Enhanced fertilizer utilization and heavy metals immobilization by ball-milling bentonite with NH4Cl: Experiments and DFT calculations.

Over-application of nitrogen fertilizer induces soil acidification, which activates heavy metals availability and poses significant challenge to crop production and food safety. In this study, we prepared a clay-based material by ball-milling bentonite with NH4Cl (NH4Cl@bentonite) and assessed its synergistic performance in enhancing nitrogen fertilizer utilization efficiency, immobilizing heavy metals, and improving crop yield and safety. The results showed that the optimal performance of NH4Cl@bentonite was achieved by milling bentonite with NH4Cl at a 4:1 mass ratio for 9 h. NH4Cl@bentonite significantly improved soil water holding and retention capacity by 1.6 and 4.3 times, respectively. In comparison to NH4Cl alone, NH4Cl@bentonite led to a 22.3% increase in N-use efficiency and a 1.5 times enhancement in crop yield. The Pb and Cd content in water spinach shoots decreased by 55.3% and 57.5%, respectively, attributed to the transformation of heavy metals into lower bioavailability states by NH4Cl@bentonite. Experiments and Density Functional Theory (DFT) calculations indicated that NH4Cl@bentonite could immobilize Pb and Cd through processes such as cation exchange, surface adsorption, complexation, and enhancement of soil pH. This work proposes a simple and efficient method for improving cropland fertilizer utilization while ensuring healthy and sustainable development. ENVIRONMENTAL IMPLICATION: Soil acidification, caused using chemical fertilizers, especially nitrogen-based ones, threatens crop production and food safety by damaging soil structure, speeding up nutrient loss, and increasing the solubility of heavy metals. To tackle this problem, we made a clay material by mixing bentonite with NH4Cl (NH4Cl@bentonite) in a ball mill. NH4Cl@bentonite increased N-use efficiency by 22.3%, boosted crop yield by 1.5 times, and reduced the Pb and Cd levels in water spinach shoots by 55.3% and 57.5%, respectively. This work suggests a simple and effective way to enhance fertilizer use in croplands while ensuring healthy and sustainable development.

Immobilization on anionic metal(loid)s in soil by biochar: A meta-analysis assisted by machine learning.

Metal pollution in soil has become one of the most serious environmental problems in China. Biochar is one of the most widely used remediation agents for soil metal pollution. However, the literature does not provide a consistent picture of the performance of biochar on the immobilization of anionic metal(loid)s, especially arsenic, in soil. To obtain a baseline understanding on the interactions of metals and biochar, 597 data records on four metal(loid)s (As, Cr, Sb and V) were collected from 70 publications for this meta-analysis, and the results are highlighted below. Biochar has a significant immobilization effect on anionic metal(loid)s in soil and reduces the bioavailability of these metals to plants. Subgroup analysis found that biochar could decrease the potential mobility of Cr, Sb and V, but the immobilization effect on As was not always consistent. Meanwhile, biochar pH and soil pH are the most key factors affecting the immobilization effect. To summarize, biochar can effectively immobilize Cr, Sb and V in soil, but more attention should be given to As immobilization in future applications. By regulating the properties of biochar and appropriate modification, anionic metal(loid)s in soil can be immobilized more effectively. Hence, both of the soil quality and crop quality can be improved.

Health risk assessment of heavy metal(loid)s in the farmland of megalopolis in China by using APCS-MLR and PMF receptor models: Taking Huairou District of Beijing as an example.

The quality of agricultural soils is important for agricultural production and food safety. The contamination of agricultural soils by heavy metal(loid)s (HMs) has aroused global attention. Fifty-two topsoil samples with 8 HMs were gathered to assess the health risks of farmland soil in Huairou District, Beijing. As a significantly enriched pollutant, the results revealed that Hg had greater ecological risks relative to other HMs. We found that the positive matrix factorization (PMF) model appears to be more physically plausible in identifying complex pollution sources compared to the absolute principal components score-multiple linear regression (APCS-MLR) model, which had a higher fit coefficient (r2 = 0.69-0.99). Five HMs from pollution sources, including agricultural activities, traffic source, natural source, fuel burning, and industrial production, were identified by integrating the PMF model with Pearson's correlation analysis, revealing corresponding contribution rates of 29.40%, 22.54%, 20.16%, 15.20%, and 12.70%, respectively. The probabilistic health risk evaluation results showed an absence of non-carcinogenic risks in all populations, but the carcinogenic risk could not be ignored, especially in children. In addition, the source-oriented health risks showed that agricultural activities made the largest contribution to the health risks of all populations. This research provides scientific evidence for preventing HMs contamination and control of farmland.

