Modeling of secondary treated wastewater disinfection by UV irradiation: Effects of suspended solids content

This work aimed to study UV-resistant strains of Pseudomonas aeruginosa, to propose a formulation of the kinetics of secondary treated wastewater disinfection and to underline the influence of suspended solids on the inactivation kinetics of these strains. Some investigations were carried out for the validation of some simulation models, from the simplest, the kinetics model of Chick-Watson reduced to first order, to rather complex models such as multi-kinetic and Collins-Selleck models. Results revealed that the involved processes of UV irradiation were too complex to be approached by a simplified formulation, even in the case of specific strains of microorganisms and the use of nearly constant UV radiation intensity. In fact, the application of Chick-Watson model in its original form is not representative of the kinetics of UV disinfection. Modification, taking into account the speed change during the disinfection process, has not significantly improved results. On the other hand, the application of Collins-Selleck model demonstrates that it was necessary to exceed a least dose of critical radiation to start the process of inactivation. To better explain the process of inactivation, we have assumed that the action of disinfectant on the survival of lonely microorganisms is faster than its action on suspended solids protected or agglomerated to each others. We can assume in this case the existence of two inactivation kinetics during the processes (parallel and independent) of the first-order. For this reason, the application of a new kinetic model by introducing a third factor reflecting the influence of suspended solids in water on disinfection kinetics appeared to be determinant for modeling UV inactivation of P. aeruginosa in secondary treated wastewater.     

Improved preparation and identification of aristolochic acid-DNA adductsby solid-phase extraction with liquid chromatography-tandemmass spectrometry

Aristolochic acid (AA) is a known nephrotoxin and potential carcinogen, which can form covalent DNA adducts after metabolicactivation in vivo and in vitro. A simple method for preparation and characterization of aristolochic acid-DNA adducts was developed.Four AA-adducts were synthesized by a direct reaction of AAI/AAII with 2’-deoxynucleosides. The reaction mixture was firstcleaned-up and pre-concentrated using solid phase extraction (SPE), and further purified by a reversed-phase high performance liquidchromatography (HPLC). By the application of developed SPE procedure, matrices and byproducts in reaction mixture could be greatlyreduced and adducts of high purity (more than 94% as indicated by HPLC) were obtained. The purified AA-DNA adducts wereidentified and characterized with liquid-electrospray ionization-quadrupole-time of flight-mass spectrometry (LC-ESI-Q-TOF-MS/MS)and LC-Diode array detector-fluorescence (LC-DAD-FL) analysis. This work provides a robust tool for possible large-scale preparationof AA-DNA adduct standards, which can promote the further studies on carcinogenic and mutagenic mechanism of aristolochic acids.     

典型规模化养猪场废水中兽用抗生素污染特征与去除效率研究

采用固相萃取结合高效液相色谱/串联质谱方法,对苕溪流域某规模化养猪场排放的典型废水进行兽用抗生素污染检测.结果表明,废水中四环素、土霉素、金霉素和强力霉素等4种四环素类抗生素污染最为严重,最高单体污染浓度可达13.65×103ng·L-1.磺胺嘧啶、磺胺甲唑和磺胺二甲嘧啶等3种磺胺类物质也有一定的检出量,但以磺胺二甲嘧啶较为突出,最高检出量为675.4ng·L-1.氧氟沙星以及红霉素和罗红霉素等喹诺酮和大环内酯类抗生素除了原水有较低的检出量,其它废水均未检出.厌氧消化废水处理系统对废水中高浓度的抗生素具有明显的去除效果,但对低浓度的抗生素去除率较低.与欧盟水环境抗生素阈值(10ng·L-1)相比,排放水中的抗生素污染浓度对周边地表水环境的污染风险仍需要引起重视.通过饲料摄入途径估算养猪场排泄物抗生素含量,并与实测值比较,结果表明,饲料摄入并不是该养猪场兽用抗生素利用的主要方式,可能存在其它用药途径,需要在今后的畜禽养殖兽用抗生素的污染调查、风险估算和消减工艺研发中引起重视.     

