Nontarget analysis of polar contaminants in freshwater sediments influenced by pharmaceutical industry using ultra-high-pressure liquid chromatography-quadrupole time-of-flight mass spectrometry

A comprehensive analytical procedure for a reliable identification of nontarget polar contaminants in aquatic sediments was developed, based on the application of ultra-high-pressure liquid chromatography (UHPLC) coupled to hybrid quadrupole time-of-flight mass spectrometry (QTOFMS). The procedure was applied for the analysis of freshwater sediment that was highly impacted by wastewater discharges from the pharmaceutical industry. A number of different contaminants were successfully identified owing to the high mass accuracy of the QTOFMS system, used in combination with high chromatographic resolution of UHPLC. The major compounds, identified in investigated sediment, included a series of polypropylene glycols (n = 3-16), alkylbenzene sulfonate and benzalkonium surfactants as well as a number of various pharmaceuticals (chlorthalidone, warfarin, terbinafine, torsemide, zolpidem and macrolide antibiotics). The particular advantage of the applied technique is its capability to detect less known pharmaceutical intermediates and/or transformation products, which have not been previously reported in freshwater sediments.     

高氯离子味精尾母液废水厌氧处理研究

味精尾母液废水COD浓度极高同时含有大最氯离子.采用UASB反应器对味精尾母液废水进行处理,其中接种污泥来自啤酒厂UASB反应器.实验表明:当氯离子浓度在4 500 mg/L以下时,对厌氧微生物没有明礁的抑制作用;5 000 mg/L的氯离子浓度可以看作一个抑制限值,但经过驯化后,仍可获得较好的COD去除效果;当氯离子浓度达到8 000mg/L左右时,COD平均去除率在80%以上.     

离子液体[BMIm][PF6]增强抗性质粒RP4介导的接合转移基因mRNA的表达水平

环境中广泛存在的抗生素和抗生素抗性基因会导致很严重的人类健康风险。在我们前期研究中发现,离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIm][PF6])作为环境选择性压力可以促进抗生素抗性基因的水平转移。本研究以E.coli DH5α(RP4)和同属的E.coli HB101,以及E.coli DH5α(RP4)和跨属的Salmonella enterica之间的纯菌接合转移体系为考察对象,从mRNA基因表达调控水平角度阐明离子液体[BMIm][PF6](0.001~2.5 g·L-1)影响质粒RP4接合转移的机理。结果表明,离子液体[BMIm][PF6]通过抑制基因kor A,kor B和trb A的mRNA表达水平来提高接合和跨膜转运基因trb Bp和trf Ap的表达;增强水平转移基因tra F的mRNA表达水平,并通过增强负调控基因kil A和kil B的mRNA表达水平抑制质粒的垂直传递过程;通过抑制基因trb K的mRNA表达水平降低接合转移体系的排斥效果,从而促进质粒RP4的接合转移。该结果有助于为抗生素抗性基因在环境中水平转移扩散的机理研究提供理论依据。     

EGSB反应器处理焦化废水的颗粒污泥反应动力学研究

为了对处理实际焦化废水微氧EGSB反应器污染物去除机理进行研究,建立了处理实际焦化废水微氧EGSB反应器内污染物质降解动力学模型,考察EGSB反应器启动和稳定运行阶段不同运行条件时COD去除效果,并分析动力学参数的变化。研究确定了处理实际焦化废水(进水COD 2 000 mg/L左右)微氧EGSB反应器在启动和稳定运行阶段所适用的基质降解模型,动力学常数vmax、KI、KS、vmax/KS、KS/KI分别为7.34×10-3h-1、197.76 mg/L、19.53 mg/L、3.7×10-4L/(h·mg)、0.10和2.4×10-2h-1、66.64 mg/L、44.07 mg/L、5.4×10-4L/(h·mg)、0.66;微氧EGSB反应器内颗粒污泥能够逐渐适应并高效降解焦化废水中污染物质,焦化废水中毒性污染物质对颗粒污泥的抑制程度是由KS/KI决定的,KS/KI越大,抑制程度越弱,处理实际焦化废水EGSB反应器启动和稳定运行阶段的KS/KI分别为0.04~0.1和0.66~0.74;液体上升流速Vup的提高能够明显提高最大比基质降解速率vmax,降低半饱和常数KS和抑制常数KI,最终强化微氧EGSB反应器的运行效果,稳定运行阶段COD去除率高达92.7%。     

改良型湿法制备活性白土清洁生产及末端治理实验研究

传统湿法制备活性白土工艺中存在水耗、酸耗大等清洁水平较低的问题,本研究提出了在生产工艺流程中循环使用硫酸酸性废液、并从循环3次的硫酸废液中回收铝盐制备无铁硫酸铝的一种改良型湿法制备活性白土工艺,对末端治理采用电石渣替代石灰作为中和剂进行了探索性实验研究。实验结果表明,改良型湿法制备活性白土工艺对活性白土产品的理化性质无明显影响,产品质量符合行业标准,且酸的利用率从20%提高到约90%,水耗减少量为原工艺的1/3,无铁硫酸铝主要参数符合相关产品技术标准(HG/T2225-2001)。用电石渣作为中和剂处理酸性废液能够实现出水水质稳定达标,处理成本从255万元降低至210万元。本研究的实施使得活性白土的生产工艺清洁生产水平有较大提高。     

