SPMD培训课程

2018/1/26,1,被动式生物模拟技术及其应用,王子健 许宜平 中国科学院生态环境研究中心2005年3月,2018/1/26,2,主要内容,主动、被动和生物模拟采样（概念）半渗透膜采样器（SPMDs）的设计与应用新技术推广：醋酸纤维素-中性类脂复合型膜,2018/1/26,3,有机污染物的样品制备,有机污染物分析中的样品制备方法,2018/1/26,4,主动和被动采样对不同极性物质富集效果的区别,2018/1/26,5,液液萃取（LLE）XAD树脂吸附固相萃取 （SPE）,传统的主动式样品制备技术,2018/1/26,6,Solid-phase Microextraction (SPME)Liquid-phase Microextraction (LPME)Semipermeable Membrane Device (SPMD),被动式样品制备技术,被动采样技术技术应用于小体积水样时的效果等同于主动采样！,2018/1/26,7,sediment,Water,有机污染物慢性毒性特点是长期富积亲脂性物质,2018/1/26,8,生物模拟和常规采样技术的比较,常规采样 生物模拟采样富集方式 主动 被动富集原理 浓缩倍数 脂/水分配系数富集组分 800 Da），填充在半渗透膜内不易渗漏,内充有机溶剂：,组成半渗透膜采样器的材料,2018/1/26,20,Water,Polyethylene,Triolein,K0,KWP,KPW,KPT,KTP,KWP(cm3/d),KPT(cm3/s),PCB-52 PE 4200 1.9PCB-52 SPMD 4200 1.9Phenanthrene 4800 12.0,Gale, 1998, ES&T,聚乙烯不仅是三油酸酯的支持材料，其本身也富集了相当部分污染物， 膜/水分配系数（KPW）低于酯/水分配系数（KTW，KPW0.1-0.5 KTW,）,SPMD 的三室富集模型及其动力学参数,2018/1/26,21,(1),(2),(3),SPMD的线性动力学模型与两室平衡分配模型,2018/1/26,22,生物淤塞,在天然水体中，水生生物往往会粘附于采样器的外壁从而影响对污染物的富集，产生biofouling（生物淤塞）现象。但实验得到的结果可以通过校正后得到应用。对生物淤塞现象，Petty（2000）引入了校正因子Fi ，显然Fi在特定的环境下为一个恒定值：Rsc = Rs Fi,2018/1/26,23,现场实验的质量控制PRCs的引入,在制作Triolein-SPMDs时加入标准参考物质（permeability reference compounds，PRCs）对结果进行监控与校正，这就使得一些如水流速度、温度等环境因素对采样速率的影响得到消除。实验证明，应用PRCs可以使监测结果的准确性提高两倍。,Huckins et al, 2002, ES&T,2018/1/26,24,2018/1/26,25,Monthly Integrated Concentration (ng/L),12/98,1/99,2/99,3/99,4/99,5/99,0,1,2,3,Anthracene,Phenanthrene,Naphthalene,4,利用 triolein-SPMDs监测黄浦江中PAHs污染状况（每月采样一次）,Time-integrated Monitoring,2018/1/26,26,-2.0,-1.5,-1.0,-0.5,0.0,0.5,1.0,1.5,2.0,-2.0,-1.5,-1.0,-0.5,0.0,0.5,1.0,1.5,2.0,Log CSPE (pg/L),Log CSPMD (pg/L),31,84,118,153,176,129,128,180,15,Congeners,利用triolein-SPMD 和 C18-SPE 两种采样方法监测污水中PCBs（北京市某污水处理厂, t = 20-d）,Time-integrated Monitoring,2018/1/26,27,利用SPMD和鱼对比研究POPs的富集/生物降解性,log KTW = log KOW + 0.106,log BCF = log KOW + , Biodegradabilty,2018/1/26,28,lindan,aldrin,Heptachlor epoxide,p,p-DDT,HCB,实验室流水暴露条件下有机氯农药在SPMD和鱼体中的富集 (Flowing-through exposure time: 480 hrs),2018/1/26,29,0.00,1.00,2.00,3.00,4.00,5.00,6.00,-2.00,-1.00,0.00,1.00,2.00,3.00,log CFish,log CSPMD,信阳log CSPMD = 0.917log Cfish + 0.777R2 = 0.974,淮南log CSPMD = 0.904log Cfish + 0.576R2 = 0.986,淮河鱼体脂肪和SPMD脂肪中多氯联苯的浓度,2018/1/26,30,0,1,2,3,4,2,3,4,5,Log KOW,Log BCF or KSPMD,Log KSPMD,Log BCF,实验室流水暴露条件下硝基苯在SPMD和鱼体中的富集 (Flowing-through exposure time: 480 hrs),2018/1/26,31,0,1,2,3,4,NB,2-NT,3-NT,4-NT,2,4-DNT,2,6-DNT,1,2-DNB,1,3-DNB,1,4-DNB,Log DCF, log BCF, or log KOW,log DCF,log BCF,log KOW,实验室流水暴露条件下硝基苯在金鱼体中的富集/降解 (Flowing-through exposure time: 480 hrs),2018/1/26,32,SPMD和同时放置“笼”鱼的对比实验,Gale, 1997, ES&T,Saginaw River, Michigan,2018/1/26,33,In-vitro Tests,In-vivo Tests,利用生物模拟采样技术作为生物测试的样品处理手段,1-30升水浓缩到小体积,在大体积水中富集,2018/1/26,34,Relative Induction,Bioassay & in-vitro Biomarker,In-vitro EROD Induction of Water Samples from the Huaihe River（Triolein-SPMD, 28-d，H4IIE Cell-Line）,2018/1/26,35,Sampling (d),PCB-52在SPMD组成之间的分配,(Gale, 1998, ES&T),2018/1/26,36,Membrane,Triolein Drops,Hydrophobic,Hydrophilic,醋酸纤维素中性类脂复合膜的构造,2018/1/26,37,专利号：ZL 02 1 42106.4,Triolein-Membrane,Blank