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.     

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＋。     

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.     

Modeling urban films using a dynamic multimedia fugacity model

A thin film coats impervious urban surfaces that can act as a source or sink of organic pollutants to the greater environment. We review recent developments in the understanding of film and film-associated pollutant behavior and incorporate them into an unsteady-state version of the fugacity based Multimedia Urban Model (MUM), focusing on detailed considerations of surface film dynamics. The model is used to explore the conditions under which these atmospherically-derived films act as a temporary source of chemicals to the air and/or storm water. Assuming film growth of 2.1 nm d⁻¹ (Wu et al., 2008a), PCB congeners 28 and 180 reach air-film equilibrium within hours and days, respectively. The model results suggest that the film acts as a temporary sink of chemicals from air during dry and cool weather, as a source to air in warmer weather, and as a source to storm water and soil during rain events. Using the downtown area of the City of Toronto Canada, as a case study, the model estimates that nearly 1 g d⁻¹ of ∑₅PCBs are transferred from air to film to storm water.     

Responses of Physical, Chemical, and Biological Indicators of Water Quality to a Gradient of Agricultural Land Use in the Yakima River Basin, Washington

The condition of 25 stream sites in the Yakima River Basin, Washington, were assessed by the U.S. Geological Survey's National Water-Quality Assessment Program. Multimetric condition indices were developed and used to rank sites on the basis of physical, chemical, and biological characteristics. These indices showed that sites in the Cascades and Eastern Cascades ecoregions were largely unimpaired. In contrast, all but two sites in the Columbia Basin ecoregion were impaired, some severely. Agriculture (nutrients and pesticides) was the primary factor associated with impairment and all impaired sites were characterized by multiple indicators of impairment. All indices of biological condition (fish, invertebrates, and algae) declined as agricultural intensity increased. The response exhibited by invertebrates and algae suggested a threshold response with conditions declining precipitously at relatively low levels of agricultural intensity and little response at moderate to high levels of agricultural intensity. This pattern of response suggests that the success of mitigation will vary depending upon where on the response curve the mitigation is undertaken. Because the form of the community condition response is critical to effective water-quality management, the National Water-Quality Assessment Program is conducting studies to examine the response of biota to gradients of land-use intensity and the relevance of these responses to water-quality management. These land-use gradient pilot studies will be conducted in several urban areas starting in 1999.     

Polymer Barrier Films

Many polymers such as polyolefins (polyethylene, polypropylene), poly(vinyl chloride), aliphatic polyamides, poly(ethylene terephthalate), polycarbonate, and others are used as protective barrier films against the mass transport of small molecules of gases, vapors, and liquids (known as diffusates, permeants) in different applications. The barrier properties depend on the polymer characteristics such as solubility, diffusion, permeability, and others, the nature of the fluid, temperature, and other factors. Mainly polymer barrier film application in packaging, construction, and agriculture are discussed.     

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.     

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.     

巢湖沉积物有效磷的原位高分辨分析研究

将两种原位被动采样技术——高分辨平衡式间隙水(HR-Peeper)与氧化锆薄膜梯度扩散技术(Zr-oxide DGT)相结合,分别对巢湖西半湖7个点位溶解态反应性磷(cPW)和有效磷(cDGT)进行原位测定分析,cPW和cDGT在大部分沉积物剖面的分布相似或局部相似,说明不同深度沉积物固相有效磷组分对间隙水SRP的缓冲能力较接近.利用界面扩散通量和cDGT/cPW比值(R)表征沉积物磷的活性,从巢湖湖心向南淝河入湖口方向,界面以下6 mm的cPW、cDGT和扩散通量的变化基本一致,均呈递增趋势,表明沉积物磷的污染水平在增加;R值变化较小,说明沉积物界面处的缓冲能力差异不明显.     

Copper complexation by tannic acid in aqueous solution

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon (OC)/l was investigated in a nine-step titration experiment (Cu/OC molar ratio = 0.0030–0.0567). We differentiated between soluble and insoluble Cu species by 0.45 μm filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations (‘free’ Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (>0.45 μm) was the dominant Cu species for Cu/OC = 0.0030–0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 × 10⁻⁶– 5.58 × 10⁻⁶ cm² s⁻¹).