Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

Effect of Fe loading quantity on reduction reactivity of nano zero-valent iron supported on chelating resin

In this study, nanoscale zero-valent iron (NZVI) were immobilized within a chelating resin (DOW 3N). To investigate the effect of Fe loading on NZVI reactivity, three NZVI-resin composites with different Fe loading were obtained by preparing Fe(III) solution in 0, 30 and 70% (v/v) ethanol aqueous, respectively; the bromate was used as a model contaminant. TEM reveals that increasing the Fe loading resulted in much larger size and poor dispersion of nanoscale iron particles. The results indicated that the removal efficiency of bromate and the rate constant (K_obs) were decreased with increasing the Fe loading. For the NZVI-resin composite with lower Fe loading, the removal efficiency of bromate declined more significantly with the increase of DO concentrations. Under acidic conditions, decreasing the pH value had the most significant influence on NZVI-R3 with highest Fe loading for bromate removal; however, under alkaline conditions, the most significant influence of pH was on NZVI-R1 with lowest Fe loading. The effects of co-existing anions NO3−, PO43− and HCO3− were also investigated. All of the co-existing anions showed the inhibition to bromate reduction.     

Remediation of arsenic contaminated soil by sulfidated zero-valent iron

• Sulfidation significantly enhanced As(V) immobilization in soil by zerovalent iron. • S-ZVI promoted the conversion of exchangeable As to less mobile Fe-Mn bound As. • Column test further confirmed the feasibility of sulfidated ZVI on As retention. • S-ZVI amendment and magnetic separation markedly reduced TCLP leachability of As. In this study, the influences of sulfidation on zero-valent iron (ZVI) performance toward As(V) immobilization in soil were systemically investigated. It was found that, compared to unamended ZVI, sulfidated ZVI (S-ZVI) is more favorable to immobilize As(V) in soil and promote the conversion of water soluble As to less mobile Fe-Mn bound As. Specifically, under the optimal S/Fe molar ratio of 0.05, almost all of the leached As could be sequestrated by>0.5 wt.% S-ZVI within 3 h. Although the presence of HA could decrease the desorption of As from soil, HA inhibited the reactivity of S-ZVI to a greater extent. Column experiments further proved the feasibility of applying S-ZVI on soil As(V) immobilization. More importantly, to achieve a good As retention performance, S-ZVI should be fully mixed with soil or located on the downstream side of As migration. The test simulating the flooding conditions in rice culture revealed there was also a good long-term stability of soil As(V) after S-ZVI remediation, where only 0.7% of As was desorbed after 30 days of incubation. Magnetic separation was employed to separate the immobilized As(V) from soil after S-ZVI amendment, where the separation efficiency was found to be dependent of the iron dosage, liquid to soil ratio, and reaction time. Toxicity characteristic leaching procedure (TCLP) tests revealed that the leachability of As from soil was significantly reduced after the S-ZVI amendment and magnetic separation treatment. All these findings provided some insights into the remediation of As(V)-polluted soil by ZVI.     

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.     

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.     

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.     

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。     

Soil biological characteristic,nutrient contents and stoichiometry as affected by different types of remediation in a smelter-impacted soil

ABSTRACT

In order to evaluate the ecological risk reductions of copper (Cu) and cadmium (Cd) and the change of nutrient contents and stoichiometry in a smelter-impacted farmland in Guixi, Jiangxi Province, China, with ～ 800?mg Cu kg^?1 soil and 0.8?mg Cd kg^?1 soil, an three years in situ experiment was conducted. The field trial consisted of 4 ×?5?m plots in a completely randomised block design. Hydroxyapatite was added at 10?g kg^?1 soil and Sedum plumbizincicola, Elsholtzia splendens, and Pennisetum sp. were planted. Post-treatment soil and plant samples were collected annually and analysed for Cu and Cd bioaccessibility, soil carbon: nitrogen: phosphorus (C:N:P), and the stoichiometries of soil β-glucosidase (BG), N-acetylglucosaminidase (NAG), and acid phosphatase (AP) activity levels. The results indicated that the hydroxyapatite treatments significantly reduced Cu and Cd bioaccessibility as well as the ratio of C:P and N:P. Moreover, BG, NAG, and AP activity levels all increased relative to those in untreated soil. Plants may also influence soil BG, NAG, and AP activity. This study demonstrated that in situ Cu and Cd stabilisation by hydroxyapatite and phytoextraction is ecologically safe and can alter soil mineral nutrient ecological stoichiometry and enzyme activity.     

