Precise Modulation of the Coordination Environment of Single Cu Site Catalysts to Regulate the Peroxymonosulfate Activation Pathway for Water Remediation.

Single atom site catalysts (SACs) with atomically dispersed active sites can be expected to be potential ideal catalysts for accurately modulating the persulfate activation pathway during the water remediation process because of their well-defined structure and the maximum metallic atom utilization. In this paper, a series of Cu SACs with different coordination environments were synthesized to elaborately regulate the peroxymonosulfate activation pathway in AOPs to clarify active species generation and transformation in water remediation. The degradation rate constants (kobs) of Cu-N2, Cu-N3, and Cu-N4 were 0.028, 0.021, and 0.015 min-1, respectively. Cu-N2 SACs exhibited a noticeable enhanced performance for bisphenol A (BPA) removal from water compared to that of the Cu-Nx SACs (x = 3, 4), accompanied by peroxymonosulfate (PMS) activation pathway variation. As shown by experimental and theoretical results, the PMS activation pathway was transformed from ROS to electron transfer with nitrogen coordination numbers decreasing from 4 to 2, which can be ascribed to the uneven charge distribution of Cu sites as well as upshifts in the d-band center, and thereby optimized electron transfer for PMS activation. Furthermore, the increasing nitrogen vacancies of single Cu site catalysts can also result in more unoccupied 3d orbitals of Cu atoms in SACs, thereby improving the intermediates' (PMS and BPA) adsorption-desorption process and BPA removal performance. These findings provided a beneficial approach for the coordination number regulation of SACs in water remediation.

Mechanism analysis of MnFe2O4/FeSX for removal of Cr(VI) from aqueous phase.

By using Na2S as a sulfur source, sulfur-doped MnFe2O4 was prepared using one-step solvent thermal method and utilized to remove hexavalent chromium. The materials were characterized through scanning electron microscopy, transmission electron microscopy, high-resolution TEM, X-ray diffraction, Fourier-transform infrared spectroscopy, Brunauer-Emmett-Teller method, zeta potential test, vibrating sample magnetometry, and X-ray photoelectron spectroscopy. When the pH was 3, the adsorption capacity of MnFe2O4/FeSX-0.5 to Cr(VI) was 43.36 mg/g, which was roughly five times that of MnFe2O4 (8.90 mg/g). MnFe2O4/FeSX-0.5 and MnFe2O4 fitted the Freundlich and pseudo-second-order kinetic models well. The electrochemical test analysis results showed that MnFe2O4/FeSX had a faster MnFe2O4 electron transfer rate and higher electron transfer capacity than MnFe2O4, and thus promoted the reduction of Cr(VI) to Cr(III). This finding could be attributed to the lower electronegativity of the sulfur element than the oxygen element. In addition, the formation of additional FeSX through sulfur doping improved the Cr(VI) removal ability of the prepared materials. The XPS and desorption results showed that more than 80% of the adsorbed Cr(VI) were reduced to Cr(III), which indicated that reduction was an important mechanism for Cr(VI) removal. This study verified that sulfur-doped manganese ferrite can be utilized in the high-efficiency removal of Cr(VI).

Recombinant human GLP-1(rhGLP-1) alleviating renal tubulointestitial injury in diabetic STZ-induced rats.

GLP-1-based treatment improves glycemia through stimulation of insulin secretion and inhibition of glucagon secretion. Recently, more and more findings showed that GLP-1 could also protect kidney from diabetic nephropathy. Most of these studies focused on glomeruli, but the effect of GLP-1 on tubulointerstitial and tubule is not clear yet. In this study, we examined the renoprotective effect of recombinant human GLP-1 (rhGLP-1), and investigated the influence of GLP-1 on inflammation and tubulointerstitial injury using diabetic nephropathy rats model of STZ-induced. The results showed that rhGLP-1 reduced urinary albumin without influencing the body weight and food intake. rhGLP-1 could increased the serum C-peptide slightly but not lower fasting blood glucose significantly. In diabetic nephropathy rats, beside glomerular sclerosis, tubulointerstitial fibrosis was very serious. These lesions could be alleviated by rhGLP-1. rhGLP-1 decreased the expression of profibrotic factors collagen I, α-SMA, fibronectin, and inflammation factors MCP-1 and TNFα in tubular tissue and human proximal tubular cells (HK-2 cells). Furthermore, rhGLP-1 significantly inhibited the phosphorylation of NF-κB, MAPK in both diabetic tubular tissue and HK-2 cells. The inhibition of the expression of TNFα, MCP-1, collagen I and α-SMA in HK-2 cells by GLP-1 could be mimicked by blocking NF-κB or MAPK. These results indicate that rhGLP-1 exhibit renoprotective effect by alleviation of tubulointerstitial injury via inhibiting phosphorylation of MAPK and NF-κB. Therefore, rhGLP-1 may be a potential drug for treatment of diabetic nephropathy.

