新型磁性聚谷氨酸吸附剂对水中Pb2+的吸附去除

德岛大学安澤幹人首次利用γ-PGA在Fe3O4磁性纳米颗粒上进行涂层,制得了γ-聚谷氨酸-Fe3O4磁性纳米颗粒（PG-M）.本实验利用透射电镜以及扫描电镜对PG-M吸附剂的形貌进行了分析,发现PG-M与未涂层的Fe3 O4具有相似的形状以及大小,均为不规则的层状结构,且晶粒直径在120～320 nm之间;实验中针对性地对水溶液中Pb2＋进行了吸附探讨.在振荡实验中,通过主要参数的变化（pH值、吸附时间、竞争离子浓度、腐殖酸浓度）,得到如下结果：吸附最佳pH值为7.0;吸附量随着吸附时间的延长而增长,吸附平衡时间为45 min;Na＋对PG-M去除Pb2＋没有很强的干扰性,而Ca2＋则显示出一定的干扰作用;腐殖酸对吸附效果的影响是复杂的,表现为先增强吸附效果,随后降低吸附效果;最佳条件时Pb2＋的最大吸附量为93.3 mg/g.PG-M对Pb2＋的吸附均能较好地符合Freundlich和Langmuir等温吸附模型,其中Langmuir方程能更好地描述PG-M的吸附特征,说明PG-M在水溶液中对金属离子的吸附为单分子层吸附.PG-M吸附符合准二级动力学模型（r2〉0.99）.不同浓度的HCl和HNO3溶液的再生实验发现,0.1 mol/L的HCl溶液作为吸附再生液,可取得较好的再生效果.表明PG-M是可再生的,具有较好的经济性和可持续性.     

不同磷水平下丛枝菌根真菌对纳米氧化锌生物效应的影响

纳米ZnO颗粒是应用最为广泛金属型纳米颗粒(nanoparticles,NPs)之一,对作物和土壤微生物的影响值得关注.丛枝菌根(arbuscular mycorrhizal,AM)是自然界中普遍存在的植物-真菌共生体,对各种环境胁迫具有一定的抵御能力,但菌根效应受土壤和植物磷含量的影响.分别设置0、20、50、100 mg·kg~(-1)这4个磷水平,在接种或不接种AM真菌Funneliformis mosseae、添加或不添加纳米ZnO(500 mg·kg~(-1))条件下在温室中利用玉米进行土壤盆栽试验.结果表明,纳米ZnO没有显著影响玉米生长,但不利于菌根侵染和磷素吸收,并引起锌在植物体内的积累.纳米ZnO和高磷降低玉米菌根侵染,但AM真菌在所有磷水平下均显著促进植物生长.施磷和接菌均可使土壤p H升高、降低纳米ZnO源锌的生物有效性,从而降低锌向玉米地上部分的转运和积累,体现出一定保护作用.接菌在多数情况下显示出积极的菌根效应,尤其在低磷、添加纳米ZnO条件下更为显著.结果首次表明,AM真菌、磷肥均有助于减轻纳米ZnO引起的土壤污染及其所产生的生态和健康风险.     

长期暴露下纳米二氧化钛对典型淡水藻体砷累积与生物转化的影响

以铜绿微囊藻(Microcystis aeruginosa)和斜生栅藻(Scenedesmus obliquus)为研究对象,通过室内培养实验,研究了长期暴露下纳米二氧化钛(nano-TiO_2)对五价砷[As(Ⅴ)]在典型淡水藻体中累积与生物转化的影响.结果表明不同藻类对无机砷的吸收和转化能力差异很大.长期暴露下斜生栅藻累积的砷(As,以DW计,下同)高达(819.66±11.25)μg·g-1,比铜绿微囊藻累积的As[(355.95±8.31)μg·g-1]高2倍多.Nano-TiO_2可增加藻体对As的吸收累积,降低了培养基中As的含量.同时,nano-TiO_2可增加藻体对As(Ⅴ)的生化转化;其中,铜绿微囊藻中有机砷以二甲基砷(DMA)为主,而斜生栅藻中有机砷以一甲基砷(MMA)为主.另外,长期暴露下nano-TiO_2处理的铜绿微囊藻和斜生栅藻向培养基释放的甲基砷小于对照组,表明长期暴露中的nano-TiO_2不能促进藻体内甲基砷的释放.研究结果可促进nano-TiO_2与As相互作用时生态风险的理解.     

