Applications of hollow nanomaterials in environmental remediation and monitoring: A review

Hollow nanomaterials have attracted significant attention because of their high chemical and thermal stability, high specific surface area, high porosity, low density, and good biocompatibility. These state-of-the-art nanomaterials have been shown to efficiently adsorb heavy metals, and volatile hazardous substances, photodegrade persistent organic pollutants, and other compounds, and inactivate bacteria. Such properties have enabled the use of these materials for environmental remediation, such as in water/wastewater treatment, soil remediation, air purification, and substance monitoring, etc. Hollow nanomaterials showed higher photocatalytic activity than those without hollow structure owing to their high active surface area, reduced diffusion resistance, and improved accessibility. And, the Doping method could improve the photocatalytic performance of hollow nanomaterials further under visible light. Moreover, the synthetic mechanisms and methods of these materials are important because their size and morphology help to determine their precise properties. This article reviews the environmental applications and potential risks of these materials, in addition to their syntheses. Finally, an outlook into the development of these materials is provided.     

碳纳米材料在环境中的转化

碳纳米材料主要包括富勒烯、碳纳米管和石墨烯.随着碳纳米材料的研究和应用范围不断扩大,其对环境的影响和在环境中的行为也逐渐受到关注,而在环境中的转化是环境行为的一个重要方面.首先,环境转化会改变碳纳米材料的性质,从而影响其它行为如聚集沉降和生态毒性.同时,作为一种以碳为骨架的材料,能否被自然界转化、从而进入碳循环是评价碳纳米材料长期环境影响的必要信息.因此,本文重点总结了碳纳米材料在自然环境条件和水处理条件下可能发生的生物或非生物转化,并分析影响碳纳米材料转化的因素,和转化过程对其环境行为的影响.     

Effects of different types of biochar on the properties and reactivity of nano zero-valent iron in soil remediation

• Biochar enhanced the mobility and stability of zero-valent iron nanoparticles. • Particle performance was best when the BC:nZVI mass ratio was 1:1. • Bagasse-BC@nZVI removed 66.8% of BDE209. The addition of nano zero-valent iron (nZVI) is a promising technology for the in situ remediation of soil. Unfortunately, the mobility and, consequently, the reactivity of nZVI particles in contaminated areas decrease due to their rapid aggregation. In this study, we determined how nZVI particles can be stabilized using different types of biochar (BC) as a support (BC@nZVI). In addition, we investigated the transport behavior of the synthesized BC@nZVI particles in a column filled with porous media and their effectiveness in the removal of BDE209 (decabromodiphenyl ether) from soil. The characterization results of N₂ Brunauer–Emmett–Teller (BET) surface area analyses, scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) indicated that nZVI was successfully loaded into the BC. The sedimentation test results and the experimental breakthrough curves indicated that all of the BC@nZVI composites manifested better stability and mobility than did the bare-nZVI particles, and the transport capacity of the particles increased with increasing flow velocity and porous medium size. Furthermore, the maximum concentrations of the column effluent for bagasse–BC@nZVI (B–BC@nZVI) were 19%, 37% and 48% higher than those for rice straw–BC@nZVI (R–BC@nZVI), wood chips–BC@nZVI (W–BC@nZVI) and corn stalks–BC@nZVI (C–BC@nZVI), respectively. A similar order was found for the removal and debromination efficiency of decabromodiphenyl ether (BDE209) by the aforementioned particles. Overall, the attachment of nZVI particles to BC significantly increased the reactivity, stability and mobility of B–BC@nZVI yielded, and nZVI the best performance.     

Removing polybrominated diphenyl ethers in pure water using Fe/Pd bimetallic nanoparticles

Polybrominated diphenyl ethers (PBDEs) have been widely used as fire-retardants. Due to their high production volume, widespread usage, and environmental persistence, PBDEs have become ubiquitous contaminants in various environments.Nanoscale zero-valent iron (ZVI) is an effective reductant for many halogenated organic compounds. To enhance the degradation efficiency, ZVI/Palladium bimetallic nanoparticles (nZVI/Pd) were synthesized in this study to degrade decabromodiphenyl ether (BDE209) in water. Approximately 90% of BDE209 was rapidly removed by nZVI/Pd within 80 min, whereas about 25% of BDE209 was removed by nZVI. Degradation of BDE209 by nZVI/Pd fits pseudo-first-order kinetics. An increase in pH led to sharply decrease the rate of BDE209 degradation. The degradation rate constant in the treatment with initial pH at 9.0 was more than 6.8 × higher than that under pH 5.0. The degradation intermediates of BDE209 by nZVI/Pd were identified and the degradation pathways were hypothesized. Results from this study suggest that nZVI/Pd may be an effective tool for treating polybrominated diphenyl ethers (PBDEs) in water.     