Erythropoietin regulates energy metabolism through EPO-EpoR-RUNX1 axis.

Erythropoietin (EPO) plays a key role in energy metabolism, with EPO receptor (EpoR) expression in white adipose tissue (WAT) mediating its metabolic activity. Here, we show that male mice lacking EpoR in adipose tissue exhibit increased fat mass and susceptibility to diet-induced obesity. Our findings indicate that EpoR is present in WAT, brown adipose tissue, and skeletal muscle. Elevated EPO in male mice improves glucose tolerance and insulin sensitivity while reducing expression of lipogenic-associated genes in WAT, which is linked to an increase in transcription factor RUNX1 that directly inhibits lipogenic genes expression. EPO treatment in wild-type male mice decreases fat mass and lipogenic gene expression and increase in RUNX1 protein in adipose tissue which is not observed in adipose tissue EpoR ablation mice. EPO treatment decreases WAT ubiquitin ligase FBXW7 expression and increases RUNX1 stability, providing evidence that EPO regulates energy metabolism in male mice through the EPO-EpoR-RUNX1 axis.

Conditional remediation performance of wheat straw biochar on three typical Cd-contaminated soils.

Undoubtedly biochar has excellent remediation performance for Cd-contaminated soil. Nevertheless, the remediation performance may be not invariable considering highly variable soil conditions including soil properties and environmental conditions. This work investigated the fate of Cd in three typical Cd-contaminated soils (acidic, neutral and saline-alkali soils) treated with wheat straw biochar and its driving mechanisms under specific soil conditions through aging and remediation experiment, Cd availability experiment and leaching column experiment. The results indicated that biochar addition facilitated Cd immobilization and reduced the uptake of Cd by green vegetables in acidic, neutral and saline-alkali soils under wetting-drying conditions. In contrast to neutral and saline-alkali soils, the release of exchangeable aluminum from biochar-treated acidic soil under flooding-drying cycles lowered the pH of leachate, thus promoting the leaching of Cd from leaching column, especially at 7 and 14 days, when the leaching of Cd increased by 25.3 and 32.6 times, respectively. This result was further supported by the increase in the exchangeable fraction and total leaching amounts of Cd in the topsoil layer (0-20 cm) of biochar-treated acidic soil of leaching column. Additionally, the leaching of Cd was positively correlated with DOC contents of leachate in biochar-treated neutral and saline-alkali soils. In summary, the remediation performance of biochar for Cd-contaminated soils is conditional, and its remediation effect is better in neutral and saline-alkali soils. Notably, the inherent conditions of soil must be fully considered when applying biochar for Cd remediation, especially in acidic Cd-contaminated paddy soils in South China.

Remediation of lead and cadmium co-contaminated mining soil by phosphate-functionalized biochar: Performance, mechanism, and microbial response.

