薄膜扩散梯度技术在重金属生物有效态监测中的应用

重金属生物有效性是评估重金属元素迁移性、生物可利用性和生态影响的关键参数。薄膜扩散梯度技术(DGT)是一种原位被动采样技术,因其具有原位富集性、形态选择性,可提供被监测物质在监测时间段内的平均浓度等优点,可作为生物对重金属摄取的模拟替代物对环境介质中重金属的生物可利用度进行预测,已被广泛应用于环境介质中重金属生物有效性的测定。研究主要介绍了DGT技术的原理、组成和特点,评述了其近年来在水体、土壤、沉积物中重金属生物有效态应用方面的新进展,提出了DGT技术未来要提高抗生物污染能力及寻找可与DGT技术联用的相关技术的观点。     

Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters

• Selective molecularly imprinted polymer (MIP) binding gel was prepared. • MIP-DGT showed excellent uptake performance for antibiotics. • In situ measurement of antibiotics in wastewaters via MIP-DGT was developed. • The MIP-DGT method was robust, reliable, and highly sensitive. Urban wastewater is one of main sources for the introduction of antibiotics into the environment. Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems. In this study, we report a novel diffusive gradient in thin films (DGT) method based on molecularly imprinted polymers (MIPs) for in situ measurement of two typical antibiotics, fluoroquinolones (FQs) and sulfonamides (SAs) in urban wastewater. MIPs show specific adsorption toward their templates and their structural analogs, resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment. The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH (4.0–9.0), ionic strength (1–750 mmol/L), and dissolved organic matter (DOM, 0–20 mg/L). MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials, where three SA (sulfamethoxazole, sulfapyridine, and trimethoprim) and one FQ (ofloxacin) antibiotics were detected, with concentrations ranging from 25.50 to 117.58 ng/L, which are consistent with the results measured by grab sampling. The total removal efficiency of the antibiotics was 80.1% by the treatment plant. This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.     

金属掺杂纳米TiO2薄膜的制备和抗菌性能研究

采用sol—gel法在载玻片表面制备了Ce,Cu,i．a,Ag掺杂的锐铁矿相TiO2薄膜,并通过SEM,XRD．FT—IR及UVVIS进行了表征,比较了薄膜的抗菌性能．UV—VIS研究表明,金属掺杂纳米TiO2薄膜在近紫外区吸光度有明显提高。抗菌实验表明掺Ag的TiO2薄膜抗菌效果最佳。     

利用DGT高分辨率研究沉积物孔隙水中重金属的浓度和释放通量

2006年5月采集了大辽河河段3个柱状沉积物,测定了沉积物的理化性质和重金属元素的含量,并利用常规离心方法和DGT方法测定了柱状沉积物孔隙水中重金属元素的含量.研究发现沉积物中Cd、Co、Cr和Cu元素含量高低的顺序依次是Cr>Cu>Co>Cd.用DGT方法测定的孔隙水中Cd、Co、Cr和Cu的浓度比用离心方法测定的浓度要低.DGT测定的孔隙水中Cd、Co、Cr和Cu的浓度c_DGT与离心方法测定的孔隙水浓度c的平均比值R分别为0.389、0.328、0.863和0.403,这说明沉积物中这几种金属从固相到液相的再补给速率大小遵循如下规律：Cr>Cu>Cd>Co.沉积物中Cd、Co、Cr和Cu元素的释放通量分别为1.12×１０^{-7～3.28×10-7　nmol/(cm2·s)、2.48×１０-7～10.40×10-7　nmol/(cm2·s)、8.80×１０-6～12.65×10-6 nmol/(cm2·s)和6.14×１０-6～13.93×10-6　nmol/(cm2·s).相关分析结果表明,Cd和Cu元素的迁移转化主要受有机质影响;而Cr元素的迁移转化除了受有机质影响外,还受铁锰氧化物影响比较显著;而Co元素可能受氧化还原电位影响较大.}     

TiO2薄膜光催化体系中羟基自由基的水杨酸分子探针法测定

以水杨酸为分子探针物,以分光光度法测定了纳米TiO2薄膜光催化体系中产生的羟基自由基(·OH).结果表明,水杨酸的自然氧化程度较低,可以作为分子探针测定·OH的产生;实验中最佳的光照时间为60min;水杨酸浓度对·OH的测定影响较大,其最佳值为50 mg·L-1;pH值对·OH的测定影响较大,最佳值为6;最佳实验条件下,分析得到·OH的稳态浓度为1.68×10-14 mol·L-1.     