天然水体中多壁纳米碳管对纳米氧化锌颗粒团聚与沉降行为的影响

研究了淡水湖泊水体中氧化多壁纳米碳管(Oxidized-multiwalled carbon nanotubes,o-MWCNTs)对纳米氧化锌(ZnO nanoparticles,nZnO)颗粒团聚与沉降行为的影响,探讨了天然胶体及o-MWCNTs的浓度对nZnO颗粒团聚粒径、团聚速率及沉降行为的作用.结果表明,nZnO在天然水体中会发生明显沉降,相比去除天然胶体的天然水而言,天然胶体的存在显著减少了nZnO的沉降.这主要归因于nZnO-天然胶体颗粒间的作用能垒高于nZnO-nZnO颗粒间的作用能垒,使得天然胶体的存在降低了nZnO-nZnO之间的颗粒碰撞效率,从而促进nZnO悬浮.o-MWCNTs对nZnO在天然水体中沉降行为的影响与天然胶体密切相关.相比于nZnO的单独沉降,在不过膜天然水中(含天然胶体),低浓度o-MWCNTs的存在增加了颗粒间的团聚速率,从而促进nZnO的沉降,而高浓度o-MWCNTs降低了颗粒间的团聚速率和团聚体粒径,从而降低了nZnO的沉降.而在过膜天然水中(不含天然胶体),o-MWCNTs的存在显著降低了颗粒间的团聚粒径和团聚速率,从而降低了nZnO的沉降,且o-MWCNTs的浓度越高,对nZnO悬浮稳定性的促进作用越明显.     

Environmental assessment of mercury dispersion, transformation and bioavailability in the Lake Victoria Goldfields, Tanzania

Environmental dispersion and transformation of mercury discharged from gold mining operations has been investigated in field and laboratory studies in order to provide better understanding of the degree of mercury (Hg) pollution and bioavailability in the Lake Victoria goldfields (LVGF) ecosystems. This paper reviews results already published elsewhere and presents additional data on Hg dynamics in the LVGF. Studies conducted at the Mugusu and Rwamagaza artisanal mines indicated different degrees of Hg contamination and dispersion in environmental matrices. Mercury concentration in contaminated river sediments near the Mugusu mine varied from 6.0 to 0.5 mg/kg on a dry weight basis. The highest Hg contamination levels (165-232 mg/kg) were associated with mine tailings at the Rwamagaza mine. Mercury concentrations in fish representing different dietary habits on the southwestern shore of Lake Victoria at the Nungwe Bay were very low (2-35 microg/kg) and thought to represent background levels. These and other results suggested that the use of Hg in gold extraction in the LVGF has not caused high Hg levels in lake fish. The study of Hg in lichens showed Parmelia lichen to be an effective bioindicator for atmospheric Hg contamination due to Hg emissions from gold-amalgam firing and purification operations. The Hg levels in the lichens around the Mugusu mine ranged from 3.1 to 0.1 microg/g; the highest levels were recorded in the lichens sampled close to gold-amalgam processing sites. The regional background level in the Parmelia lichen was 0.05-0.10 microg/g, with a mean level of 0.07 microg/g. Studies of Hg transformation in the mine tailings revealed unexpectedly high methylmercury (MeHg) levels in the tailings (629-710 ng/g), which indicated that oxidation and methylation of metallic Hg in the tailings occurred at significant levels under tropical conditions. Re-equilibration of the tailings with freshwater (FW) indicated the MeHg was firmly bound in the tailings and therefore very little MeHg was released to the water column (0.2-1.5 ng/L). The methylation of Hg in tropical loamy clay soil contaminated with HgCl(2) (5 mg Hg/kg) yielded MeHg concentrations of 11 and 14 ng/g when inundated with seawater and FW, respectively, for 4 weeks. Little MeHg was transferred from the soil to the equilibrated water (< or = 0.4 ng/L). Atmospheric exposure of the soil pre-inundated with FW resulted in net degradation of MeHg during the 1st week of exposure, followed by net production and accumulation of MeHg in the soil (up to 15.5 ng/g) during atmospheric desiccation. Mercury uptake by fish from the Hg(0)-contaminated aquatic sediment-tailings system in the aquarium experiment was found to be low, suggesting the low availability of MeHg for bioaccumulation in the system. These and other results provide useful insights into Hg transformation, mobility and bioavailability in tropical aquatic systems affected by Hg pollution from gold mining operations.     

