Cd in sediment, with the exploration of their stability to Cd at various pH values and Fe dissolution rate. Compared with the control, the toxicity characteristic leaching procedure (TCLP) leachable Cd decreased by 52.66-96.28%, and the physiologically based extraction test (PBET) extractable Cd decreased by 44.68-70.21% after 56 days of incubation with the immobilization efficiency varying according to GNZVI > RNZVI > SNZVI > NZVI. Besides, the adsorption behavior of Cd on materials was fitted with the Freundlich model and classified as an endothermic, spontaneous, and chemical adsorption process. SEM-EDX, XRD, and FTIR results verified that the stabilization mechanisms of Cd were principally based on the adsorption, complexation of Cd2+ with secondary Fe minerals (including Fe2O3, γ-Fe2O3, and γ-FeOOH) and precipitation (Cd(OH)2). From the risk assessment results, it was observed that the materials were favorable for Cd stabilization at a pH range from 7 to 11, meanwhile, the leaching concentration of Fe in the overlying water was detected below the limit value. These findings pave the way to developing an effective strategy to remediate Cd contaminated river sediments.

Recent advances in sulfidized nanoscale zero-valent iron materials for environmental remediation and challenges.

Over the past decade, sulfidized nanoscale zero-valent iron (S-nZVI) has been developed as a promising tool for the remediation of contaminated soil, sediment, and water. Although most studies have focused on applying S-nZVI for clean-up purposes, there is still a lack of systematic summary and discussion from its synthesis, application, to toxicity assessment. This review firstly summarized and compared the properties of S-nZVI synthesized from one-step and two-step synthesis methods, and the modification protocols for obtaining better stability and reactivity. In the context of environmental remediation, this review outlined an update on the latest development of S-nZVI for removal of heavy metals, organic pollutants, antibiotic resistance genes (ARGs), and antibiotic resistant bacteria (ARB) and also discussed the underlying removal mechanisms. Environmental factors affecting the remediation performance of S-nZVI (e.g., humic acid, coexisting ions, S/Fe molar ratio, pH, and oxygen condition) were highlighted. Besides, the application potential of S-nZVI in advanced oxidation processes (AOP), especially in activating persulfate, was also evaluated. The toxicity impacts of S-nZVI on the environmental microorganism were described. Finally, the future challenges and remaining restrains to be resolved for better applicability of S-nZVI are also proposed. This review could provide guidance for the environmental remediation with S-nZVI-based technology from theoretical basis and practical perspectives.

Chromium(III) adsorption removal from acidic solutions by isomeric and tunnel-structural iron oxyhydroxides.

Iron oxyhydroxides for heavy metal treatment have attracted wide attention. In this work, iron oxyhydroxides of isomeric FeOOH (GpI) and tunnel-structural schwertmannite/akaganéite (GpII) were selected to study chromium (Cr(III)) adsorption removal from acidic aqueous solutions by batch experiments, under various reaction time, adsorbate/adsorbent level, pH and anions. Adsorption processes well fitted to pseudo-second-order kinetics (R2 = 0.992-0.999, except for 0.829 for Lep). Isotherm data could be fitted by Langmuir (R2 = 0.901-0.985), Freundlich (R2 = 0.884-0.985) and Temkin (R2 = 0.845-0.961) models at pH 3.7. Langmuir maximum adsorption capacities (mg/g) were 10.4-18.8 (FeOOH, except for 3.08 for Gth2) in GpI, and 20.60/43.40 (Sch-Chem/Sch-Bio) and 12.80/24.70 (Aka-Chem/Aka-Bio) in GpII. Adsorption capacities would gradually increase as Cr(III) concentrations increased within 0-40 mg/L, and could be markedly affected by the SO42- and H2PO4- anions. There were stable adsorption capacities at about pH 3.7, and then increased at pH 3.7-4.1. The Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) results showed that adsorption mechanisms were electrostatic interaction and surface complexation. In addition, three optimal bio-/chem-schwertmannite and lepidocrocite adsorbents had good reusable properties and treating abilities of Cr(III)-polluted waters at pH 4.0. These results could provide a theoretical basis for the application of iron oxyhydroxides in removing Cr(III) from acid wastewaters.

Comparative study of dual energy CT iodine imaging and standardized concentrations before and after chemoradiotherapy for esophageal cancer.

BACKGROUND: To compare dual energy CT iodine imaging and standardized iodine concentration before and after chemoradiotherapy (CRT) for esophageal cancer and evaluate the efficacy of CRT for EC by examining DECT iodine maps and standard CT values. METHODS: The clinical data of 45 patients confirmed by pathology with newly diagnosed esophageal cancer who underwent concurrent CRT from February 2012 to January 2017 in our department of radiology were collected. All patients underwent dual-source dual-energy CT (DECT) before and after CRT. Normalized iodine concentration (NIC) and normalized CT (NCT) corresponding to the overall cancer lesion and its maximum cross-sectional area were observed and compared. Additionally, 30 healthy individuals were compared as control group. After treatment, the patients were divided into two groups according to RECIST1.1: treatment effective group and ineffective group. RESULTS: There were 33 patients (CR 9, PR 24) in the effective group and 12 patients (SD 12, PD 0) in the ineffective group. There was no significant difference in the NIC-A, NIC-V, NCT-A and NCT-A indexes between the effective group (B group) and the ineffective group (C group) before treatment (P > 0.05). After the treatment, the above-mentioned indexes in the effective group of patients were significantly lower than before treatment, and compared with the ineffective group, the NIC-A, NIC-V, NCT-A and NCT-V values of the effective group were significantly lower than those of ineffective group (P < 0.05). After treatment, the NIC-V and NCT-V in the ineffective group were lower than before treatment, and the difference was statistically significant (P < 0.05). However, their NIC-A and NCT-A were not statistically different from those before treatment (P > 0.05). CONCLUSION: Using DECT iodine map, the changes of NIC and NIC before and after CRT in patients with esophageal cancer can evaluate the effect of CRT, and does not increase the radiation dose, so it is suitable for clinical use.

[Characterization and spectral analysis of the stable mineral phases alpha, beta-FeOOH included in iron oxyhydroxides].

In the present work, based on the stable phase of alpha-FeOOH and beta-FeOOH easily formed in ferric solutions of Fe (NO3)3 and FeCl3 at the appropriate pH values, respectively, the phase and crystallizability, morphologies and sizes for the particles of FeOOH minerals prepared under the conditions of heating at 40 and 70 degreeC, and magnetic stirring at 25 degreeC were identified and examined by X-ray diffraction (XRD), transmission/scanning electron microscopy (TEM/SEM) and laser scattering particle analyzer. Meanwhile the surface chemistry properties were also detected and analyzed by Fourier transform infrared spectrometer (FTIR). Investigation results showed that the prepared minerals Gth-T70 (alpha-FeOOH), Aka-T40 and Aka-T70 (beta-FeOOH) have good properties of nanocrystallity, homogeneous particles and higher specific surface areas, which induced that the above alpha, beta-FeOOH are potentially excellent adsorbent materials for removal of some contaminants in circumstances.