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.     

废铁屑修复汞污染土壤的实验研究

应用工厂废弃物—铁屑做原料,探讨不同铁屑投加量对修复不同土壤类型、不同程度汞污染土壤的能力,并与修复水体汞污染作了对比;另外,首次将淋滤法与国际上新兴的土壤、地下水修复技术-PRB技术结合,研究其修复土壤汞污染的效果。结果表明,废铁屑可很快去除水体中的汞,去除率可达93%;在铁屑存在下,能一定程度预防和修复土壤汞污染,在相同水体汞污染程度条件下,时间是影响土壤汞污染程度的主要因素;在CaCl2淋洗液作用下的模拟PRB实验中,土壤有效汞含量降低,同时淋洗液中汞质量浓度低于1μg·L-1。因此,用废铁屑能有效预防和修复土壤汞污染,且将淋滤法与PRB技术联用,与将铁屑直接撒入土壤中相比效果好得多,且不会引起后续的水体二次污染,是一种很有应用潜力、值得深入研究的土壤修复方法。     

十溴联苯醚(BDE209)对蜡状芽胞杆菌吸附/释放金属离子的影响

针对重金属及多溴联苯醚(PBDEs)复合污染问题,以蜡状芽孢杆菌(Bacillus cereus)复合菌为吸附材料,研究了十溴联苯醚(BDE209)对蜡状芽孢杆菌复合菌吸附及释放金属离子的影响.结果表明,蜡状芽孢杆菌复合菌对低浓度的Pb(II)(0.712mg·L-1)、Zn(II)(4.844mg·L-1)具有快速、高效、稳定的吸附能力,最高吸附率分别达到98.31%和97.83%;对低浓度的Cu(II)(1.915mg·L-1)也能起到一定的去除作用,吸附率最高可达59.90%.复合菌吸附重金属离子的同时,释放了其他金属离子:Ca(II)、K(I)、Na(I),且释放总量大于吸附总量.不同浓度的BDE209对复合菌吸附重金属产生不同的影响.1mg·L-1的BDE209基本表现为促进复合菌对重金属的吸附;而10mg·L-1的BDE209在0～4h之间促进复合菌对Pb(II)、Zn(II)的吸附,在反应4h后明显抑制吸附作用,而对Cu(II)则始终表现为促进作用.BDE209对金属离子释放的影响主要体现在反应的初始阶段(0～4h),表现为高浓度的BDE209减缓K(I)、Na(I)的释放.     

The inactivation of bacteriophages MS2 and PhiX174 by nanoscale zero-valent iron: Resistance difference and mechanisms

• The resistance of phage PhiX174 to nZVI was much stronger than that of MS2. • The nZVI damaged the surface proteins of both bacteriophages. • The nZVI could destroy the nucleic acid of MS2, but not that of PhiX174. •The phage inactivation was mainly attributed to the damage of the nucleic acid. Pathogenic enteric viruses pose a significant risk to human health. Nanoscale zero-valent iron (nZVI), a novel material for environmental remediation, has been shown to be a promising tool for disinfection. However, the existing research has typically utilized MS2 or f2 bacteriophages to investigate the antimicrobial properties of nZVI, and the resistance difference between bacteriophages, which is important for the application of disinfection technologies, is not yet understood. Here, MS2 and PhiX174 containing RNA and DNA, respectively, were used as model viruses to investigate the resistances to nZVI. The bacteriophage inactivation mechanisms were also discussed using TEM images, protein, and nucleic acid analysis. The results showed that an initial concentration of 10⁶ PFU/mL of MS2 could be completely inactivated within 240 min by 40 mg/L nZVI at pH 7, whereas the complete inactivation of PhiX174 could not be achieved by extending the reaction time, increasing the nZVI dosage, or changing the dosing means. This indicates that the resistance of phage PhiX174 to nZVI was much stronger than that of MS2. TEM images indicated that the viral particle shape was distorted, and the capsid shell was ruptured by nZVI. The damage to viral surface proteins in both phages was examined by three-dimensional fluorescence spectrum and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). However, the nucleic acid analysis demonstrated that the nucleic acid of MS2, but not PhiX174, was destroyed. It indicated that bacteriophage inactivation was mainly attributed to the damage of nucleic acids.     