The remediation of heavy metals contaminated soils is of great significance for reducing their risk to human health. Here, pristine pinewood sawdust biochar (BC) and phosphate-functionalized biochar (PBC) were conducted to investigate their immobilization performance towards lead (Pb) and cadmium (Cd) in arable soils severely polluted by Pb (9240.5 mg kg-1) and Cd (10.71 mg kg-1) and microbial response in soils. Compared to pristine BC (2.6-12.1%), PBC was more effective in immobilizing Pb and Cd with an immobilization effectiveness of 45.2-96.2% after incubation of 60 days. Moreover, the labile Pb and Cd in soils were transformed to more stable species after addition of PBC, reducing their bioavailability. The immobilization mechanisms of Pb and Cd by PBC were mainly to facilitate the formation of stable phosphate precipitates e.g., Cd3(PO4)2, Cd5(PO4)3OH, Cd5H2(PO4)4‧4H2O, and pyromorphite-type minerals. Further, PBC increased pH, organic matter, cation exchange capacity, and available nutrients (phosphorus and potassium) in soils. High-throughput sequencing analysis of 16 S rRNA genes indicated that the diversity and composition of bacterial community responded to PBC addition due to PBC-induced changes in soil physicochemical properties, increasing the relative abundance of beneficial bacteria (e.g., Brevundimonas, Bacillus, and norank_f__chitinophagaceae) in the treated soils. What's more, these beneficial bacteria could not only facilitate Pb and Cd immobilization but also alter nutrient biogeochemical transformation (nitrogen and iron) in co-contaminated soils. Overall, PBC could be a promising material for immobilization of Pb and Cd and the simultaneous enhancement of soil quality and available nutrients in co-contaminated mining soils.

Carbon matrix of biochar from biomass modeling components facilitates electron transfer from zero-valent iron to Cr(VI).

Biochar-harbored zero-valent iron (ZVI/BC) has been extensively used to detoxify hexavalent chromium (Cr(VI)). However, the role played by biochar in promoting electron transfer of ZVI and Cr(VI) reduction was not fully uncovered. Herein, three biomass modeling components (cellulose, hemicellulose, and lignin) and their blends were utilized to synthesize ZVI/BC via co-pyrolysis with hematite. X-ray diffraction analysis showed that hematite was successfully reduced to ZVI in nitrogen ambience. Batch sorption experiment showed that mass ratio (hematite to lignocellulosic component) of 1:20 is most optimal for reduction of Cr(VI) by ZVI/BCs. ZVI supported by BC derived from cellulose, hemicellulose, and their binary mixture demonstrated better Cr(VI) removal capacity (23.8-38.3 mg g-1) owing to higher ordered and graphitic carbon structure as revealed by Raman spectrum. In addition, lower Tafel corrosion potentials and smaller electrochemical impedance arc radiuses were observed based on electrochemical analysis, suggesting their higher electrical conductivity and faster electron transfer, whereas the BCs derived from lignin and lignin-containing hybrids were not conducive to electron transfer of ZVI due to lower degree of graphitization, thus compromising Cr(VI) removal by ZVI/BC (7.7-17.7 mg g-1). As per X-ray photoelectron spectroscopy analysis, reduction, complexation, and co-precipitation were the main mechanisms for Cr(VI) removal. The present study provided a scientific evidence for screening plant-derived biomass feedstock with high contents of cellulose and hemicellulose and low lignin content to fabricate ZVI/BC to achieve high Cr(VI) removal.

Does biochar application in heavy metal-contaminated soils affect soil micronutrient dynamics?

Biochar has been practically used as a soil conditioner in degraded or contaminated soils. Whether biochar would simultaneously affect soil micronutrient bioavailability in heavy metal-contaminated soils warrants research. A 90-d incubation of rice straw biochar with either Pb- or Cd-contaminated soils was conducted to investigate the biochar effect on Fe, Mn, Cu and Zn bioavailability. Biochar amendment decreased the DTPA-extractable, acid extractable and reducible Pb and Cd but increased the oxidizable and residual Pb and Cd. It decreased the DTPA-extractable Fe by 73.8% and 23.1% but increased the DTPA-extractable Mn by 9.8% and 44.3% in the neutral and acidic soil, respectively. The lower Fe availability was attributed to the liming effect and the increased numbers of oxygen-containing groups and organic-mineral phases of biochar over time. Biochar amendment increased soil bacterial richness and diversity in both soils. Rice straw biochar can effectively immobilize heavy metals and reduce soil Fe bioavailability but increase Mn bioavailability, which would potentially affect soil micronutrient fertility and productivity.

Pyrolysis temperature and feedstock affected Cr(VI) removal capacity of sulfidated zerovalent iron: Importance of surface area and electrical conductivity.