离子液体负载型分子筛的制备及对染料的吸附

为了有效地处理活性黑染料废水,对离子液体负载型分子筛去除水中的活性黑染料进行了研究。首先制备了离子液体负载型吸附材料,分别考察了分散剂种类、离子液体加入量、浸渍时间3种因素对离子液体负载率的影响,确定负载工艺条件为:二氯甲烷作为分散剂、[OMim]BF4离子液体与分子筛质量比1∶2,浸渍时间12 h。其次研究了负载型吸附材料对染料废水的处理效果,考察了吸附材料添加量、溶液pH值、吸附时间对模拟废水活性黑染料去除率的影响,确定吸附工艺条件为:[OMim]BF4离子液体为最佳离子液体、吸附材料添加量0.40 g、pH=6、吸附时间12 h。在此最佳工艺条件下,染料去除率达98.23%。     

Simultaneous determination of seven anticoagulant rodenticides in agricultural products by gel permeation chromatography and liquid chromatography–tandem mass spectrometry

A sensitive and reliable method for the simultaneous determination of hydroxycoumarin-type (brodifacoum, bromadiolone, coumatetralyl, and warfarin) and indandione-type (chlorophacinone, diphacinone, and pindone) rodenticides in agricultural products by gel permeation chromatography (GPC) and liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed. The procedure involved extraction of the rodenticides from samples with acetone, followed by liquid–liquid partitioning with hexane/ethyl acetate (1:1, v/v) and 10% sodium chloride aqueous solution, then cleanup using GPC, and finally, analysis using LC–MS/MS. High recoveries from the GPC column were obtained for all rodenticides tested using a mobile phase of acetone/cyclohexane/triethylamine (400:1600:1, v/v/v). An ODS column, which contains low levels of metal impurities, gave satisfactory peak shapes for both hydroxycoumarin- and indandione-type rodenticides in the LC–MS/MS separation. The average recoveries of rodenticides from eight agricultural foods (apple, eggplant, cabbage, orange, potato, tomato, brown rice, and soybean) fortified at 0.0005–0.001 mg/kg ranged from 76 to 116%, except for bromadiolone in orange (53%) and diphacinone in soybean (54%), and the relative standard deviations ranged from 1 to 16%. The proposed method effectively removed interfering components, such as pigments and lipids, and showed high selectivity. In addition, the matrix effects were negligible for most of the rodenticide/food combinations. The results suggest that the proposed method is reliable and suitable for determining hydroxycoumarin- and indandione-type rodenticides in agricultural products.     

典型液氯泄漏危害的ALOHA软件估算

以瞬时泄漏和连续泄漏两种典型液氯泄漏事故为例,分别运用ALOHA软件和公式计算两种方法对液氯泄漏危害进行量化评估。估算结果表明:ALOHA软件对泄漏毒物的危害区域和敏感点毒物浓度的预测结果均具有良好的精度;软件模拟与公式计算的结果对于液氯瞬时泄漏的相对误差仅为7%,对于连续泄漏的相对误差为8%,二者均在可接受范围内。ALOHA软件计算过程简单、表达形象直观,在泄漏事故应急中具实用性。     

硅胶固载季鏻离子液体对CO_2的吸附

采用嫁接法制备了硅胶固载季鏻双三氟甲烷磺酰亚胺盐离子液体,并将其用于对CO2的吸附,考察了吸附剂的吸附等温线及循环使用性,并运用均相表面扩散模型(HSDM)研究了吸附动力学。采用FTIR和TG等技术对试样进行了表征。表征结果显示:离子液体已成功固载到硅胶上;煅烧活化硅胶对季鏻离子液体(C-Si O2-P4T)的固载量为5.39%(w);固载试样基本保持了硅胶的孔道特征。实验结果表明:C-Si O2-P4T具有较高的CO2平衡吸附量,且能显著提高CO2/N2吸附选择性,循环使用6次仍保持良好的吸附能力;HSDM可较好地拟合CO2在C-Si O2-P4T内的扩散行为,40℃下的扩散系数在10-7 m2/s数量级,与硅胶同级,优于纯季鏻离子液体。     

大气粉尘中常见多环芳烃类化合物的提取及含量测定

采用便携式PM2.5采样器和玻璃纤维滤膜对大气粉尘进行采样,以加压液体萃取、超声波辅助提取和微波辅助提取3种方法对多环芳烃类化合物进行提取,以超高效液相色谱和质谱联用方法进行测定。共检测出16种多环芳烃类化合物,分别为:萘、苊、苊烯、芴、菲、蒽、荧蒽、芘、苯并[a]蒽、■、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、二苯并[a,h]蒽、茚并[1,2,3-c,d]芘和苯并[g,h,i]苝。3种提取方法均可有效提取大气粉尘中的多环芳烃类化合物,加压液体萃取法的提取效率最高、超声波辅助提取法次之、微波辅助提取法最低。超高效液相色谱和质谱连用方法可有效地分析大气粉尘中的多环芳烃类化合物,线性方程的相关系数不低于0.998 3,测定值的相对标准偏差不超过0.80%,检出限不高于0.27 ng/g。