Agar-stabilized sulfidated microscale zero-valent iron: Its stability and performance in chromate reduction.

Sulfidated microscale zero-valent iron (SmZVI) attracts much attention recently in remediation of contaminated groundwater, but whether polymer coating on SmZVI would impact on its reactivity and capacity is yet to be understood. In this work, SmZVI was prepared by milling mZVI with elemental sulfur, and its stability in agar solution was evaluated. The impact of polymer coating on SmZVI grains' capacity and reactivity for chromate reduction was then examined. Experimental results indicated that SmZVI having the best overall performance was attained by grinding mZVI with elemental sulfur at 0.05 S/Fe molar ratio for 10 h. SmZVI's stability can be substantially improved if dispersed in 2.0 g/L agar solution. Existence of agar films on the SmZVI grain (A-SmZVI) lowered the material's capacity for chromate reduction by 56%, and the associated reaction kinetics by 70.4%, as estimated by pseudo first-order reaction model using the early-stage experimental data. Analysis of XPS spectra of A-SmZVI post reaction with chromate indicated that multiple reductive species including Fe0, Fe(II), FeS, and S(-II) may have jointly participated in the redox reaction taking place on the A-SmZVI-water interface. Fitting of XPS data supported that S(-II) was oxidized to SO42-, S2O32-, and S0, in order of decreasing surface concentration.

Optimization of biochar production based on environmental risk and remediation performance: Take kitchen waste for example.

Two major obstacles that need to be addressed for environmental application of biochar include its environmental risk and remediation performance for target pollutants. In this study, kitchen waste was taken as an example to optimize the pyrolysis temperature for biochar production based on its heavy metal risk and Cd(II) remediation performance. The results showed that the pH and ash content of kitchen waste biochar (KWB) increased; however, the yield, H/C, and N/C decreased with increasing pyrolysis temperature. Total content of heavy metals in KWB got enriched after pyrolysis, while heavy metals' risk was reduced from moderate to low due to the transformation of directly toxic heavy metal fractions into potentially and/or non-toxic fractions. The equilibrium adsorption capacities of biochar for Cd(II) ranked as follows: 49.0 mg/g (600 °C), 46.5 mg/g (500 °C), 23.6 mg/g (400 °C), 18.2 mg/g (300 °C). KWB pyrolyzed at 500 °C was found to be the most suitable for green, efficient, and economic remediation of Cd(Ⅱ) contaminated water. SEM-EDS and XPS characterization results indicated that KWB removed Cd(II) via precipitation, complexation with carboxyl/hydroxyl, ion exchange with metal cations, and coordination with π-electrons. This study puts forward a new perspective for optimizing biochar production for environmental application.

Health risk assessment based on source identification of heavy metals: A case study of Beiyun River, China.

Long-term retention and accumulation of heavy metals in rivers pose a great threat to the stability of ecosystems and human health. In this study, Beiyun River was taken as the example to quantitatively identify pollution sources and assess the pollution source-oriented health risk. A total of 8 heavy metals (Mn, Ni, Pb, Zn, As, Cr, Cd, and Cu) in Beiyun River were measured. Ordinary kriging (OK) and inverse distance weight (IDW) methods were used to predict the distribution of heavy metals. The results showed that the OK method is more accurate, and heavy metal pollution in the midstream and downstream is much more serious than that in the upstream. Principal component analysis-multiple linear regressions (PCA-MLR) and positive matrix factorization (PMF) methods were used to quantitatively identify pollution sources. The coefficient of determination (R2) of PMF is closer to 1, and the analyzed pollution source is more refined. Furthermore, the result of source identification was imported into the health risk assessment to calculate the hazard index (HI) and carcinogenic risk (CR) of various pollution sources. The results showed that the HI and CR of As and Ni to local residents were serious in the Beiyun River. Industrial activities (23.0%) are considered to be the largest contribution of heavy metals in Beiyun River, followed by traffic source (17%), agricultural source (16%), and atmospheric deposition (16%). The source-oriented risk assessment indicated that the largest contribution of HI and CR is agricultural source in the Beiyun River, followed by industrial activities. This study provides a "target" for the precise control of pollution sources, which is of great significance for improving the fine management of the water environment in the basin.

Evaluation of biochar pyrolyzed from kitchen waste, corn straw, and peanut hulls on immobilization of Pb and Cd in contaminated soil.