Herein, feedstock (pinewood, rice straw, and dairy manure) and pyrolysis temperature (300, 500, and 700 °C) were selected as the influencing factors of properties of biochar (BC) to identify the contribution of biochar's matrix on Cr(VI) removal by BC-supported sulfidated zero-valent iron (S-ZVI/BC). Results showed that higher temperature was more conducible to improve the electrochemical properties and specific surface areas of composites. Raman spectra of S-ZVI supported by pinewood-derived BC (S-ZVI/PBC) showed the ID/IG ratio increased from 0.639 to 0.975 for the composites prepared at 300-700 °C, indicating the increased structural defects and resulting in the greatest Cr(VI) removal (35.81 mg g-1) and reduction (30.21 mg g-1) amounts of S-ZVI/PBC700. Besides, S-ZVI/PBC exhibited greater electrochemical reactivity and surface area than S-ZVI harbored by BC from dairy manure and rice straw. Additionally, Pearson correlation analysis revealed that Cr(VI) removal was significantly positively correlated to surface area (R2 = 0.90) and negatively correlated to Tafel corrosive potential (R2 = 0.88). Both desorption experiment and XPS spectra of spent sorbents showed that reduction predominated the detoxifying mechanism of Cr(VI) followed by adsorption (due to corrosively-generated iron oxides and BC) and precipitation (Cr2S3). This suggested that biochar with greater specific surface area and electrical conductivity is more favorable to immobilize S-ZVI with respect to Cr(VI) removal.

Elevated CO2 and biochar differentially affect plant C:N:P stoichiometry and soil microbiota in the rhizosphere of white lupin (Lupinus albus L.).

Biochar application is a potent climate change mitigation strategy in agroecosystems. However, little is known about the interactive effects of elevated CO2 (eCO2) and biochar on plant nutrient uptake and soil microbial processes. A pot experiment was conducted to investigate the effects of eCO2 and biochar addition on plant C:N:P stoichiometry and rhizobacterial community for better management of nutrient balance and use efficiency in a future climate scenario. White lupin (Lupinus albus L.) was grown for 30 days in topsoil and subsoil with or without 2% corn-stubble biochar under ambient CO2 (aCO2: 390 ppm) or eCO2 (550 ppm). Elevated CO2 increased, but biochar decreased, plant biomass and shoot N and P uptake, with no interactions in either soil layer. Elevated CO2 decreased shoot N concentration by 16% and biochar decreased shoot P concentration by 11%. As a result, eCO2 increased shoot C:N ratio by 20% and decreased the N:P ratio by 11%. Biochar decreased shoot C:N ratio by 8% in the subsoil under eCO2. However, biochar increased shoot C:P ratio by an average of 13% and N:P ratio by 23% in the subsoil. Moreover, plants grown in the subsoil showed lower shoot N (35%) and P (70%) uptake compared to the topsoil. The results indicate that N and P are the more limiting factors that regulate plant growth under eCO2 and biochar application, respectively. Elevated CO2 and biochar oppositely affected dominant rhizobacterial community composition, with the eCO2 effect being greater. The microbiota in the subsoil held a greater diversity of contrasting species than the topsoil, which were associated with nutrient cycling, hydrocarbon degradation and plant productivity. These results enrich our understanding of potential soil nutrient cycling and plant nutrient balance in future agroecosystems.

The significant role of electron donating capacity and carbon structure of biochar to electron transfer of zerovalent iron.

Herein, the major biochar properties were correlated with electron transfer of zerovalent iron (ZVI) and contribution of biomass constituents to biochar property was ascertained to optimize electron transfer of ZVI. To this end, five respective stalk-type and wood-type lignocellulosic biomasses were pyrolzed at 600 °C to prepare biochars to harbor ZVI (ZVI/BC). Thermogravimetric analysis demonstrated woody biomasses decomposed more intensively at higher temperature relative to stalky biomass. ZVI/BC were characterized with Raman, X-ray diffraction, and electrochemical analyses including electron donating capacity (EDC) and electron accepting capacity (EAC). Pearson correlation and partial least-squares (PLS) analyses confirmed that Cr(VI) reduction capacity was negatively related to Tafel corrosion potential and intensity ratio of ID/IG, but significantly positively-related to EDC of BC, in which EDC was a predominant attribute to contribute to reductive capacity toward Cr(VI) reduction. That is, greater EDC and higher graphitic carbon structure of biochar due to cellulose and hemicellulose components favor electron transfer of ZVI toward Cr(VI) reduction.