超快速液相色谱-串联质谱法测定制药废水中阿维菌素的研究

建立了采用固相萃取-超快速液相色谱-串联质谱（SPE-RRLC-MS/MS）测定制药废水中阿维菌素残留的方法.水样经离心、沉淀蛋白质后,上清液采用HLB固相萃取柱富集和净化;以0.1%甲酸水溶液和50%～90%甲醇为流动相,采用AgilentPlusC18柱进行RRLC分离,在串联质谱ESI（＋）模式下采用多反应监测模...     

Heavy-metal contents in suspended solids of Meiliang Bay, Taihu Lake and its environmental significances

Surface water was taken from river mouth to the central area of Meiliang Bay, Taihu Lake, a large shallow eutrophic lake in China. Suspended solids were condensed by centrifugation 25L surface water samples from each selected site. Suspended solids and surface sediments were further freeze-dried and microwave digested before determining the metals by ICP-AES. Among the metals analyzed in suspended solids and sediments, contents of Cr, Cu, Mn, Ni, and Zn in suspended solids were significantly higher than those in sediments while contents of AI, Ba, Be, Ca, Co, Fe, K, Mg, Pb, and V in suspended solids were 10%-30% higher than those in sediments. Sr and Ti contents in suspended solids and sediments were very similar. Na content in suspended solids was lower than that in sediments. Heavy metals were significantly accumulated in suspended solids. From the river mouth to the center of Meiliang Bay, contents of Cr, Cu, Pb, and Zn in suspended solids showed a gradual decreasing trend indicating the river(Zhihugang River) still discharged large quantity of heavy metals to Meiliang Bay. The study suggests that the geochemical behaviors and ecological effects of heavy metals in suspended solids may serve as a good indicator for the pollution of lake.     

长江南京段水、悬浮物及沉积物中多氯有毒有机污染物

对长江南京段水、悬浮物及沉积物中多氯有毒有机污染物进行了分析测定,由色谱/质谱测得的结果表明,水和沉积物中多氯有机污染物的浓度较低,低于欧洲主要河流中的含量水平.悬浮物中这类污染物总含量较高,为56.45～62.35μg/kg,而水中总含量仅为14.61～15.83ng/L.由于长江中污染物被充分稀释与混匀,各采样点的水和悬浮物中该类污染物的浓度变化不大,两相间具有较好的相关性.但各采样点的沉积物中多氯有机污染物含量差异甚大,表明悬浮物的沉积极不均一.沉积物中主要污染物是六氯苯（HCB）和它的代谢产物五氯苯（PeCB）以及滴滴涕（DDT）的代谢产物,其他多氯有机污染物含量很低.     

混凝前处理对猪场沼液MAP回收时抗生素残留的影响

养猪废水磷酸铵镁（MgNH₄PO₄·6H₂O,MAP）回收时会有大量抗生素转移至回收MAP固体中,采用混凝前处理去除沼液中抗生素减少后续回收MAP中抗生素残留.首先对比聚合硫酸铁（PFS）、壳聚糖（CTS）、阳离子型聚丙烯酰胺（CPAM）和非离子型聚丙烯酰胺（PAM）四种典型无机和有机混凝剂对抗生素去除效果.实验结果显示CPAM去除抗生素效果最好,四环素类抗生素（TCs）去除率为22.8%-44.8%,喹诺酮类抗生素（FQs）去除率为32.2%~70.3%,回收MAP固体中抗生素含量为TCs 8.6mg/kg~19.6mg/kg,FQs 0.8~12.33mg/kg.在此基础上,考察了pH值和CPAM投加量对CPAM去除抗生素的影响.当pH7.5-8.0、CPAM投加量为17.5mg/L时,TCs去除42.5%~50.6%,FQs去除率42.9%~66.3%;与没有混凝处理的沼液MAP回收相比,产物中TCs含量下降43.2%~54.1%,FQs含量下降50.1%~69.5%.     

