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.     

Determination of 4-tert-octylphenol in surface water samples of Jinan in China by solid phase extraction coupled with GC-MS

Octylphenols, considered as xenoestrogens, mainly exist as 4-tert-octylphenol (OP) in aquatic environments. The high stability and accumulation of OP in aquatic systems have caused endocrine disruption. The OP in surface water in Jinan, China was analyzed by gas chromatography-mass spectrometry (GC-MS) coupled with solid phase extraction (SPE). Water samples were extracted by SPE on a cartridge system containing C-18 as sorbent. To increase sensitivity and selectivity, OP was derivatized to 4-tert-octyl-phenoxy silane. With the use of phenanthrene-d10 as internal standard, the detection limit based on signal-to-noise ratio (S/N = 3) was 0.06 ng/mL. The average recovery was from 84.67% to 109.7%. The precision of the method given as the relative standard deviations (RSD) was within the range 6.24%-12.96%. In the target water samples, the concentrations of OP were as follows: 15.88-71.24 ng/L for Jinxiuchuan Reservoir, 3.850-26.68 ng/L for the city moat, 6.930-41.56 ng/L for Daming Lake, 66.03-474.2 ng/L for Xiaoqing River, 14.66-17.72 ng/L for the Yellow River, and 10.60-26.43 ng/L for Queshan Reservoir. The Xiaoqing River was seriously polluted due to the discharge of wastewater from Jinan. Jinxiuchuan Reservoir had a higher concentration of OP compared with the Yellow River and Queshan Reservoir, which is ascribed to the surrounding human activities. These data are reported for the first time, providing strong support for the control of OP pollution in Jinan.     

An online monitoring system for atmospheric nitrous acid (HONO) based on stripping coil and ion chromatography

A new instrument for measuring atmospheric nitrous acid(HONO) was developed,consisting of a double-wall glass stripping coil sampler coupled with ion chromatography(SC-IC).SC-IC is featured by small size(50 × 35 × 25 cm) and modular construction,including three independent parts:the sampling unit,the transfer and supporting unit,and the detection unit.High collection efficiency(> 99%) was achieved with 25 μmol/L Na2CO3 as absorption solution even in the presence of highly acidic compounds.This instrument has a detection limit of 8 pptv at 15 min time resolution,with a measurement uncertainty of 7%.Potential interferences from NOx,NO2+SO2,NO2+VOCs,HONO+O3,HNO3,peroxyacetyl nitrite(PAN) and particle nitrite were quantified in laboratory studies and were found to be insignificant under typical atmospheric conditions.Within the framework of the 3C-STAR project,inter-comparison between the SC-IC and LOPAP(long path liquid absorption photometer) was conducted at a rural site in the Pearl River Delta.Good agreement was achieved between the two instruments over three weeks.Both instruments determined a clear diurnal profile of ambient HONO concentrations from 0.1 to 2.5 ppbv.However,deviations were found for low ambient HONO concentrations(i.e.< 0.3 ppbv),which cannot be explained by previous investigated interference species.To accurately determine the HONO budget under illuminated conditions,more intercomparison of HONO measurement techniques is still needed in future studies,especially at low HONO concentrations.     

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。     

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。     

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%。     

餐厨垃圾生物好氧堆肥的影响因素研究

使用自制的餐厨垃圾处理设备对餐厨垃圾进行生物好氧堆肥,采用L(93)4正交试验法研究了环境温度、含水率和接种量对餐厨垃圾生物好氧堆肥的影响,确定了考察因子的主次顺序以及最优工艺条件,并针对3个影响因素进行了单因素验证试验。实验结果表明:当环境温度为40℃、含水率为40%,接种量为菌种(含辅料)∶餐厨垃圾=4∶3时,含菌量增长速度快,菌种活性强,降解持续的时间长;各因素对含菌量影响的大小的顺序依次为环境温度、含水率和接种量。产出物经检验满足有机肥NY 525-2011标准。