Applications of nanomaterials in water treatment and environmental remediation

Nanotechnology has revolutionized plethora of scientific and technological fields; environmental safety is no exception. One of the most promising and well- developed environmental applications of nanotechnology has been in water remediation and treatment where different nanomaterials can help purify water through different mechanisms including adsorption of heavy metals and other pollutants, removal and inactivation of patho- gens and transformation of toxic materials into less toxic compounds. For this purpose, nanomaterials have been produced in different shapes, integrated into various composites and functionalized with active components. Nanomaterials have also been incorporated in nanostructured catalytic membranes which can in turn help enhance water treatment. In this article, we have provided a succinct review of the most common and popular nanomaterials （titania, carbon nanotubes （CNTs）, zero-valent iron, dendrimers and silver nanomaterials） which are currently used in environmental remediation and particularly in water purification. The catalytic properties and functionalities of the mentioned materials have also been discussed.     

有机肥与植物种类对铁肥形态转化及其有效性的影响

通过盆栽试验的方法,研究了牛粪和植物种类对石灰性土壤中铁肥形态转化及其有效性的影响。结果表明,牛粪施用改变了土壤中铁(含外源铁)的有效性及其在各形态铁间的分配。从长期的观点来看,牛粪施用能提高土壤铁的有效性,有利于土壤铁有效供给的维持。与花生相比,油莱对土壤铁具有更高的利用和活化能力,种植油菜后,土壤交换态铁被耗竭,而有效铁、氧化锰结合态铁和无定形氧化铁结合态铁的含量明显提高。有机肥的合理施用和铁效率差异性植物间的轮作或间作是增加、维系土壤铁有效性的重要农艺措施。     

马尾松不同林型对土壤理化性质的影响

以安徽省枞阳县大山村3种马尾松不同林型（马尾松纯林、马尾松-麻栎混交林、马尾松-枫香混交林）0~60 cm土层为研究对象,探讨3种马尾松林型的土壤理化性质变化规律,旨在为该区马尾松人工林的可持续发展和生产提供科学依据。结果表明：（1）0~60 cm土层,3种马尾松林型土壤容重随深度的增加而逐渐增加,混交林土壤容重显著低于纯林;土壤含水量随土层的加深而逐渐减小,其大小为：马尾松-枫香混交林>马尾松-麻栎混交林>马尾松纯林,马尾松-枫香混交林在土壤容重降低,土壤孔隙度增加及土壤含水量方面优于马尾松-麻栎混交林;（2）土壤pH值介于4.5~5.0之间,3种林型pH值随土层深度的增加而增大,但差异均不显著,其中马尾松-枫香混交林土壤pH值较高;（3）3种林型土壤有机质、全N、有效P和速效K均随土层深度的增加而减少,呈现明显的“表聚”现象,其质量分数表现为：马尾松-枫香混交林>马尾松-麻栎混交林>马尾松纯林;（4）土壤容重与土壤水分质量分数、有机质、全N、有效P和速效K等养分质量分数均呈负相关,土壤有机质与全N、有效P和速效K呈极显著的正相关,这说明土壤有机质在改善土壤理化性质和促进养分循环方面起着非常重要的作用。     

纳米零价铁颗粒去除水中重金属的研究进展

重金属是毒性大、难降解、易累积的环境污染物,纳米零价铁作为一种新型功能修复材料在去除水体和土壤中重金属方面有着广阔的应用前景.本文综述了纳米零价铁颗粒去除水中重金属的研究进展,包括纳米零价铁的常用制备方法及特性、去除效能、对不同重金属的去除机理以及发展前景和今后的研究方向,以期为该领域的深入研究提供借鉴并拓展新的思路.     

安普霉素对不同土壤中微生物活动的影响

研究了兽药抗生素安普霉素对不同土壤中微生物呼吸活动和对土壤中微生物种群生长的影响，了解该药物对土壤生态系统生态毒理学效应，以便为药物的环境安全性评价提供依据。利用直接吸收法(密闭法)测定安普霉素对土壤微生物呼吸活动的影响，结果表明：安普霉素对不同土壤中微生物呼吸活动的影响有所差异。在污染的中后期，长春土中加入一定量的安普霉素能刺激土壤的呼吸作用。在染毒的前期，安普霉素对成都土中CO2的释放量均有抑制作用。采用稀释平板法测定了药物对不同土壤中细菌、真菌生长的影响。实验结果显示：安普霉素对土壤中的细菌的生长具有明显的抑制作用，成都土和长春土的抑菌作用最为明显；同时安普霉素的这种抑制作用还表现出时间差异，24h的抑制率高于48h。安普霉素对土壤中真菌生长的影响表现出地域差异，低质量分数的安普霉素对成都土和武汉土中的真菌没有抑制作用。在所测的四种土壤中，南京土中药物对真菌的平均抑制率最高。这可能与土壤中微生物的种类和种群结构有关。安普霉素对不同土壤中对真菌的抑制作用，随药物质量分数的降低和作用时间的延长而降低。     

