Synthesis of hybrid carbon nanotubes using Brassica juncea L. application to photodegradation of bisphenol A

Hyperaccumulators contain tubular cellulose and heavy metals, which can be used as the sources of carbon and metals to synthesize nanomaterials. In this paper, carbon nanotubes (CNTs), Cu_0.05Zn_0.95O nanoparticles, and CNTs/Cu_0.05Zn_0.95O nanocomposites were synthesized using Brassica juncea L. plants, and the ultraviolet (UV)-light-driven photocatalytic degradations of bisphenol A (BPA) using them as photocatalysts were studied. It was found that the outer diameter of CNTs was around 50 nm and there were a few defects in the crystal lattice. The synthesized Cu_0.05Zn_0.95O nanocomposites had a diameter of around 40 nm. Cu_0.05Zn_0.95O nanocomposites have grown on the surface of the CNTs and the outer diameter of them was around 100 nm. The synthesized hybrid carbon nanotubes using B. juncea could enhance the efficiency of photocatalytic degradation on BPA. The complete equilibration time of adsorption/desorption of BPA onto the surface of CNTs, Cu_0.05Zn_0.95O nanoparticles, and CNTs/Cu_0.05Zn_0.95O nanocomposites was within 30, 20, and 30 min, and approximately 14.9, 8.7, and 17.4 % BPA was adsorbed by them, respectively. The combination of UV light irradiation (90 min) with CNTs, Cu_0.05Zn_0.95O nanoparticles, and CNTs/Cu_0.05Zn_0.95O nanocomposites could lead to 48.3, 75.7, and 92.6 % decomposition yields of BPA, respectively. These findings constitute a new insight for synthesizing nanocatalyst by reusing hyperaccumulators.     

Occurrence and distribution of heavy metals and tetracyclines in agricultural soils after typical land use change in east China

Land use in east China tends to change from paddy rice to vegetables or other high-value cash crops, resulting in high input rates of organic manures and increased risk of contamination with both heavy metals (HMs) and antibiotics. This investigation was conducted to determine the accumulation, distribution and risks of HMs and tetracyclines (TCs) in surface soils and profiles receiving different amounts of farmyard manure. Soil samples collected from suburbs of Hangzhou city, Zhejiang province were introduced to represent three types of land use change from paddy rice to asparagus production, vineyards and field mustard cultivation, and divided into two portions, one of which was air-dried and sieved through 2-, 0.3- and 0.149-mm nylon mesh for determination of pH and heavy metals. The other portion was frozen at ?20 °C, freeze-dried and sieved through a 0.3-mm nylon mesh for tetracyline determination. HM and TC concentrations in surface soils of 14-year-old mustard fields were the highest with total Cu, Zn, Cd and ∑TCs of 50.5, 196, 1.03 mg?kg^?1 and 22.9 μg?kg^?1, respectively, on average. The total Cu sequence was field mustard?>?vineyards?>?asparagus when duration of land use change was considered; oxytetracycline (OTC) and doxycycline were dominant in soils used for asparagus production; OTC was dominant in vineyards and chlortetracycline (CTC) was dominant in mustard soils. There were positive pollution relationships among Cu, Zn and ∑TCs, especially between Cu and Zn or Cu and ∑TCs. Repeated and excessive application of manures from intensive farming systems may produce combined contamination with HMs and TCs which were found in the top 20 cm of the arable soil profiles and also extended to 20–40 cm depth. Increasing manure application rate and cultivation time led to continuing increases in residue concentrations and movement down the soil profile.     

Bioaccessibility of polychlorinated biphenyls in workplace dust and its implication for risk assessment

Human exposure to bioaccessible PCBs via indoor dust is limited around the world. In the present study, the workplace dust sample from commercial office, hospital, secondary school, shopping mall, electronic factory and manufacturing plant were collected from Hong Kong for PCBs analyses. Total PCBs concentrations ranged from 46.8 to 249 ng g⁻¹, with a median of 107 ng g⁻¹. Manufacturing plant showed the highest concentration among all of sampling sites. PCB 77 was found as the dominant congeners. The bioaccessibility of PCBs in small intestinal juice ranging from 8.3% to 26.0% was significantly higher than that in gastric condition, ranging from 4.8% to 12.4%. In addition, significant negative correlations (p < 0.05) were observed between K_OW and bioaccessibility for all workplace dust samples. Risk assessment indicated that the averaged daily dose of dioxin-like PCBs via non-dietary intake of workplace dust, considering the bioaccessibility of PCBs, were much lower than the TDI of dioxins (2.3 pg WHO-TEQ kg bw⁻¹ d⁻¹) established by Joint FAO/WHO Expert Committee on Food Additives.     