Biochar has a wide range of feedstocks, and different feedstocks often resulted in different properties, such as element distribution and heavy metal immobilization performance. In this work, batch experiments were conducted to assess the effectiveness of biochar pyrolyzed from kitchen waste (KWB), corn straw (CSB), and peanut hulls (PHB) on immobilization of Cd and Pb in contaminated soil by planting swamp cabbage (Ipomoea aquatica Forsk.) with a combination of toxicological and physiological tests. The results showed that biochar could all enhance the soil pH, and reduce extractable Pb and Cd in soil by 22.61%-71.01% (KWB), 18.54%-64.35% (CSB), and 3.28%-60.25% (PHB), respectively. The biochar led to a drop in Cd and Pb accumulation in roots, stems, and leaves by 45.43%-97.68%, 59.13%-96.64%, and 63.90%-99.28% at the dosage of 60.00 mg/kg, respectively. The root length and fresh weight of swamp cabbage were promoted, while superoxide dismutase (SOD) and peroxidase (POD) decreased after biochar treatment. The distribution of heavy metal fractions before and after biochar treatment indicated that biochar could transform Cd and Pb into a state of lower bioavailability, thus inhibiting Cd and Pb uptake by swamp cabbage. Biochar with different feedstocks could be ranked by the following order according to immobilization performance: KWB > CSB > PHB.

Manganese-modified biochar for highly efficient sorption of cadmium.

In this study, corn stalk was modified by manganese (Mn) before (MBC1) and after (MBC2) pyrolysis at different temperatures (400~600 °C) under anaerobic conditions for Cd sorption in both water and soil. Batch experiments in aqueous solution were conducted to evaluate the optimum sorption capability by biochar with and without manganese-modified. Both types of manganese modification can improve the sorption capacity of Cd(II) on biochar, which is superior to the corresponding pristine biochar without modification, especially, pyrolyzed at 500 °C with 5:1 modification ratio. Under the optimal preparation conditions, the sorption percentage on MBC2 was 11.01% higher than that of MBC1. The maximum sorption capacity of MBC2 was 191.94 mg g-1 calculated by isotherm model. The performance of MBC2 was also verified in soil stabilization experiments in Cd-contaminated soil. We can conclude from the results of BCR extraction that all the application rates of MBC2 (1%, 2%, and 3%) can reduce the mild acid-soluble fraction Cd. The reducible, oxidizable, and residual fraction Cd showed an upward trend, thus controlling the migration, transformation, and enrichment of Cd in soil. The characteristic analysis showed biochar has more irregular fold and more particle-aggregated surface after modification. The main components of these aggregated particles are manganese oxides (MnOx) with high sorption capacity, such as the MnOx crystal structure loaded on MBC2 is a mixed structure of δ-MnO2 and MnO. However, these particles may block the biochar pores, or some of the pores may collapse at high temperatures during the modification process. The specific surface area was reduced, even if the sorption effect of MBC was strongly enhanced. Meanwhile, under the action of the secondary pyrolysis of MBC2 modification process, the MBC2 has a higher degree of aromatization with more potential active sorption sites for Cd. The study concluded that the MBC2 could be a promising amendment for Cd in both water and soil real field applications.

Enhanced phytoremediation of PAHs-contaminated soil from an industrial relocation site by Ochrobactrum sp.

Nowadays, the remediation of polycyclic aromatic hydrocarbons (PAHs)-contaminated soil has received wide attention. In this work, Ochrobactrum sp. (PW) was isolated through selective enrichment from PAHs-contaminated soil in coking plant of Beijing, and the effects of PW on phytoremediation of that soil by alfalfa (Medicago sativa L.) and ryegrass (Lolium multiflorum Lam.) were investigated through pot experiments. Plant biomass, peroxidase (POD) activity, malondialdehyde (MDA) contents, soil enzyme activity (polyphenol oxidase and dehydrogenase activity), and residual concentration of PAHs in soils were determined to illustrate the ability of PW for enhancing the degradation of PAHs by plants. The results showed that the fresh weight of ryegrass and alfalfa inoculated with PW was significantly (p < 0.05) increased while the activity of POD and MDA contents were notably (p < 0.05) reduced than that without inoculation. Additionally, PW enhanced the activity of polyphenol oxidase and dehydrogenase in soil significantly (p < 0.05), and further enhanced the degradability of the system to PAHs. Different treatment methods could be ranked by the following order according to the degradability: SP (alfalfa + PW) > RP (ryegrass + PW) > PW (PW) > S (alfalfa) > R (ryegrass). The combined action of PW and alfalfa/ryegrass could accelerate the degradability of PAHs from soil contaminated by coking plants. PW could be used as potential bacteria to promote phytoremediation of the soil contaminated by PAHs.