Applications and genotoxicity of nanomaterials in the food industry

The use of nanomaterials in industrial sectors is currently widely accepted because of their unique beneficial properties. However, those unique properties can also induce toxic effects. Toxicity responses are induced by kinetic, dynamic, and catalytic properties, and by functionalization, net particle reactivity, agglomeration, and functional environment. Here, we review nanomaterial applications in food and consumer industries, genotoxic mechanisms, methods to study nanomaterials, and factors of toxicity.     

植物油改性纳米铁修复硝基苯污染地下水的研究

实验室条件下,液相还原法FeSO4·7H2O和KBH4反应制备纳米铁,用XRD、TEM对其性能进行表征,结果表明该纳米铁平均粒径为50 nm,主要成分为α-Fe0。实验室进一步制备植物油改性纳米铁,TEM表明油膜均匀包覆在纳米铁颗粒表面,且纳米铁粒子分布均匀,分散较好。厌氧条件下,纳米铁与硝基苯反应,研究纳米铁和植物油改性纳米铁对硝基苯的降解性能,以及不同初始铁投加量、植物油质量分数、初始 pH 对硝基苯降解的影响。研究表明,纳米铁和植物油改性纳米铁均对硝基苯有较强的降解能力,理论摩尔比下,1 h内纳米铁和改性纳米铁对硝基苯的降解率达99.85%和56.74%;油膜质量分数为1%和2%的改性纳米铁降解硝基苯效果较好;随着初始纳米铁投加量的增加,硝基苯的降解越快;初始pH对改性纳米铁降解硝基苯有一定影响,酸性条件有利于改性纳米铁降解硝基苯。     

纳米Fe~0协同微生物对PCB77的降解研究

研究了纳米零价铁协同微生物降解水溶液中的PCB77。从污染土样中分离出一株多氯联苯（PCBs）降解菌,对其进行革兰氏染色形态观察,并用降解菌降解PCB77。结果表明：培养温度30℃、溶液pH 7.0、微生物接种量109 cfu·mL-1、PCB77初始质量浓度1.0 mg·L-1时,降解菌对PCB77的降解率为58.63%。纳米零价铁对PCB77的降解是一个还原脱氯过程,7 d时的降解率为82.99%。采用纳米零价铁/微生物联合体系降解水溶液中PCB77,降解率显著高于微生物和纳米零价铁单一体系,降解率可达93.30%。研究结果将为环境中PCBs残留提供了一种高效去除的方法,并为PCBs污染土壤的修复提供理论依据。     

不同螯合剂对零价铁活化过硫酸盐降解对氯苯胺的影响

研究了螯合剂EDTA、草酸(OA)、柠檬酸(CA)以及2,2-联吡啶(BPY)对零价铁(ZVI)活化过硫酸盐(PS)降解对氯苯胺(PCA)的影响;考察了溶液中PCA的降解率、PS消耗量和溶液中的Fe2+含量对反应的影响.结果表明,在中性条件下,EDTA、OA、CA等3种螯合剂抑制PCA在零价铁活化过硫酸盐体系中降解.而BPY促进了PCA的降解,增加溶液中BPY浓度,PCA的降解率增大;且PCA的降解是拟一级反应,其速率和BPY浓度呈正比;溶液初始p H值为3.0—11.0时,PCA在中性和碱性条件下的降解效率高于酸性条件.相对未加入BPY的体系,在中性和碱性条件下,BPY促进ZVI中Fe2+的溶出而提高PS活化效率,在酸性条件下,BPY由于减少了溶液中游离的Fe2+浓度,表现出对PCA的降解抑制.本文结果进一步证明了零价铁活化过硫酸盐非均相体系中,零价铁是作为活化PS的Fe2+的替代来源.     