土壤中13种有机氯农药超声波提取方法研究

应用超声波提取江西红壤和南京黄棕壤中的 13种有机氯农药 (α 、β 、γ 和δ HCH ,2 ,4′ DDT ,2 ,4′ DDE ,4 ,4′ DDT ,4 ,4′ DDE ,4 ,4′ DDD ,α endosulfan ,dieldrin ,endrin ,HCB) ,固相萃取柱进行纯化 ,气相色谱进行定量分析 .对不同提取溶剂 (正己烷、二氯甲烷、正己烷和甲醇、正己烷和丙酮、正己烷和二氯甲烷 )、提取时间 (0 .5～ 2h)、提取次数 (1～ 5次 )与提取效率的关系进行了研究 .研究表明以正己烷 甲醇 (4∶1)作为混合提取溶剂 ,超声提取一次 ,提取 2h能取得较高的提取效率 .此技术节省溶剂且提取方法简单 .     

Simultaneous determination of ten taste and odor compounds in drinking water by solid-phase microextraction combined with gas chromatography-mass spectrometry

Taste and odor （T＆O） problems in drinking water frequently occur because of many compounds present in the water, of which trans-1,10-dimethyl-trans-9-decalol （geosrnin） and 2-methylisoborneol （MIB） are well-known. In this study, a fast and effective method was established for simultaneous determination of 10 T＆O compounds, including geosmin, MIB, 2,4,6-trichloroanisole （TCA）, 2-methylbenzofuran, 2-isopropyl-3-methoxypyrazine （IPMP）, 2-isobutyl-3-methoxypyrazine （IBMP）, cis-3-hexenyl acetate, trans,trans-2,4-heptadienal, trans, cis-2,6-nonadienal, and trans-2-decenal in water samples by headspace solid-phase microextraction （SPME） coupled with gas chromatography-mass spectrometry. An orthogonal array experimental design was used to optimize the effects of SPME fiber, extraction temperature, stirring rate, NaC1 content, extraction time, and desorption time. The limits of detection ranged from 0.1 to 73 ng/L were lower than or close to the odor threshold concentrations （OTCs）. All the 10 T＆O compounds were detected in the 14 water samples including surface water, treatment process water and tap water, taken from a waterworks in Lianyungang City, China. MIB and geosmin were detected in most samples at low concentration. Six T＆O compounds （IPMP, IBMP, trans,cis-2,6-nonadienal, 2-methylbenzofuran, trans-2-decenal, and TCA） were effectively decreased in water treatment process （sedimentation and filtration） that is different from cis-3-hexenyl acetate, MIB and geosmin. It is noted that the TCA concentrations at 15.9-122.3 ng/L and the trans,cis-2,6-nonadienal concentrations at 79.9-190.1 ng/L were over 10 times higher than their OTCs in tap water. The variation of the analytes in the all water samples, especially distribution system indicated that distribution system cannot be ignored as a T＆O compounds source.     

黄河耗氧性有机物污染特征及泥沙对其参数测定的影响

对黄河干流1980,1992～1999年耗氧性有机物污染监测数据进行了分析,并通过对高锰酸盐指数(CODMn)与泥沙含量监测数据间的相关分析和模拟实验研究,探讨了泥沙对CODMn测定的影响.结果表明:(1)由于泥沙中腐殖质的成分之一富里酸能溶解于酸,在水样加酸处理过程中将进入水相,且富里酸能被化学氧化剂所氧化,但在自然条件下很难发生生物氧化和消耗水体的溶解氧,因此,由于泥沙的影响,CODMn夸大了耗氧性有机物的污染;(2)黄河干流河水的生化需氧量(BOD5)从上游至下游存在增加的趋势;(3)1992年干流河水的BOD5显著大于1980年的BOD5,在1992～1999年间,河水BOD5的年均值存在上升的趋势,枯水期均值存在上升的趋势,而丰水期均值的增长趋势不明显,由此表明,耗氧性有机污染物的点源排放在增加,而面源排放的增长趋势不明显,甚至存在降低的趋势;(4)黄河干流的耗氧性有机污染物主要来自点源排放,BOD5的点源与面源负荷的多年均值之比为2 81.     