Membrane,Triolein drops,Triolein-Embedded Cellulose Acetate Membrane (TECAM),2018/1/26,38,LDPE-triolein，1800 cm2/g triolein, 93% of equilibrium could be reached within 1 month（Hofelt, 1997）,LDPE-triolein，1000 cm2/g triolein, equilibrium could not be reached within 1 month (Huckins, 1990）,Specific Surface of SPMDs and TECAM,TECAM，4800 cm2/g triolein, equilibrium could be reached within 1 week,2018/1/26,39,20,40,60,WaterExtracts,CyclohexaneExtract,0,CyclohexaneExtract after Mulling,DichloromethaneExtract(dissolved),Triolein在TECAM中的稳定性,2018/1/26,40,Lipid Content in Membranes and Fish,Lipid content (%): 1-10%,Lipid-to-membrane mass ratio (%): 7.5%,Lipid-to-membrane mass ratio (%): 20%,Fish,TECAM,Triolein-SPMD,2018/1/26,41,Uptake kinetics of Organochlorine Pesticides (OCPs) in water by TECAMs (Static system, exposure time: 48 hrs),OCPs could actively and rapidly distribute from the aqueous phase into the membrane. Faster equilibrium times were observed for TECAMs than triolein-SPMDs, for target compounds with similar hydrophobicity. TECAMs 6 OCPs, logKow: 3.71 - 6.14, All within 24 hrsSPMDs 7 PAHs, logKow: 3.45 - 5.30, At least 72 hrs,2018/1/26,42,Two-compartment Kinetics Model for Uptake of OCPs by TECAMs,Water PhaseCw,Membrane PhaseCm,k1,k2,Cw0,kv0,2018/1/26,43,Estimated TECAMs Uptake Kinetics Parameters of the selected OCPs,n=11, p0.01,2018/1/26,44,Linear Equilibrium Partitioning,TECAM,CAM,r : 0.964-0.997n=8, P0.01,2018/1/26,45,Three-Compartment Equilibrium Partitioning Model,2018/1/26,46,Correlations of logKpTECAM, logKtw and log Ktc versus logKow,2018/1/26,47,Correlations Between logKtw and logBCF,A significant correlation (P0.01) was found between logKtw and logBCF (n=6), with r = 0.952 a Bioconcentration factor of rainbow trout, calculated from empirical equation in literature (Oliver et al., 1985),2018/1/26,48,利用TECAMs监测表层水有机氯农药（太湖梅梁湾），未净化样品谱图,-HCH, (2) -HCH, (3) -HCH, (4) -HCH, (5) -endosulfan, (6) cis-chlordane, (7) p,p-DDE, (8) endosulfan sulfate,2018/1/26,49,现场实验（太湖梅梁湾）定量分析,2018/1/26,50,利用 TECAM膜萃取替代常规监测（征询合作伙伴）,Water sample(Definite volume),TECAM(0.2 g/L water),Organicsolvents,Hydrophobic pollutants,Short exposure time: within 24 hrs,Using magnetic stirring to accelerate enrichment,Dialysis,DCM,Hexane,Analysis,Cleanup,优点：价格便宜，操作简单，溶剂用量小，不需要净化！,2018/1/26,51,Recoveries of OCPs Extracted by TECAMs,Recoveries of 17 OCPs dialysis with DCM (with a cleanup procedure): 84.0 16.6%, for laboratory control spikesRecoveries of 17 OCPs dialysis with n-hexane (without a cleanup procedure): 51.2 13.0%, for laboratory control spikes,2018/1/26,52,Correlations of Recoveries % and log Kow of OCPs(Preconcentrated by TECAMs),2018/1/26,53,Chromatogram of a sewage effluent sample preconcentrated by TECAMs,1=TMX (S.S.), 2=-HCH, 3=-HCH, 4=-HCH, 5=PCNB (I.S.),Dialysis in hexane without cleanup,2018/1/26,54,Monitoring OCPs in the Sewage: Membrane extraction using TECAMs, Compared with SPE,2018/1/26,55,Method for Long-term Monitoring Using TECAMs,Hydrophobic pollutants,