Neuronal accumulation of peroxidated lipids promotes demyelination and neurodegeneration through the activation of the microglial NLRP3 inflammasome.

Peroxidated lipids accumulate in the presence of reactive oxygen species and are linked to neurodegenerative diseases. Here we find that neuronal ablation of ARF1, a small GTPase important for lipid homeostasis, promoted accumulation of peroxidated lipids, lipid droplets and ATP in the mouse brain and led to neuroinflammation, demyelination and neurodegeneration, mainly in the spinal cord and hindbrain. Ablation of ARF1 in cultured primary neurons led to an increase in peroxidated lipids in co-cultured microglia, activation of the microglial NLRP3 inflammasome and release of inflammatory cytokines in an Apolipoprotein E-dependent manner. Deleting the Nlrp3 gene rescued the neurodegenerative phenotypes in the neuronal Arf1-ablated mice. We also observed a reduction in ARF1 in human brain tissue from patients with amyotrophic lateral sclerosis and multiple sclerosis. Together, our results uncover a previously unrecognized role of peroxidated lipids released from damaged neurons in activation of a neurotoxic microglial NLRP3 pathway that may play a role in human neurodegeneration.

The contribution of lignocellulosic constituents to Cr(VI) reduction capacity of biochar-supported zerovalent iron.

Biochars (BCs) derived from individual and blending lignocellulosic constituents were prepared to harbor zerovalent iron (ZVI/BC) in an effort to discriminate significance of each constituent or combination in ZVI/BC for Cr(VI) removal. BCs and ZVI/BC were characterized by TGA/GSC, XRD, Raman and BET analyses. Cellulose (BCC) and hemicellulose (BCH)-derived BCs has greater C content, H/C ratio, surface area and mass loss than BCs derived from lignin or lignin-containing biopolymer blends (BCLX). As per sorption and XPS analysis, ZVI/BC demonstrated greater Cr(VI) removal capacity than respective BCs, in which reduction accounted for over 77% Cr(VI) detoxification. Cr(VI) reduction by ZVI harbored by BCC and BCH was 19.72-16.54 g kg-1, compared to 5.97-4.26 g kg-1 for BCLX. ZVI/BC prepared by three-biopolymer blends with (12.63 g kg-1) or without (12.32 g kg-1) mineral approximated pinewood-BC (BCP) (13.02 g kg-1) for Cr(VI) reduction, suggesting minerals are not important constituent. Tafel analysis showed BCC and BCH, with lower ID/IG ratio owing to greater graphitization, were more conducible to transfer electron of ZVI in Cr(VI) reduction than BCLX. Thus, cellulose, hemicellulose and lignin can offer a good prediction of property of natural biomass, in which BCC and BCH favor electron transfer of ZVI but BCL is not electroactive.

Preparation of highly-conductive pyrogenic carbon-supported zero-valent iron for enhanced Cr(â ¥) reduction.

In this work, electron transfer (ET) moiety of PC was ascertained in chromate (Cr(Ⅵ)) reduction by zero-valent iron supported by pyrogenic carbon (PC) (ZVI/PC) prepared by pyrolysis of hematite (α-Fe2O3)-treated pinewood. X-ray diffraction analysis suggested successive phase transformation of α-Fe2O3→magnetite (Fe3O4)→wustite (FeO)→ZVI (Feo). Raman spectra and Brunauer-Emmett-Teller analysis revealed that ZVI/PC is characterized with more ordered graphitic carbon and greater surface area than pristine PC. Maximal Cr(Ⅵ) removal capacity (pH = 3) as predicted by Langmuir isotherm model were 5.78, 36.12 and 8.39 g kg-1 for PC, ZVI/PC and ZVI, respectively. ZVI/PC maintained significantly greater Cr(Ⅵ) removal capacity than ZVI and PC at pH 3-9, but Cr(Ⅵ) removal dropped rapidly to 6.78 g kg-1 at pH 4 and above. X-ray photoelectron spectroscopy and successive desorption of Cr-laden ZVI/PC and ZVI showed trivalent Cr was the dominant species, suggesting reduction was an important mechanism for Cr(Ⅵ) detoxification. Electrochemical analysis demonstrated that ZVI/PC exhibited greater Tafel corrosion rate and ET quantity, with lower electrical resistance. Besides, Cr(Ⅵ) reduction showed reversal trend with electrical resistance of ZVI/PC. To conclude, ET capacity was closely associated with electrical conductivity of ZVI/PC due to intensified conductive graphitic carbon structure of PC at higher pyrogenic temperatures.