湘江衡阳段重金属在水体、悬浮颗粒物及表层沉积物中的分布特征研究

采用ICP-MS研究湘江衡阳段上覆水、悬浮颗粒物、表层沉积物及孔隙水中重金属的含量及分布特征.结果表明,湘江衡阳段主要的重金属污染元素是Cd,上覆水中Cd的平均含量为0.26μg·L-1,高于美国水质基准的持续基准浓度CCC(USEPA2009),已经对部分水生生物表现出潜在的毒性效应;悬浮颗粒物和表层沉积物中Cd的富集含量较高,分别为42.03μg·g-1和29.62μg·g-1,达到加拿大淡水沉积物保护准则最初影响水平TEL的70倍和50倍,其中,从沉积物中取得的孔隙水中Cd平均含量为3.8μg·L-1,该值是CCC的15倍甚至高于最大基准浓度(CMC),已经对部分水生生物表现出实际的急性毒性效应.湘江衡阳段重金属的空间分布特征表现为中下游污染较上游严重,在衡阳水口山地区等污染企业密集区,重金属含量较高,表明人类活动输入已经成为湘江重金属的重要来源.研究结果还表明,悬浮颗粒物及沉积物相作为水体重金属污染物的主要赋存介质,对重金属污染的迁移、沉积、转化及生物富集作用具有决定性的意义,其重要性不容忽视.     

养猪废水和污泥中11种兽用抗生素的同时分析技术及其在生物降解过程的应用

优化了固相萃取与高效液相色谱串联质谱联用的分析条件,使之适用于检测长三角地区养猪废水和污泥中常见的11种兽用抗生素(包括4种四环素类、2种磺胺类、3种喹诺酮类和2种大环内酯类).该分析方法对养猪废水的平均加标回收率(n=3)为73.0%~105.2%,相对标准偏差为3.1%~10.2%;对污泥的平均加标回收率(n=3)为57.4%~104.6%,相对标准偏差为1.9%~10.9%.研究膜生物反应器中抗生素的浓度变化,发现废水中抗生素以四环素类和磺胺类为主,而污泥中以四环素类为主.反应器对废水中四环素类抗生素的去除率为85.2%,其中最主要的去除途径是生物分解(51.9%),其次是污泥吸附(33.2%);而磺胺类抗生素去除率为95.8%,几乎全部是依靠生物分解,污泥吸附很少.摇瓶实验结果显示,污泥中积累的抗生素未对活性污泥的有机物降解活性和硝化活性产生明显影响.     

Rapid detection of multiple class pharmaceuticals in both municipal wastewater and sludge with ultra high performance liquid chromatography tandem mass spectrometry

This work described the development, optimization and validation of an analytical method for rapid detection of multiple-class pharmaceuticals in both municipal wastewater and sludge samples based on ultrasonic solvent extraction, solid-phase extraction, and ultra high performance liquid chromatography-tandem mass spectrometry quantification. The results indicated that the developed method could effectively extract all the target pharmaceuticals （25） in a single process and analyze them within 24 min. The recoveries of the target pharmaceuticals were in the range of 69%-131% for wastewater and 54%-130% for sludge at different spiked concentration levels. The method quantification limits in wastewater and sludge ranged from 0.02 to 0.73 ng/L and from 0.02 to 1.00μg/kg, respectively. Subsequently, this method was validated and applied for residual pharma- ceutical analysis in a wastewater treatment plant located in Beijing, China. All the target pharmaceuticals were detected in the influent samples with concentrations varying from 0.09 ng/L （tiamulin） to 15.24 μg/L （caffeine）; meanwhile, up to 23 pharmaceuticals were detected in sludge samples with concentrations varying from 60 ng/kg （sulfamethizole） to 8.55 mg/kg （ofloxacin）. The developed method demonstrated its selectivity, sensitivity, and reliability for detecting multiple-class pharmaceuticals in complex matrices such as municipal wastewater and sludge.     