Fabrication and photoelectrocatalytic properties of nanocrystalline monoclinic BiVO4 thin-film electrode

Monoclinic bismuth vanadate(BiVO4) thin film was fabricated on indium-tin oxide glass from an amorphous heteronuclear complex via dip-coating.After annealation at 400,500,and 600°C,the thin films were characterized by X-ray diffraction,field emission scanning electron microscopy,X-ray photoelectron spectroscopy,and UV-Vis spectrophotometry.The BiVO4 particles on the ITO glass surface had a monoclinic structure.The UV-Visible diffuse reflection spectra showed the BiVO4 thin film had photoabsorption propertie...     

Mobility and sulfidization of heavy metals in sediments of a shallow eutrophic lake,Lake Taihu,China

The technique of DGT (diffusive gradients in thin films) using three diffusive gel thicknesses was applied to estimate the mobility and bioavailability of heavy metals in sediments and porewater of Lake Taihu, China. The DGT results showed significantly positive correlations between Co, Pb, Cd and Mn, and Ni and Fe concentrations in porewater. Cu and Zn showed a significantly negative correlation with Mn, due to Cu combination with carbonates and Zn derived from agricultural pollution, respectively. The rank order of average concentrations of Co, Ni and Cd at each station was DGT_1.92 > DGT_0.78 > DGT_0.39, suggesting stronger resupply from sediments to porewater when using thicker diffusive gels. Comparing centrifugation and DGT measurements, Co, Ni and Cd are highly labile; Mn and Fe are moderately labile; and Cu, Zn and Pb are slightly labile. The variations of AVS concentrations in sediment cores indicate that metal sulfides in deeper layers are easily diffused into surface sediments.     

Effect of fatty acids and oils on photodegradation of azadirachtin‐A

Abstract

Azadirachtin‐A on exposure to UV‐light (254 nm) as a thin film on glass surface gave a isomerised (Z)‐2‐ methylbut‐2‐enoate product. Half‐life of azadirachtin‐A as thin film under UV light was found to be 48 min. Azadirachtin ‐A was irradiated along with saturated and unsaturated fatty acids, and fatty oils under ultra‐violet light as thin film. Saturated fatty acid increased the rate of photodegradation of azadirachtin‐A, whereas unsaturated fatty acids such as oleic, linoleic and elaidic acid reduced the rate of degradation. Castor, linseed and olive oil accelerated the rate of degradation, whereas neem oil showed no or little change in the rate of degradation of azadirachtin‐A. None of these fatty acids and fatty oils were effective in controlling the rate of degradation of azadirachtin‐A under UV‐light as thin film.     

水体中常见无机阳离子对TiO2薄膜光催化还原Cr（Ⅵ）的影响

选择了6种水体中常见的阳离子（Na^＋、Mg^2＋、Ca^2＋、Al^3＋、Cu^2＋、Ni^2＋）,分别考查了其对TiO2薄膜光催化还原Cr（Ⅵ）的影响;从光吸收、无机离子本身的性质对光生电子的捕获及传递等讨论了上述离子影响TiO2薄膜光催化还原Cr（Ⅵ）的反应速率的原因。结果表明：由于其不能捕获光生电子,Na^＋、Mg^2＋、Ca^2＋本身对TiO2薄膜光催化还原Cr（Ⅵ）的反应速率影响不大;Al^3＋吸引电子能力较强,成为光生电子和Cr（Ⅵ）之间的桥梁,促进了Cr（Ⅵ）的还原;浓度为1 mmmol/L时,Cu^2＋显著地促进了Cr（Ⅵ）的光催化还原,其主要原因是Cu^2＋捕获光生电子的能力很强,起到了催化剂的作用,而浓度大于10 mmol/L时,Cu^2＋形成单质Cu以及对紫外光的吸收都使促进作用降低;Ni^2＋未充满的d轨道具有获得并传递光生电子的能力,也促进了Cr（Ⅵ）的还原;在浓度同为1mmol/L时,对Cr（Ⅵ）光催化还原的促进作用依次为：Cu^2＋〉Al^3＋〉Ni^2＋〉Na^＋、Ca^2＋、Mg^2＋。     

Al3+离子掺杂对负载TiO2薄膜光催化活性的影响

以钛酸丁酯和Al2(SO4)3·18H2O为原料,采用溶胶凝胶法在钛片、玻璃、釉面瓷砖、陶瓷、不锈钢和铝片六种载体上制备了Al3+掺杂TiO2薄膜,讨论了不同Al3+掺杂浓度下,不同载体表面上制备的TiO2薄膜对甲基橙脱色率的影响。试验结果表明Al3+对TiO2薄膜的掺杂效果与载体的类型密切相关,并且不同载体其Al3+掺杂的最佳浓度也不同。Al3+掺杂后,TiO2薄膜光催化活性提高最大的是玻璃,其次是釉面瓷砖、铝片、钛片、陶瓷,最差的是负载不锈钢。