碘掺杂Ti02可见光光催化性能研究

在低于100℃温度条件下,采用溶胶一凝胶法以钛酸正丁酯为钛源,碘酸钾为碘源,制备了I掺杂纳米TiO2催化剂（I-TiO2）,运用x-射线衍射（XRD）、透射电镜（TEM）及x-射线光电子能谱（XPS）等对催化剂进行表征,结果表明,TiO2及I-TiO2催化剂均为锐钛矿,I吸附并包裹在TiO2表面或以间隙进入的形式存在,并未进入TiO2晶格。通过在可见光照射下（A〉420nm）以罗丹明B（RhodamineB,RhB）的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能,结果表明,掺杂比为n1：n^ti=0．05：l,焙烧温度为400℃,降解介质条件pH=7时,l-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱（IR）,总有机碳（TOC）跟踪测定,比较了TiO2掺杂前后降解RhB和对氯苯酚（4-CP）的光催化特性差异;同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种,表明在可见光下,I-TiO2光催化体系中产生·OH高活性氧化物种从而氧化降解目标化合物。     

膜电解法在线再生酸性蚀刻液及回收铜新技术

采用极化曲线法研究了酸性蚀刻液阴、阳极电化学行为,并构建了离子膜电解反应体系,考察了在线再生酸性蚀刻液及回收铜的效果。结果表明,阳极氧化过程发生浓差极化,存在极限电流密度,Cu＋含量越高,极限电流密度越大;阴极还原分4步反应进行,存在极限电流密度;强化溶液传质可有效提高阴、阳极极限电流密度,有利于避免电解过程中析出氯气和氢气;在线实验表明,通过监控阳极液ORP,可避免析出氯气;分步降低电流电解有利于避免析出氢气,形成致密的金属铜块;在电流为9～24A范围内分4步电解23．5h可再生酸性蚀刻液23．5L,同时电沉积回收510g铜,纯度高达99．98％。阴极电流效率达到95．2％,吨铜电耗3251kWh。电解过程中无氯气和氢气析出,无废液排放,表明膜电解法在线再生酸性蚀刻液具有良好的应用前景。     

湿法净化黑烟中添加剂对炭黑沉降性能的影响

湿法净化黑烟中炭黑颗粒物的关键在于降低吸收液的表面张力并以高性能絮凝剂使其从溶液中絮凝、沉降以利于分离。选用十六烷基三甲基溴化胺(CTAB)为主要表面活性剂,使之与十二烷基苯磺酸钠(SDBS)和月桂醇聚氧乙烯(9)醚(AEO-9)进行复配实验,研究了复配液的表面张力,再向最低表面张力的复配表面活性剂溶液中投加絮凝剂聚合氯化铝(PAC)和聚丙烯酰胺(PAM),探讨絮凝剂的添加对黑烟颗粒沉降和絮凝的影响.实验结果表明:同时添加表面活性剂CTAB,SDBS和PAC,并使之浓度分别为0.5 mmol/L,0.4 mmol/L和200 mg/L时,炭黑颗粒的沉降效果最好,沉降率高达94%,且絮凝体较大,沉降时间仅为2 min。     

羟基铝及复合改性蒙脱石对As(V)的去除性能

采用无机羟基铝及阳离子表面活性剂十六烷基三甲基溴化铵对天然蒙脱石进行无机及复合改性。在吸附过程中研究了反应时间、投加量和pH等变量对吸附性能的影响,同时进行吸附动力学及吸附等温线研究,吸附规律符合Langmuir等温方程式。采用X射线衍射、X射线荧光、傅里叶红外光谱等表征手段对未改性及改性蒙脱石进行性能表征。研究结果表明,羟基铝及复合改性蒙脱石对As(V)具有良好的吸附性能,在pH为4～10,初始砷浓度为2 mg/L,改性蒙脱石对As(V)的去除率接近99%。吸附机理主要为羟基铝表面络合吸附和静电吸附。     