固相萃取-高效液相色谱法同时测定水体中的10种磺胺类抗生素

建立了一种采用固相萃取-高效液相色谱法同时测定水体中10种磺胺类抗生素的方法.样品经自制PEP固相萃取小柱富集净化、乙腈-二氯甲烷(2∶1,体积比)洗脱后,用高效液相色谱-紫外检测器测定.检测波长λ=268 nm,柱温33℃,流动相为乙腈-0.4%乙酸/水(体积比),采用梯度洗脱程序,实现了10种待测组分的基线分离,线性范围为10～2 000μg.L-1.去离子水和实际水样的加标回收率范围分别为73.4%～95.6%和70.2%～92.5%(磺胺除外,分别为8.5%和8.0%).整个分析方法的检出限为1.42～7.25 ng.L-1.应用此方法对上海市黄浦江部分河段江水、崇明岛地表水及地下水的测定表明在这几种不同水体环境中,不同频率地检出了磺胺类药物,浓度范围为13.3～241.5 ng.L-1,从而证明该方法具有快速简便、灵敏高效等优点,可满足实际工作的需要.     

Analysis of trace dicyandiamide in stream water using solid phase extraction and liquid chromatography UV spectrometry

An improved method for trace level quantification of dicyandiamide in stream water has been developed. This method includes sample pretreatment using solid phase extraction. The extraction procedure (including loading, washing, and eluting) used a flow rate of 1.0 mL/min, and dicyandiamide was eluted with 20 mL of a methanol/acetonitrile mixture (V/V = 2:3), followed by pre-concentration using nitrogen evaporation and analysis with high performance liquid chromatography–ultraviolet spectroscopy (HPLC–UV). Sample extraction was carried out using a Waters Sep-Pak AC-2 Cartridge (with activated carbon). Separation was achieved on a ZIC^®-Hydrophilic Interaction Liquid Chromatography (ZIC-HILIC) (50 mm × 2.1 mm, 3.5 μm) chromatography column and quantification was accomplished based on UV absorbance. A reliable linear relationship was obtained for the calibration curve using standard solutions (R² > 0.999). Recoveries for dicyandiamide ranged from 84.6% to 96.8%, and the relative standard deviations (RSDs, n = 3) were below 6.1% with a detection limit of 5.0 ng/mL for stream water samples.     

A new method of simultaneous determination of atmospheric amines in gaseous and particulate phases by gas chromatography-mass spectrometry

As more attention is being paid to the characteristics of atmospheric amines, there is also an increasing demand for reliable detection technologies. Herein, a method was developed for simultaneous detection of atmospheric amines in both gaseous and particulate phases using gas chromatography-mass spectrometry (GC-MS). The amine samples were collected with and without phosphoric acid filters, followed by derivatization with benzenesulfonyl chloride under alkaline condition prior to GC-MS analysis. Furthermore, the method was optimized and validated for determining 14 standard amines. The detection limits ranged from 0.0408-0.421 µg/mL (for gaseous samples) and 0.163-1.69 µg/mL (for particulate samples), respectively. The obtained recoveries ranged from 68.8%-180% and the relative standard deviation was less than 30%, indicating high precision and good reliability of the method. Seven amines were simultaneously detected in gaseous and particulate samples in an industrial park using the developed method successfully. Methylamine, dimethylamine and diethylamine together accounted for 76.7% and 75.6% of particulate and gaseous samples, respectively. By comparing the measured and predicted values of gas-particle partition fractions, it was found that absorption process of aqueous phase played a more important role in the gas-partition of amines than physical adsorption. Moreover, the reaction between unprotonated amines and acid (aq.) in water phase likely promoted water absorption. Higher measured partition fraction of dibutylamine was likely due to the reaction with gaseous HCl. The developed method would help provide a deeper understanding of gas-particle partitioning as well as atmospheric evolution of amines.     