Photocatalytic behavior of biochar-modified carbon nitride with enriched visible-light reactivity.

Ultra-thin layered structures and modified bandgaps are two efficient strategies to increase the photocatalytic performance of various materials for the semiconductor industry. In the present study, we combined both strategies in one material to form carbon-doped graphitic carbon nitride (g-C3N4) nano-layered structures by the method of melamine thermal condensation, in the presence of different mass ratios of biochar. The characterization showed that the composite with the best ratio retained the g-C3N4 polymeric framework and the bond with g-C3N4. The biochar was established via π-π stacking interactions and ether bond bridges. The π-conjugated electron systems provided from biochar can elevate charge separation efficiency. The ultra-thin structure also curtailed the distance of photogenerated electrons migrating to the surface and enlarge specific surface area of materials. The presence of carbon narrowed the bandgap and increased light absorption at a wider range of wavelengths of g-C3N4. The biochar/melamine ratio of 1:15 presented the best performance, 2.8 and 5 times faster than g-C3N4 degradating Rhodamine and Methyl Orange, respectively. Moreover, the catalyst presented a good stability for 4 cycles. In addition to that, biochar from waste biomass can be considered a sustainable, cost-effective, and efficient option to modify g-C3N4-based photocatalysts.

Arf1-mediated lipid metabolism sustains cancer cells and its ablation induces anti-tumor immune responses in mice.

Cancer stem cells (CSCs) may be responsible for treatment resistance, tumor metastasis, and disease recurrence. Here we demonstrate that the Arf1-mediated lipid metabolism sustains cells enriched with CSCs and its ablation induces anti-tumor immune responses in mice. Notably, Arf1 ablation in cancer cells induces mitochondrial defects, endoplasmic-reticulum stress, and the release of damage-associated molecular patterns (DAMPs), which recruit and activate dendritic cells (DCs) at tumor sites. The activated immune system finally elicits antitumor immune surveillance by stimulating T-cell infiltration and activation. Furthermore, TCGA data analysis shows an inverse correlation between Arf1 expression and T-cell infiltration and activation along with patient survival in various human cancers. Our results reveal that Arf1-pathway knockdown not only kills CSCs but also elicits a tumor-specific immune response that converts dying CSCs into a therapeutic vaccine, leading to durable benefits.

Protein kinase C and protein kinase A are involved in the protection of recombinant human glucagon-like peptide-1 on glomeruli and tubules in diabetic rats.

AIMS/INTRODUCTION: Blockade or reversal the progression of diabetic nephropathy is a clinical challenge. The aim of the present study was to examine whether recombinant human glucagon-like peptide-1 (rhGLP-1) has an effect on alleviating urinary protein and urinary albumin levels in diabetic rats. MATERIALS AND METHODS: Streptozotocin-induced diabetes rats were treated with rhGLP-1 insulin and saline. Using immunostaining, hematoxylin-eosin, electron microscopy and periodic acid-Schiff staining to study the pathology of diabetic nephropathy, and we carried out quantitative reverse transcription polymerase chain reaction, western blot and immunohistochemistry to identify the differentially expressed proteins. The mechanism was studied through advanced glycation end-products-induced tubular epithelial cells. RESULTS: rhGLP-1 inhibits protein kinase C (PKC)-ß, but increases protein kinase A (PKA), which reduces oxidative stress in glomeruli and in cultured glomerular microvascular endothelial cells. In tubules, rhGLP-1 increased the expression of two key proteins related to re-absorption - megalin and cubilin - which was accompanied by downregulation of PKC-ß and upregulation of PKA. On human proximal tubular epithelial cells, rhGLP-1 enhanced the absorption of albumin, and this was blocked by a PKC activator or PKA inhibitor. CONCLUSIONS: These findings suggest that rhGLP-1 can reverse diabetic nephropathy by protecting both glomeruli and tubules by inhibiting PKC and activating PKA.