Fe~0体系降解2,4二氯酚的影响因素及其反应机理

采用铁屑、炉渣及河砂混合介质降解2,4-二氯酚（2,4-DCP）模拟废水,研究铁屑粒径、铁屑投加量、铁屑与炉渣配比、pH值等因素对2,4-DCP脱氯效果的影响,探讨Fe0体系降解2,4-DCP的反应机理。结果表明,铁屑粒径、铁屑投加量、铁屑与炉渣配比、pH对2,4-DCP脱氯效果均有显著影响,在铁屑粒径为2～5 mm、不改变废水pH、铁屑与炉渣质量比为31∶9条件下,Fe0体系对2,4-DCP去除率高达97%。2,4-DCP经脱氯后主要产物为2-氯酚、4-氯酚和苯酚,反应后废水的可生化性明显提高,利于后续的生物处理。     

零价铁还原和过硫酸盐氧化联合降解水中硝基苯

将零价铁(Fe0)的还原和过硫酸盐(persulfate,PS)的高级氧化技术结合用于水中难降解有机污染物硝基苯的去除.研究结果表明,Fe0在常温常压下可将硝基苯还原生成苯胺,随着Fe0投加量的增加,硝基苯还原为苯胺的速率逐渐增大.PS本身对硝基苯氧化作用不明显,但在Fe0与PS二者联合体系中,硝基苯和苯胺同时被去除,而且随着PS投加量的增加二者被去除的速度也随之增加.在Fe0还原和PS氧化联合处理硝基苯的体系中可能存在两个过程,一是Fe0还原硝基苯产生苯胺和二价铁离子Fe2+,二是Fe2+催化PS产生强氧化性的硫酸根自由基将苯胺氧化降解.     

三维荧光光谱技术在水环境修复和废水处理中的应用

近年来我国水环境污染问题情况日益严重,其引发的水华问题频发,藻类生长代谢过程释放的各类衍生物对水生生态系统及原水处理工艺性能造成影响。为此,分析环境水体、废水处理系统中溶解性有机污染物（DOM）的组成、性质和来源,对水环境安全及水污染控制具有重要意义。三维荧光光谱技术通过在不同的激发波长上扫描发射荧光谱以获得激发．发射矩阵（EEM）,基于EEM数据构建三维立体图或等高线（指纹图）描绘监测对象特性,可分析水体溶解性有机物、藻类及藻毒素等,近年来已在饮用水源水质监测、湖库富营养化成因分析及废水生物处理性能评价等方面得到应用。与传统分析方法相比,该技术具有灵敏度高、操作简便、检测快速、试剂消耗量少等优点。文章从荧光光谱分析技术基本原理出发,对三维荧光峰的分类、影响因素及其在水环境中的应用进行了综述,并对今后该技术在环境领域的研究方向进行了展望,以期为水污染控制、污染环境修复提供先进可靠的分析方法。     

Process control factors for continuous microbial perchlorate reduction in the presence of zero-valent iron

Process control parameters influencing microbial perchlorate reduction via a flow-through zero-valent iron （ZVI） column reactor were investigated in order to optimize perchlorate removal from water. Mixed perchlorate reducers were obtained from a wastewater treatment plant and inoculated into the reactor without further acclimation. Examined parameters included hydraulic residence time （HRT）, pH, nutrients requirement, and perchlorate reduction kinetics. The minimum HRT for the system was concluded to be 8 hr. The removal efficiency of 10 mg. L-1 influent perchlorate concentration was reduced by 20%-80% without control to the neutral pH （HRT = 8 hr）. Therefore pH was determined to be an important parameter for microbial perchlorate reduction. Furthermore, a viable alternative to pH buffer was discussed. The microbial perchlorate reduction followed the first order kinetics, with a rate constant （K） of 0.761 hr-1. The results from this study will contribute to the implementation of a safe, cost effective, and efficient system for perchlorate reduction to below regulated levels.     

生物炭/铁复合材料的制备及其在环境修复中的应用研究进展

生物炭/铁复合材料(比如生物炭/纳米零价铁(nZVI),生物炭/硫化亚铁和生物炭/氧化铁),由于其优异的理化性质而被广泛应用于环境污染修复.本文首先总结了生物炭/铁复合材料的制备方法和表征手段,制备方法主要有热解法,水热碳化,沉淀和球磨法等.其次,通过综述生物炭/铁复合材料在有机污染和无机污染修复中的应用,阐明生物炭/铁复合材料的在环境修复中的应用机制以及复合材料中铁与生物炭的协同作用机理.总体而言,由于铁和生物炭之间的协同作用,提高了复合材料的比表面积,官能团和电子传递效率,从而增强生物炭/铁复合材料的性能.最后,提出了未来生物炭/铁复合材料的研究方向,进一步推动生物炭/铁复合材料在环境修复中的应用.     

