spmd培训课程.ppt

Click to edit Master title style,Click to edit Master text styles,Second level,Third level,Fourth level,Fifth level,*,*,2026/10/22,1,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,2026/10/22,2,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,2026/10/22,3,有机污染物的样品制备,环境介质,（水、沉积物等）,有机相,（有机溶剂、高分子聚合物等）,相似相溶,浓集,主动式,被动式,在外力作用下的主动浓缩,在没有外力作用下被动扩散,有机污染物分析中的样品制备方法,2026/10/22,4,主动和被动采样对不同极性物质富集效果的区别,亲水性化合物,A,亲脂性化合物,B,主动,被动,2026/10/22,5,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,2026/10/22,8,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,2026/10/22,20,Water,Polyethylene,Triolein,K,0,K,WP,K,PW,K,PT,K,TP,K,WP,(cm,3,/d),K,PT,(cm,3,/s),PCB-52 PE 4200 1.9,PCB-52 SPMD 4200 1.9,Phenanthrene 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（,K,PW,）低于酯,/,水分配系数（,K,TW,，,K,PW,0.1-0.5,K,TW,）,SPMD,的三室富集模型及其动力学参数,2026/10/22,21,(1),(2),(3),SPMD,的线性动力学模型与两室平衡分配模型,2026/10/22,22,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,F,i,，显然,F,i,在特定的环境下为一个恒定值：,R,sc,=R,s,F,i,2026/10/22,23,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,2026/10/22,24,2026/10/22,25,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,2026/10/22,26,-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 C,SPE,(pg/L),Log C,SPMD,(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,2026/10/22,27,利用,SPMD,和鱼对比研究,POPs,的富集,/,生物降解性,log,K,TW,=log,K,OW,+0.106,log,BCF,=,log,K,OW,+,Biodegradabilty,2026/10/22,28,3.5,4,4.5,5,5.5,6,3.5,4,4.5,5,5.5,6,6.5,7,Log,K,OW,BCF or log,K,SPMD,Rainbow Trout,Trolein-SPMD,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),2026/10/22,29,0.00,1.00,2.00,3.00,4.00,5.00,6.00,-2.00,-1.00,0.00,1.00,2.00,3.00,log,C,Fish,log,C,SPMD,信阳,log,C,SPMD,=0.917log,C,fish,+0.777,R,2,=0.974,淮南,log,C,SPMD,=0.904log,C,fish,+0.576,R,2,=0.986,淮河鱼体脂肪和,SPMD,脂肪中多氯联苯的浓度,2026/10/22,30,0,1,2,3,4,2,3,4,5,Log,K,OW,Log BCF or,K,SPMD,Log,K,SPMD,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),2026/10/22,31,0,1,2,3,4,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 K,OW,log DCF,log BCF,log K,OW,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),2026/10/22,32,SPMD,和同时放置“笼”鱼的对比实验,Background Effect in Fish,Potentially Metabolized Components,Gale,1997,ES&T,Saginaw River,Michigan,2026/10/22,33,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,2026/10/22,34,0,40,80,120,160,蚌埠,Bengbu,府阳,Fuyang,信阳,Xinyang,淮南,Huainan,24hr,72hr,Relative Induction,Bioassay&in-vitro Biomarker,In-vitro EROD Induction of Water Samples from the Huaihe River,（,Triolein-SPMD,28-d,，,H4IIE Cell-Line,）,2026/10/22,35,15,甘油脂,PE,膜,器件,0,30,Sampling (d),PCB-52,在,SPMD,组成之间的分配,(Gale,1998,ES&T),2026/10/22,36,Membrane,Triolein Drops,Hydrophobic,Hydrophilic,醋酸纤维素中性类脂复合膜的构造,2026/10/22,37,专利号：,ZL 02 1 42106.4,Triolein-Membrane,Blank Membrane,Triolein drops,Triolein-Embedded Cellulose Acetate Membrane(TECAM),2026/10/22,38,LDPE-triolein,，,1800 cm,2,/g triolein,93%of equilibrium could be reached within 1 month,（,Hofelt,1997,）,LDPE-triolein,，,1000 cm,2,/g triolein,equilibrium could not be reached within 1 month(Huckins,1990,）,1,1,1,1,Specific Surface of SPMDs and TECAM,1,1,TECAM,，,4800 cm,2,/g