Biomass facilitated phase transformation of natural hematite at high temperatures and sorption of Cd2+ and Cu2.

Phase changes of natural hematite are often practiced to improve heavy metal removal and magnetism for easy recycling. In this work, pinewood biomass (PB) and natural hematite (H) admixtures were pyrolyzed at 300, 450 and 600 °C under N2 environment to prepare HBC nanocomposites (HBC300, HBC450 and HBC600). The X-ray diffraction (XRD) confirmed the reductive transformation of hematite (crystallite size ≈ 47 nm) into magnetite (25 nm) and further to wustite (25 nm) and zerovalent iron (48 nm). The Langmuir isotherms showed that the maximum sorption capacities of HBC300, HBC450, and HBC600 were 173, 138, and 130 mmol kg-1 for Cd2+, and 359, 172, and 197 mmol kg-1 for Cu2+, respectively. The higher pH up to 5 increased sorption of both Cd2+ and Cu2+, whereas the higher ionic strength (0.05-0.4 M) decreased Cd2+ sorption. Sorption of Cd2+ and Cu2+ by HBC300 was accompanied by one order of magnitude greater cation release than HBC450 and HBC600. In a binary system, Cd2+ sorption was depressed by over four times in presence of Cu2+. Overall, ion exchange was more pronounced for HBC300, and Cu2+ was more favorably retained by specific sorption than Cd2+. The greater magnetism of HBC nanoparticles favors separation from aqueous solutions.

Biochar-supported nZVI (nZVI/BC) for contaminant removal from soil and water: A critical review.

The promising characteristics of nanoscale zero-valent iron (nZVI) have not been fully exploited owing to intrinsic limitations. Carbon-enriched biochar (BC) has been widely used to overcome the limitations of nZVI and improve its reaction with environmental pollutants. This work reviews the preparation of nZVI/BC nanocomposites; the effects of BC as a supporting matrix on the nZVI crystallite size, dispersion, and oxidation and electron transfer capacity; and its interaction mechanisms with contaminants. The literature review suggests that the properties and preparation conditions of BC (e.g., pore structure, functional groups, feedstock composition, and pyrogenic temperature) play important roles in the manipulation of nZVI properties. This review discusses the interactions of nZVI/BC composites with heavy metals, nitrates, and organic compounds in soil and water. Overall, BC contributes to the removal of contaminants because it can attenuate contaminants on the surface of nZVI/BC; it also enhances electron transfer from nZVI to target contaminants owing to its good electrical conductivity and improves the crystallite size and dispersion of nZVI. This review is intended to provide insights into methods of optimizing nZVI/BC synthesis and maximizing the efficiency of nZVI in environmental cleanup.

Carboxymethyl cellulose stabilized ZnO/biochar nanocomposites: Enhanced adsorption and inhibited photocatalytic degradation of methylene blue.

Biochar(BC)-supported nanoscaled zinc oxide (nZO) was encapsulated either with (nZORc/BC) or with no (nZOR/BC) sodium carboxymethyl cellulose (CMC). The X-ray diffraction and ultraviolet (UV)-visible-near infrared spectrophotometry revealed that nZO of 16, 10, and 20 nm with energy band gaps of 2.79, 3.68 and 2.62 eV were synthesized for nZOR/BC, nZORc/BC and nZO/BC, respectively. The Langmuir isotherm predicted saturated sorption of methylene blue (MB) was 17.01 g kg-1 for nZORc/BC, over 19 times greater than nZOR/BC and nZO/BC. Under UV irradiation, 10.9, 61.6, 83.1, and 41.6% of MB were degraded for nZORc/BC, nZO/BC, nZOR/BC and BC. The scavenging experiment revealed hydroxyl radical dominated CMC degradation. Exogenous CMC (2 g L-1) increased MB sorption from 10.6% to 73.1%, but decreased MB degradation from 80.7% to 41.1%, relative to nZOR/BC. Thus, CMC could increase MB sorption by electrostatic attraction and other possible mechanisms. The compromised MB degradation may be ascribed to reduced availability of hydroxyl and superoxide radicals to degrade MB, and increased band gap energy of ZnO.