Cadmium removal mechanistic comparison of three Fe-based nanomaterials: Water-chemistry and roles of Fe dissolution

● nZVI, S-nZVI, and nFeS were systematically compared for Cd(II) removal. ● Cd(II) removal by nZVI involved coprecipitation, complexation, and reduction. ● The predominant reaction for Cd(II) removal by S-nZVI and nFeS was replacement. ● A simple pseudo-second-order kinetic can adequately fit Fe(II) dissolution. Cadmium (Cd) is a common toxic heavy metal in the environment. Taking Cd(II) as a target contaminant, we systematically compared the performances of three Fe-based nanomaterials (nano zero valent iron, nZVI; sulfidated nZVI, S-nZVI; and nano FeS, nFeS) for Cd immobilization under anaerobic conditions. Effects of nanomaterials doses, initial pH, co-existing ions, and humic acid (HA) were examined. Under identical conditions, at varied doses or initial pH, Cd(II) removal by three materials followed the order of S-nZVI > nFeS > nZVI. At pH 6, the Cd(II) removal within 24 hours for S-nZVI, nFeS, and nZVI (dose of 20 mg/L) were 93.50%, 89.12% and 4.10%, respectively. The fast initial reaction rate of nZVI did not lead to a high removal capacity. The Cd removal was slightly impacted or even improved with co-existing ions (at 50 mg/L or 200 mg/L) or HA (at 2 mg/L or 20 mg/L). Characterization results revealed that nZVI immobilized Cd through coprecipitation, surface complexation, and reduction, whereas the mechanisms for sulfidated materials involved replacement, coprecipitation, and surface complexation, with replacement as the predominant reaction. A strong linear correlation between Cd(II) removal and Fe(II) dissolution was observed, and we proposed a novel pseudo-second-order kinetic model to simulate Fe(II) dissolution.     

纳米Fe0对Cr（VI）的还原及其影响因素

采用纳米Fe0还原水溶液中的Cr（Ⅵ）,考察纳米Fe0投加量、Cr（Ⅵ）初始浓度、溶液pH值和有机酸等因素对cr（Ⅵ）还原的影响。结果表明,纳米Fe。对Cr（Ⅵ）的还原效果明显,其对Cr（Ⅵ）的还原率分别是铁粉和铁屑的7和13倍。Cr（Ⅵ）溶液初始质量浓度为20mg·L-1、Fe。投加量为5g·L“条件下,反应24h时纳米Fe0对Cr（Ⅵ）的还原率达82．7％。溶液低pH值可以促进Fe。的腐蚀速度,提高反应速率,当pH值为3．0时还原效果最好。草酸、丙二酸和丁二酸对纳米Fe。还原Cr（Ⅵ）均有明显的促进作用,3种有机酸对Cr（Ⅵ）还原率的提高幅度由高到低依次为草酸、丙二酸和丁二酸。     

零价铁对土壤中4-氯苯酚还原脱氯研究

氯苯酚是常见的环境污染物，它们在土壤中的加速分解可以减少对人类健康的危害。以恒温培养为方法，GC-MS为检测手段，研究了在常温常压下土壤中4-氯苯酚(4-CP)在零价铁作用下的还原脱氯反应。结果表明：4-CP可以被来自零价铁的电子还原，零价铁能够有效促进土壤中的4-CP脱除苯环上的氯原子，从而达到降低毒性、增加可生化性目的。反应条件如初始pH、时间、零价铁用量等均对4-CP还原脱氯效率有重要影响，特别是当初始pH值控制在偏酸时更有利于反应的进行。在零价铁加入量500mg、初始pH=4、反应时间7d的条件下，零价铁对土壤中4-CP还原脱氯效率最高可以达到65％。利用实验数据，对零价铁作用下4-CP还原脱氯的反应机理也进行了初步探讨。     

人工纳米颗粒的植物毒性及其在植物中的吸收和累积

人工纳米颗粒(engineered nanoparticles,ENPs)在被广泛应用的同时,其潜在的环境风险和对健康的影响引起国内外的广泛重视。植物是人们的主要食物来源,ENPs可能被植物吸收并累积在可食部分,随食物链进入人体而引起健康风险。因此,ENPs的植物毒性及其在植物中的吸收和累积受到越来越多的关注。总结了ENPs的植物毒性及植物对ENPs的吸收、运输和累积,讨论了可能的致毒机制、影响其毒性的因素以及植物的解毒机制,并对未来应该注重开展的研究进行了展望。     