4种典型纳米材料对小鼠胚胎成纤维细胞毒性的初步研究

为探讨不同种类纳米材料对原代培养小鼠胚胎成纤维细胞(Mouse embryo fibroblasts,MEF)的毒性效应及作用机制,选择4种典型的纳米材料(纳米碳、单壁碳纳米管、纳米氧化锌、纳米二氧化硅)制备颗粒悬液,设立5个剂量组(5、10、20、50、100μg·mL-1)对BALB/c小鼠MEF细胞进行24、48、72h染毒培养,利用细胞形态学观察和噻唑蓝实验(MTT比色法)检测上述4种纳米材料对MEF细胞活性的影响,同时,测定染毒24h后细胞培养液上清中乳酸脱氢酶(LDH)活性以探讨纳米颗粒对细胞膜完整性的影响.结果显示:1)4种纳米材料均能明显影响MEF细胞的生长形态.染毒24h后,MEF细胞发生不同程度的回缩变形,细胞间隙增大,排列稀疏,胞内颗粒物增多,细胞透明度下降.2)纳米碳、纳米氧化锌、纳米二氧化硅对MEF细胞增殖的抑制作用和对细胞膜完整性的损伤作用均随染毒剂量的升高而增强,具有明显的剂量-效应关系,其半数致死浓度(24h-IC50)分别为21.85、21.94、461.10μg·mL-1;碳纳米管组的剂量-效应之间不呈对数线性关系,未能得出其24h-IC50.3)在不同染毒剂量水平上,4种纳米材料的毒性对比差异显著:低剂量水平上纳米碳与碳纳米管的毒性强于纳米氧化锌和纳米二氧化硅,随着剂量的升高纳米氧化锌的细胞毒性升高最为显著.结果提示,纳米材料能够对MEF细胞造成毒性损伤,破坏细胞膜的完整性可能只是作用途径之一;纳米材料的毒性可能受粒径、形状、化学组成等许多因素的影响.     

In situ formation of bimetallic FeNi nanoparticles on sand through green technology: Application for tetracycline removal

• In situ preparation of FeNi nanoparticles on the sand via green synthesis approach. • Removal of tetracycline using GS-FeNi in batch and column study. • Both reductive degradation and sorption played crucial role the process. • Reusability of GS-FeNi showed about 77.39±4.3% removal on 4th cycle. • TC by-products after interaction showed less toxic as compared with TC. In this study, FeNi nanoparticles were green synthesized using Punica granatum (pomegranate) peel extract, and these nanoparticles were also formed in situ over quartz sand (GS-FeNi) for removal of tetracycline (TC). Under the optimized operating conditions, (GS-FeNi concentration: 1.5% w/v; concentration of TC: 20 mg/L; interaction period: 180 min), 99±0.2% TC removal was achieved in the batch reactor. The removal capacity was 181±1 mg/g. A detailed characterization of the sorbent and the solution before and after the interaction revealed that the removal mechanism(s) involved both the sorption and degradation of TC. The reusability of reactant was assessed for four cycles of operation, and 77±4% of TC removal was obtained in the cycle. To judge the environmental sustainability of the process, residual toxicity assay of the interacted TC solution was performed with indicator bacteria (Bacillus and Pseudomonas) and algae (Chlorella sp.), which confirmed a substantial decrease in the toxicity. The continuous column studies were undertaken in the packed bed reactors using GS-FeNi. Employing the optimized conditions, quite high removal efficiency (978±5 mg/g) was obtained in the columns. The application of GS-FeNi for antibiotic removal was further evaluated in lake water, tap water, and ground water spiked with TC, and the removal capacity achieved was found to be 781±5, 712±5, and 687±3 mg/g, respectively. This work can pave the way for treatment of antibiotics and other pollutants in the reactors using novel green composites prepared from fruit wastes.     

Biogenic palladium prepared by activated sludge microbes for the hexavalent chromium catalytic reduction: Impact of relative biomass

• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable. Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.     

Ecotoxicity of nanoparticles of CuO and ZnO in natural water

The acute toxicity of CuO and ZnO nanoparticles in artificial freshwater (AFW) and in natural waters to crustaceans Daphnia magna and Thamnocephalus platyurus and protozoan Tetrahymena thermophila was compared. The L(E)C₅₀ values of nanoCuO for both crustaceans in natural water ranged from 90 to 224 mg Cu/l and were about 10-fold lower than L(E)C₅₀ values of bulk CuO. In all test media, the L(E)C₅₀ values for both bulk and nanoZnO (1.1-16 mg Zn/l) were considerably lower than those of nanoCuO. The natural waters remarkably (up to 140-fold) decreased the toxicity of nanoCuO (but not that of nanoZnO) to crustaceans depending mainly on the concentration of dissolved organic carbon (DOC). The toxicity of both nanoCuO and nanoZnO was mostly due to the solubilised ions as determined by specific metal-sensing bacteria.     

Immobilization of non-point phosphorus using stabilized magnetite nanoparticles with enhanced transportability and reactivity in soils

Laboratory batch and column experiments were conducted to investigate the immobilization of phosphorus (P) in soils using synthetic magnetite nanoparticles stabilized with sodium carboxymethyl cellulose (CMC-NP). Although CMC-stabilized magnetite particles were at the nanoscale, phosphorus removal by the nanoparticles was less than that of microparticles (MP) without the stabilizer due to the reduced P reactivity caused by the coating. The P reactivity of CMC-NP was effectively recovered when cellulase was added to degrade the coating. For subsurface non-point P pollution control for a water pond, it is possible to inject CMC-NP to form an enclosed protection wall in the surrounding soils. Non-stabilized “nanomagnetite” could not pass through the soil column under gravity because it quickly agglomerated into microparticles. The immobilized P was 30% in the control soil column, 33% when treated by non-stabilized MP, 45% when treated by CMC-NP, and 73% when treated by both CMC-NP and cellulase.