十溴联苯醚(BDE209)在虹鳟体内的羟基代谢产物及其对甲状腺激素水平影响的初步研究

十溴联苯醚(Decabromodiphenyl ether,BDE209)被认为是可疑甲状腺素(TH)干扰物,但干扰机制目前尚不清楚.采用单次腹腔注射的暴露方式,考察了在28d的实验周期内,不同浓度组的十溴联苯醚在虹鳟(Oncorhynchus mykiss)体内的羟基化代谢产物浓度与甲状腺激素(T3和T4)水平.结果表明:十溴联苯醚在虹鳟的肝脏和血液中均可代谢为低溴代羟基多溴联苯醚,且羟基代谢产物在整个实验周期中浓度不断累积;与此同时,血浆中T3和T4浓度均出现下降趋势.进一步的统计分析结果表明,羟基代谢产物与T3和T4浓度水平分别呈显著的负线性相关关系,这说明血浆中的甲状腺激素水平下降可能是由羟基化产物所引起的.     

十溴联苯醚(BDE 209)孕哺期及出生后暴露对子代小鼠血液系统影响初探

本研究旨在探讨BDE 209长期暴露对出生后不同发育阶段子鼠血液系统的影响。将75只雌性昆明小鼠随机分为对照组、低剂量组(1.5 mg·kg-1·d-1)和高剂量组(225 mg·kg-1·d-1)。BDE 209暴露10 d后,将雌鼠与雄鼠合笼。选取怀孕时间相近(相差不过2 d)的10只孕鼠持续染毒直至自然分娩。出生后子鼠在哺乳期通过母乳染毒,断乳后则按照与母鼠相同的方式进行染毒,并在不同时间点进行外周血常规、外周血形态学、骨髓细胞形态学、骨髓细胞染色体组型和数目分析。血常规结果显示,低、高剂量BDE 209暴露对出生后不同发育阶段子鼠的白细胞计数没有影响,即白细胞、中性粒细胞、淋巴细胞及单核细胞的数量均无显著变化(P0.05);红细胞系统检查显示一定性别差异,即低剂量和高剂量BDE 209染毒的雄性小鼠在PND30出现红细胞(RBC)(P0.05)、血红蛋白(Hb)(P0.05或P0.01)及红细胞压积(P0.05或P0.01)的显著降低;而雌性小鼠只在PND 30出现红细胞压积的降低(P0.05);在PND 30,高剂量暴露组的雌性及雄性小鼠,低剂量暴露组的雌性小鼠均出现血小板计数的显著降低(P0.05或P0.01);而PND 60、PND 90的实验组血小板均未观察到显著改变(P0.05)。外周血形态学检查表明,低剂量组在PND 30、PND 60,及高剂量组在PND 90检测到典型异常结果多表现为白细胞数的增多。而低剂量组在PND 90检测到的典型异常结果多表现为异型深染淋巴细胞(P0.05)。骨髓形态学检测表明,低剂量组子代雄性及雌性小鼠在PND 60、PND 90骨髓涂片可检测到骨髓细胞的异常结果,表现为骨髓增生活跃,高剂量组雄性小鼠在PND 90观察到3例异常涂片,表现为骨髓增生异常(P0.05)。研究结果表明,BDE 209长期暴露可能导致出生子代外周血和骨髓的毒性,提示具有血液系统发育毒性。     

生物炭对玉米苗期生长、养分吸收及土壤化学性状的影响

采用田间盆栽试验,研究了生物炭（biochar）对玉米（Gramineae）苗期生长（60 d）及土壤化学性质的影响。结果表明,在玉米苗期的前33 d,生物炭（48 t.hm-2）对玉米株高的生长有显著抑制作用,但随着玉米的生长发育,生物炭的抑制作用逐渐消失。收获时（播种后60 d）,生物炭对玉米植株干质量,N、P养分的吸收量没有显著影响;生物炭（12、48 t.hm-2）能显著提高土壤全N、有机碳质量分数,但对土壤全P、有效P、pH值没有显著影响。土壤全N、有机碳质量分数与生物炭用量（0、2.4、12、48 t.hm-2）为显著正相关（n=12,p〈0.01）。