Simultaneous preconcentration of cadmium and lead in water samples with silica gel and determination by flame atomic absorption spectrometry

A new method that utilizes pretreated silica gel as an adsorbent has been developed for simultaneous preconcentration of trace Cd(Ⅱ) and Pb(Ⅱ) prior to the measurement by flame atomic absorption spectrometry. The effects of pH, the shaking time, the elution condition and the coexisting ions on the separation/preconcentration conditions of analytes were investigated. Under optimized conditions, the static adsorption capacity of Cd(Ⅱ) and Pb(Ⅱ) were 45.5 and 27.1mg/g, the relative standard deviations were 3.2% and 1.7% (for n = 11), and the limits of detection obtained were 4.25 and 0.60 ng/mL, respectively. The method was validated by analyzing the certified reference materials GBW 07304a (stream sediment) and successfully applied to the analysis of various treated wastewater samples with satisfactory results.     

Simultaneous preconcentration of cadmium and lead in water samples with silica gel and determination by flame atomic absorption spectrometry

A new method that utilizes pretreated silica gel as an adsorbent has been developed for simultaneous preconcentration of trace Cd(II) and Pb(II) prior to the measurement by flame atomic absorption spectrometry. The effects of pH, the shaking time, the elution condition and the coexisting ions on the separation/preconcentration conditions of analytes were investigated. Under optimized conditions, the static adsorption capacity of Cd(II) and Pb(II) were 45.5 and 27.1mg/g, the relative standard deviations were 3.2% and 1.7% (for n = 11), and the limits of detection obtained were 4.25 and 0.60 ng/mL, respectively. The method was validated by analyzing the certified reference materials GBW 07304a (stream sediment) and successfully applied to the analysis of various treated wastewater samples with satisfactory results.     

Simultaneous determination of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in Guanting Reservoir using gas chromatography-mass spectrometry with selected ion monitoring

The wide occurrence of estrogenic compounds 4-tert-octylphenol, 4-nonylphenol, bisphenol A in surface water of Guanting Reservoir was successfully determined. The target compounds in water samples were preconcentrated by liquid-liquid extraction with dichloromethane, derivatized by trifluoroacetic anhydride, and quantified by gas chromatography-mass spectrometry(GC-MS) with selected ion monitoring(SlM). In the selected seven sampling sites(S1-S7), the concentration of NP in sample S7 was significantly higher than the other in reservoir. The status of pollution in S3 and S7 were much more serious. The concentrations of OP, NP and BPA were in the range of 44.5-48.8, 221.6-349.6 and 30.2-82.7 ng/L, respectively. The pollutants were mainly inputted from the upper river and released from sediments in Guanting Reservoir.     

广州大气总悬浮颗粒物中可提取有机物的分布及源析

采用N,O-双(三甲基硅烷基)三氟乙酰胺(BSTFA)衍生化预处理和GC/MS分析技术,于2002~2003年对广州市大气气溶胶中的有机化合物进行了定量检测.结果表明,在广州市TSP样品中有机物的种类共分为9大类:烷烃、多环芳烃、酯类、正烷醇、酚类、酸类、甾类、二萜类、糖类化合物.在总定性有机化合物中,酸类(24.65%~40.38%)化合物的百分含量最高,其次为糖类(15.57%~36.18%).全年样品中最丰富的脂肪酸为正十六酸、正十八酸,高碳数脂肪酸(>C20)含量最高的酸是正二十四酸.广州市二元羧酸的浓度以冬季最高,气象条件(风向、雨水和逆温)是影响二元羧酸浓度变化的主要因素.利用分子标志物可以讨论源解析和源贡献,化石燃料对有机质的贡献率最高(平均值为64.28%),其次为植物蜡脂质 (平均值为10.99%)和生物质燃烧(平均值为8.58%).