Supercritical water oxidation of polyvinyl alcohol and desizing wastewater：Influence of NaOH on the organic decomposition

Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. However, it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment. Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol. It appears that the OH ion participated in the C-C bond cleavage of polyvinyl alcohol molecules, the CO2-capture reaction and the neutralization of intermediate organic acids, promoting the overall reactions moving in the forward direction. Acetaldehyde was a typical intermediate product during reaction. For supercritical water oxidation of desizing wastewater, a high destruction rate (98.25%) based on total organic carbon was achieved. In addition, cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment, but salt precipitation and blockage issues arising during the process need to be taken into account seriously.     

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.     

Photocatalytic degradation of carbofuran in TiO2 aqueous solution：Kinetics using design of experiments and mechanism by HPLC/MS/MS

The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.     

亚微米颗粒在Sierpinski海绵模型中热泳沉积研究

亚微米颗粒由于其特殊的粒径尺度,具有很多不同于与传统细颗粒的物理和化学性质,同时极易吸入人体,对人体造成很大危害。谢尔宾斯基海绵模型作为一种理想化的结构模型,具有内比表面积大、多通道等特点。通过建立可工程应用的谢尔宾斯基海绵模型通道,并结合热泳沉积相关数学模型开展计算,可以发现:随着谢尔宾斯基海绵阶数的上升,内部通道的增加是引起亚微米颗粒热泳沉积率上升的主要因素;在海绵通道中运动的亚微米颗粒较之其他粒径的颗粒,更容易受到热泳沉积的影响;同时温差对其热泳沉积影响较为剧烈,呈现线性变化。建立具有工程特征的谢尔宾斯基海绵模型通道,可为研究亚微米颗粒沉积及脱除开辟一条新途径。     

不同类型湖泊沉积物中氮释放规律研究

通过对武汉市东湖子湖郭郑湖、庙湖以及南湖这3个不同类型的湖泊进行释氮模拟实验,结果表明:(1)在厌氧条件下,不同污染程度的湖泊中沉积物释氮作用均比较明显。为了抑制沉积物向上覆水释氮,控制湖泊富营养化,保持湖泊较高的溶解氧水平是必要的。(2)在厌氧条件下,高温对不同类型湖泊总氮和氨氮的释放均能起到促进作用。(3)沉积物与上覆水间污染物的浓度梯度越大,总氮和氨氮的释放速率与释氮量也越大,此时温度的影响不明显。(4)通过比较3类湖泊沉积物上覆水中总氮和氨氮两者的释放浓度可知,氨氮的释放贡献十分显著,因此控制氨氮的释放量对于控制湖泊氮释放量具有显著效果。     

水中氨氮测定不确定度的评定

采用蒸馏-中和滴定法测定水中氨氮,建立数学模型,找出影响不确定度的来源并进行各分量不确定度的评价,如实反映测量的置信度和准确度.     

取代苯类化合物对斑马鱼急性毒性的QSAR研究

该文基于定量-构效关系(QSAR)原理,研究了26种取代苯类化合物与斑马鱼的48 h急性毒性(-lgLC50)之间的内在定量关系。利用AM1量子化学计算方法,首先计算了8种典型量子化学参数与斑马鱼48 h-lgLC50的相关性;然后通过逐步多元线性回归(MLR)方法建立了取代苯类化合物对斑马鱼48 h-lgLC50的QSAR模型,并对所建模型分别进行了内部验证和外部验证,所得复相关系数R2=0.942;最后利用QSAR模型,分析了取代苯类化合物量子化学参数对斑马鱼48 h-lgLC50的影响。结果表明:正辛醇—水分配系数(LogP)与-lgLC50的相关性最大,负电性[-(L+H)/2]与-lgLC50负相关。所得QSAR模型具有较高的稳定性及预测能力,可以用来预测取代苯类化合物对斑马鱼的急性毒性。     

基于LandsatTM数据的济宁市水体识别方法研究

文章基于济宁市2009年LANDSAT TM影像,根据影像各波段间的相关性和地物在各影像上的灰度差异,分别采用单波段阈值法、多波段谱间关系法、改进的水体指数法(MNDWI)及HIS空间水体提取模型法对济宁市水体信息进行识别提取。在此基础上,结合归一化指数法和HIS空间水体提取模型,提出了一种综合性的水体信息提取方法,并对各方法提取结果进行了精度评价。结果表明,已有方法对济宁市水体识别存在一定的缺陷,而综合法集成了归一化指数法和HIS空间水体模型的优点,很好地弥补了已有方法的不足,对济宁市水体信息进行了较好的提取,尤其是细小水体,同时也很好地消除了建筑物、阴影、水生植被等的影响,提高了济宁市水体信息识别的精度,为更好地定量评价济宁市地表水体时空演变规律等提供帮助。     

胶东半岛农村地区地下水重金属健康风险评价——以山东省莱阳市为例

重金属健康风险评价对居民身体健康具有重要意义。使用电感耦合等离子体发射光谱仪(ICP-OES)测定了莱阳市农村的31个地下水体中重金属Cu、Fe、Zn、Mn、Cd和Cr的含量水平,阐明了该地区重金属的空间分布特征、来源及其迁移规律,并运用美国环保局推荐的健康风险评价模型对其引起的健康风险进行了评价。结果表明,该地区地下水中Cr未检出,Cu、Fe、Zn、Mn和Cd的浓度范围分别是0～59、23～905、29～50 700、3～2 999、0～1μg/L。根据我国饮用水质量标准,所有样点中Cu和Cd的浓度未超标,Zn、Mn和Fe的超标率分别为22.58%、16.13%和6.45%,个别样点超标倍数甚高。健康风险评价结果表明,Cu、Fe、Zn、Mn通过饮用水途径产生的健康风险平均值分别为3.49×10-10、1.91×10-10、100.50×10-10、37.40×10-10a-1,均远低于ICRP(5×10-5a-1)和USEPA(1×10-4a-1)的最大可接受风险水平。但是Zn和Mn对人体健康危害的平均个人年风险明显高于其他地区,因此,该研究区非致癌物Zn和Mn的污染来源及其环境行为应该引起重视。该研究为该区域水质污染状况研究及治理监管工作提供理论依据,为其他地区重金属的监测和质量控制提供参考。     

磁性纳米Fe_3O_4对毒死蜱的增效和催化降解研究

应用溶剂热法制备了磁性纳米Fe3O4(NMFO),并用聚乙二醇-6000对其进行改性,使纳米Fe3O4表面由亲水性转变为亲脂性,从而实现与亲脂性毒死蜱的复合。纳米Fe3O4的加入使毒死蜱的生物活性明显提高。室内毒力试验结果表明:含0.2%纳米Fe3O4的Fe3O4/毒死蜱制剂的毒力在室内和紫外光照下分别是同浓度纯毒死蜱的3.84倍和4.17倍;其降解率也显著提高,纳米Fe3O4/毒死蜱制剂在太阳光照下放置10 d,其降解率可达93.2%,相同条件下纯毒死蜱的降解率是10.14%,而将添加或未添加纳米Fe3O4的毒死蜱于暗处放置相同的时间,其降解率分别为1.21%和0.23%。