Wastewater treatment meets artificial photosynthesis: Solar to green fuel production,water remediation and carbon emission reduction

• Mitigating energy utilization and carbon emission is urgent for wastewater treatment. • MPEC integrates both solar energy storage and wastewater organics removal. • Energy self-sustaining MPEC allows to mitigate the fossil carbon emission. • MPEC is able to convert CO₂ into storable carbon fuel using renewable energy. • MPEC would inspire photoelectrochemistry by employing a novel oxidation reaction. Current wastewater treatment (WWT) is energy-intensive and leads to vast CO₂ emissions. Chinese pledge of “double carbon” target encourages a paradigm shift from fossil fuels use to renewable energy harvesting during WWT. In this context, hybrid microbial photoelectrochemical (MPEC) system integrating microbial electrochemical WWT with artificial photosynthesis (APS) emerges as a promising approach to tackle water-energy-carbon challenges simultaneously. Herein, we emphasized the significance to implement energy recovery during WWT for achieving the carbon neutrality goal. Then, we elucidated the working principle of MPEC and its advantages compared with conventional APS, and discussed its potential in fulfilling energy self-sustaining WWT, carbon capture and solar fuel production. Finally, we provided a strategy to judge the carbon profit by analysis of energy and carbon fluxes in a MPEC using several common organics in wastewater. Overall, MPEC provides an alternative of WWT approach to assist carbon-neutral goal, and simultaneously achieves solar harvesting, conversion and storage.     

Cation exchange resin supported nanoscale zero-valent iron for removal of phosphorus in rainwater runoff

Self-made cation exchange resin supported nanoscale zero-valent iron （R-nZVI） was used to remove phosphorus in rainwater runoff. 80% of phosphorus in rainwater runoff from grassland was removed with an initial concentration of 0.72 mg. L-1 phosphorus when the dosage of R-nZVl is 8 g per liter rainwater, while only 26% of phosphorus was removed when using cation exchange resin without supported nanoscale zero-valent iron under the same condition. The adsorption capacity of R-nZVI increased up to 185 times of that of the cation exchange resin at a saturated equilibrium phosphorous concentration of 0.42 mg. L-1. Various techniques were implemented to characterize the R-nZVI and explore the mechanism of its removal of phosphate. Scanning electron microscopy （SEM） indicated that new crystal had been formed on the surface of R-nZVI. The result from inductive coupled plasma （ICP） indicated that 2.1% of nZVI was loaded on the support material. The specific surface area was increased after the load of nanoscale zero-valent iron （nZVI）, according to the measurement of BET-N2 method. The result of specific surface area analysis also proved that phosphorus was removed mainly through chemical adsorption process. X-ray photoelectron spectroscopy （XPS） analysis showed that the new product obtained from chemical reaction between phosphate and iron was ferrous phosphate.     

Characteristics and mechanisms of 4A zeolite supported nanoparticulate zero-valent iron as Fenton-like catalyst to degrade methylene blue

4A zeolite supported nanoparticulate zero-valent iron (nZVI/4A zeolite), synthesized through borohydride reduction method, was used as a catalyst with H₂O₂ to build Fenton-like reaction system to degrade methylene blue (MB) in model wastewater. The characteristics and primary mechanisms of the catalyst were investigated. The results show that nZVI/4A zeolite has the potential as a Fenton-like catalyst, and (about 30 mg/L) MB was degraded completely in 3 h with 10 mM H₂O₂, 0.2 g/L catalyst, and initial pH of 3.0. The MB degradation rates were obtained at least 70% in the tests with initial pH ranged from 2.0 to 9.0 and the catalyst dose rose from 0.2 to 5.0 g/L. Importantly, the catalyst also has a distinctive ability to increase the solution pH value from its initial acidic pH and then maintain the value at close to neutrality. This ability was controlled by both the initial pH and the catalyst dose. MB degradation clarified that hydroxyl radical was the dominated active oxidative specie in the tests with initial acidic pH and low catalyst dose (less 2.5 g/L); otherwise, Fe(VI) oxidation was the main mechanism for MB degradation; and the two processes shared synergistic effect in MB degradation in the present test. The catalyst has high operational stability in both of the composites with low iron leaching (less 2%) and catalyzing ability. Therefore, nZVI/4A zeolite has great potential as a Fenton-like catalyst and is used with H₂O₂ to build Fenton-like system which could be used to degrade MB efficiently.