Polyethylene glycol-stabilized nano zero-valent iron supported by biochar for highly efficient removal of Cr(VI).

In this study, polyethylene glycol (PEG)-stabilized nano zero-valent iron (nZVI) supported by biochar (BC) (PEG-nZVI@BC) was prepared to remedy Cr(VI) with high efficiency. The morphology, functional groups, and crystalline structure of PEG-nZVI@BC composites were characterized, revealing that when PEG was added, a large number of -OH functional groups were introduced, and nZVI was effectively dispersed on the BC surface with a smaller particle size. The results of Cr(VI) remediation experiments showed Cr(VI) removal rate by PEG-nZVI@BC (97.38%) was much greater than that by BC-loaded nZVI (nZVI@BC) (51.73%). The pseudo second-order and Sips isotherm models provide the best simulation for Cr(VI) removal experimental data, respectively. The main remediation mechanism of Cr(VI) was reduction and co-precipitation of Cr-containing metal deposits onto PEG-nZVI@BC. Ecotoxicity assessment revealed PEG-nZVI@BC (1.00 g/L) has little influence on rice germination and growth, but resisted the toxicity of Cr(VI) to rice. The modified Community Bureau of Reference (BCR) sequential extraction showed pyrolysis could increase the percentage of oxidizable and residual Cr and diminish the environmental risk of Cr release from post-removal composites.

MicroRNA-559 plays an inhibitory role in the malignant progression of glioblastoma cells by directly targeting metadherin.

Purpose: Several microRNAs (miRNAs) that are aberrantly expressed in glioblastoma multiforme (GBM) play a significant role in GBM formation and progression. The expression profile and functions of miR-559 in GBM remain unclear. Here, we quantified the expression and investigated the involvement of miR-559 in the oncogenicity of GBM cells in vitro and in vivo. Material and methods: Reverse-transcription quantitative polymerase chain reaction (RT-qPCR) was carried out to determine miR-559 expression in GBM tissues and cell lines. A series of functional assays was performed to evaluate the effects of miR-559 overexpression on GBM cell proliferation, apoptosis, migration, and invasion in vitro and on GBM tumor growth in vivo. The regulatory mechanisms of miR-559 action in GBM cells were then explored. Results: The expression of miR­559 was lower in GBM tissues and cell lines and significantly correlated with the Karnofsky performance score and tumor size among patients with GBM. Exogenous miR­559 expression inhibited GBM cell proliferation, migration, and invasion and promoted apoptosis. MiR-559 overexpression decreased tumor growth in vivo. Mechanistic experiments confirmed metadherin (MTDH) as a direct target gene of miR-559 in GBM. Silencing of MTDH induced effects similar to those of miR-559 upregulation in GBM cells, whereas MTDH expression restoration attenuated the antitumor effects of miR­559 in GBM cells. Protein kinase B (AKT) in the phosphatase and tensin homolog (PTEN)-AKT signaling pathway was found to be deactivated in GBM cells after upregulation of miR-559 both in vitro and in vivo. Conclusion: MiR-559 acts as a tumor suppressor in GBM cells in vitro and in vivo, at least in part through the downregulation of MTDH and inhibition of AKT in the PTEN-AKT pathway. Therefore, targeting the miR-559-MTDH axis may be a promising therapeutic strategy for patients with GBM.

Immobilization of heavy metals in vegetable-growing soils using nano zero-valent iron modified attapulgite clay.

Nowadays, the problem of heavy metal pollution in vegetables is received wide attention. In this work, attapulgite clay (ATTP), as a cheap and readily available inorganic mineral material, was modified with nano zero-valent iron (nFe0@ATTP) for heavy metal immobilization in soil. Batch experiments were employed to evaluate the optimal remediation performance by ATTP before and after modified with nFe0 through planting Pakchoi (Brassica chinesis L.) in Cd, Cr, and Pb contaminated soil from Changsha. The results showed that amendments can all increase the pH value of soils, and notably decrease the concentration of extractable Cd, Cr, and Pb in soil. The germination rate and root length of Pakchoi were promoted, and the activities of peroxidase (POD), catalase (CAT), and malondialdehyde (MDA) contents were notably reduced besides superoxide dismutase (SOD) activity after treatments with ATTP and nFe0@ATTP. Vicia faba-micronucleus test indicated that the application of amendments reduced the toxicity of heavy metals on the genetic material of Vicia faba root tip cells. The nFe0@ATTP were found to well convert Cd, Cr, and Pb into less bioavailable state in soil, thus blocking heavy metal uptake by plants. This material could be a promising amendment for heavy metals contaminated soil.