天然膨润土还原吸附Cr（Ⅵ）

以天然膨润土为吸附剂,还原吸附处理含Cr（Ⅵ）模拟废水。实验结果表明：以（NH₄）₂FeSO₄为还原剂吸附效果最佳;在还原剂加入量为理论值的0.8倍、膨润土加入量为6 g/L、吸附时间为30 min、吸附温度为30 ℃、初始Cr（Ⅵ）质量浓度为1 mg/L的条件下,Cr（Ⅵ）去除率可达99.6%,处理后模拟废水中总铬质量浓度低至0.003 mg/L。天然膨润土对Cr（Ⅵ）的还原吸附符合准二级动力学模型及Freundlich等温吸附模型。     

Accumulation and quantitative estimates of airborne lead for a wild plant (Aster subulatus)

Foliar uptake of airborne lead is one of the pathways for Pb accumulation in plant organs. However, the approximate contributions of airborne Pb to plant organs are still unclear. In the present study, aerosols (nine-stage size-segregated aerosols and total suspended particulates), a wild plant species (Aster subulatus) and the corresponding soils were collected and Pb contents and isotopic ratios in these samples were analyzed. Average concentration of Pb was 96.5 ± 63.5 ng m⁻³ in total suspended particulates (TSP) and 20.4 ± 5.5 ng m⁻³ in the fine fractions of size-segregated aerosols (SSA) (<2.1 μm), higher than that in the coarser fractions (>2.1 μm) (6.38 ± 3.71 ng m⁻³). Enrichment factors show that aerosols and soils suffered from anthropogenic inputs and the fine fractions of the size-segregated aerosols enriched more Pb than the coarse fractions. The order of Pb contents in A. subulatus was roots > leaves > stems. The linear relationship of Pb isotope ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) among soil, plant and aerosol samples were found. Based on the simple binary Pb isotopic model using the mean ²⁰⁶Pb/²⁰⁷Pb ratios in TSP and in SSA, the approximate contributions of airborne Pb into plant leaves were 72.2% and 65.1%, respectively, suggesting that airborne Pb is the most important source for the Pb accumulation in leaves. So the combination of Pb isotope tracing and the simple binary Pb isotope model can assess the contribution of airborne Pb into plant leaves and may be of interest for risk assessment of the exposure to airborne Pb contamination.     

Development of enzyme-linked immunosorbent assays for plasma vitellogenin in Chinese rare minnow (Gobiocypris rarus)

Due to the wide occurrence of endocrine disrupting chemicals in the environment, it is much of importance to develop high throughput screening method for the analysis of this kind of pollutants. Using anion-exchange membrane chromatography, vitellogenin (VTG) from the plasma of 17β-estradiol (E₂) treated Chinese rare minnow was rapidly purified within 15 min. Both polyclonal antibody (PcAb) and monoclonal antibody (McAb) against rare minnow VTG (R-VTG) were prepared in rabbit and Balb/c mice, respectively. The competitive enzyme-linked immunosorbent assays (ELISA) based on either PcAb or McAb were developed to identify and quantify R-VTG in the plasma, and these two methods showed similar characteristics. The detection limits of both assays were lower than 3 ng mL⁻¹ with the working ranges covering three magnitudes. The recovery efficiencies of PcAb and McAb based ELISA were 104.2% and 102.6%, respectively; and the intra-assay and inter-assay of these two assays were 6.2% and 9.2%, 8.6% and 12.8%, respectively. These results indicated that the described competitive ELISA methods were sensitive and valuable tools for quantifying vitellogenin in rare minnow plasma. These methods were then applied to measure R-VTG concentrations in plasma of male fish exposed to a series of E₂ concentrations. When E₂ levels were less than 10 ng L⁻¹, R-VTG levels in plasma were comparable to that in solvent control, while R-VTG levels significantly increased 15-folds and 350-folds, respectively when E₂ exposure concentrations were controlled at 10 and 50 ng L⁻¹. The high sensitivity of Chinese rare minnow to E₂ was demonstrated, making it a valuable model species to study environmental estrogens.