Performance and mechanism of Cr(VI) removal by zero-valent iron loaded onto expanded graphite.

Zero-valent iron (ZVI) was loaded on expanded graphite (EG) to produce a composite material (EG-ZVI) for efficient removal of hexavalent chromium (Cr(VI)). EG and EG-ZVI were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy and Brunauer-Emmett-Teller (BET) analysis. EG-ZVI had a high specific surface area and contained sub-micron sized particles of zero-valent iron. Batch experiments were employed to evaluate the Cr(VI) removal performance. The results showed that the Cr(VI) removal rate was 98.80% for EG-ZVI, which was higher than that for both EG (10.00%) and ZVI (29.80%). Furthermore, the removal rate of Cr(VI) by EG-ZVI showed little dependence on solution pH within a pH range of 1-9. Even at pH11, a Cr(VI) removal rate of 62.44% was obtained after reaction for 1hr. EG-ZVI could enhance the removal of Cr(VI) via chemical reduction and physical adsorption, respectively. X-ray photoelectron spectroscopy (XPS) was used to analyze the mechanisms of Cr(VI) removal, which indicated that the ZVI loaded on the surface was oxidized, and the removed Cr(VI) was immobilized via the formation of Cr(III) hydroxide and Cr(III)-Fe(III) hydroxide/oxyhydroxide on the surface of EG-ZVI.

Adsorption and regeneration of expanded graphite modified by CTAB-KBr/H3PO4 for marine oil pollution.

The cleaning-up of viscous oil spilled in ocean is a global challenge, especially in Bohai, due to its slow current movement and poor self-purification capacity. Frequent oil-spill accidents not only cause severe and long-term damages to marine ecosystems, but also lead to a great loss of valuable resources. To eliminate the environmental pollution of oil spills, an efficient and environment-friendly oil-recovery approach is necessary. In this study,1expanded graphite (EG) modified by CTAB-KBr/H3PO4 was synthesized via composite intercalation agents of CTAB-KBr and natural flake graphite, followed by the activation of phosphoric acid at low temperature. The resultant modified expanded graphite (M-EG) obtained an interconnected and continuous open microstructure with lower polarity surface, more and larger pores, and increased surface hydrophobicity. Due to these characteristics, M-EG exhibited a superior adsorption capacity towards marine oil. The saturated adsorption capacities of M-EG were as large as 7.44  g/g for engine oil, 6.12 g/g for crude oil, 5.34 g/g for diesel oil and 4.10 g/g for gasoline oil in 120min, exceeding the capacity of pristine EG. Furthermore, M-EG maintained good removal efficiency under different adsorption conditions, such as temperature, oil types, and sodium salt concentration. In addition, oils sorbed into M-EG could be recovered either by a simple compression or filtration-drying treatment with a recovery ratio of 58-83%. However, filtration-drying treatment shows better performance in preserving microstructures of M-EG, which ensures the adsorbents can be recycled several times. High removal capability, fast adsorption efficiency, excellent stability and good recycling performance make M-EG an ideal candidate for treating marine oil pollution in practical application.

Preparation of thiol-functionalized activated carbon from sewage sludge with coal blending for heavy metal removal from contaminated water.

Sewage sludge produced from wastewater treatment is a pressing environmental issue. Mismanagement of the massive amount of sewage sludge would threat our valuble surface and shallow ground water resources. Use of activated carbon prepared from carbonization of these sludges for heavy metal removal can not only minimize and stabilize these hazardous materials but also realize resources reuse. In this study, thiol-functionalized activated carbon was synthesized from coal-blended sewage sludge, and its capacity was examined for removing Cu(II), Pb(II), Cd(II) and Ni(II) from water. Pyrolysis conditions to prepare activated carbons from the sludge and coal mixture were examined, and the synthesized material was found to achieve the highest BET surface area of 1094 m2/g under 500 °C and 30 min. Batch equilibrium tests indicated that the thiol-functionalized activated carbon had a maximum sorption capacity of 238.1, 96.2, 87.7 and 52.4 mg/g for Pb(II), Cd(II), Cu(II) and Ni(II) removal from water, respectively. Findings of this study suggest that thiol-functionalized activated carbon prepared from coal-blended sewage sludge would be a promising sorbent material for heavy metal removal from waters contaminated with Cu(II), Pb(II), Cd(II) and Ni(II).