triolein,equilibrium could be reached within 1 week,2026/10/22,39,20,40,60,Water,Extracts,Cyclohexane,Extract,0,Cyclohexane,Extract after Mulling,Dichloromethane,Extract,(dissolved),Triolein,在,TECAM,中的稳定性,2026/10/22,40,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,2026/10/22,41,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,log,Kow,:3.71-6.14,All within 24 hrs,SPMDs 7 PAHs,log,Kow,:3.45-5.30,At least 72 hrs,25000,time(h),0,5000,10000,15000,20000,0,10,20,30,40,50,C,TECAM,(ng g,1,),-HCH,-HCH,heptachlor epoxide,aldrin,endrin,p,p-DDE,2026/10/22,42,Two-compartment,Kinetics Model for Uptake of OCPs by TECAMs,Water,Phase,C,w,Membrane,Phase,C,m,k,1,k,2,C,w,0,k,v,0,2026/10/22,43,Estimated TECAMs Uptake Kinetics Parameters of the selected OCPs,compound,k,1,(h,1,),k,2,(h,1,),K,p,TECAM,R,2,-HCH,368,0.230,1600,0.976,-HCH,497,0.184,2700,0.893,heptachlor epoxide,658,0.0487,13500,0.839,endrin,564,0.0271,20800,0.965,aldrin,499,0.0161,31000,0.970,p,p-DDE,612,0.0115,53100,0.991,n=11,p0.01,2026/10/22,44,Linear Equilibrium Partitioning,15,-HCH,0,30000,60000,90000,120000,150000,0,5,10,15,20,25,-HCH,0,3,6,9,12,C,w,(g L,1,),C,m,(ng g,1,),C,w,(g L,1,),TECAM,CAM,r:0.964-0.997,n=8,P0.01,C,m,(ng g,1,),Aldrin,0,30000,60000,90000,120000,150000,0,1,2,3,4,5,p,p-DDE,0,1,2,3,4,5,C,w,(g L,1,),C,w,(g L,1,),C,m,(ng g,1,),Heptachlor epoxide,0,30000,60000,90000,120000,150000,Endrin,0,2,3,4,5,6,1,0,2,3,4,5,6,1,C,w,(g L,1,),C,w,(g L,1,),2026/10/22,45,Three-Compartment Equilibrium Partitioning Model,Water,CA,Triolein,K,p,TECAM,K,p,CA,K,tc,K,tw,2026/10/22,46,Correlations of log,K,p,TECAM,log,K,tw,and,log,K,tc,versus log,K,ow,log,K,p,TECAM,log,K,tw,log,K,tc,3,4,5,6,7,log,K,p,0,1,2,3,4,3,4,5,6,7,log,K,ow,2026/10/22,47,Correlations Between log,K,tw,and logBCF,compound,log,K,ow,log,K,tw,log BCF,a,-HCH,3.71,3.70,3.00,-HCH,3.86,3.98,3.15,heptachlor epoxide,4.51,4.75,3.77,endrin,4.63,5.02,3.88,aldrin,5.31,5.30,4.54,p,p-DDE,6.14,5.65,5.33,A significant correlation(,P,0.01)was found between log,K,tw,and logBCF(n=6),with,r,=0.952,a,Bioconcentration factor of rainbow trout,calculated from empirical equation in literature(Oliver et al.,1985,),2026/10/22,48,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,min,10,12,14,16,18,20,22,24,26,28,Hz,500,1000,1500,2000,2500,3000,3500,4000,4500,1,2,3,4,5,7,6,8,-HCH,(2)-HCH,(3)-HCH,(4)-HCH,(5)-endosulfan,(6),cis,-chlordane,(7)p,p-DDE,(8)endosulfan sulfate,2026/10/22,49,现场实验（太湖梅梁湾）,定量分析,compd,concentration in TECAMs,(ng g,1,),concentration in water,(g L,1,),48 hr,96 hr,192 hr,384 hr,estimate,measure,RE,(%),-HCH,10.41,12.64,12.38,12.80,4.6710,-3,5.2410,-3,11.0,-HCH,3.06,3.44,3.40,3.54,2.2110,-3,2.8010,-3,21.5,2026/10/22,50,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),Organic,solvents,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！,2026/10/22,51,Recoveries of OCPs Extracted by TECAMs,Recoveries of 17 OCPs dialysis with DCM(with a cleanup procedure):84.0 16.6%,for laboratory control spikes,Recoveries of 17 OCPs dialysis with,n,-hexane(without a cleanup procedure):51.2 13.0%,for laboratory control spikes,2026/10/22,52,Recovery%=12.99 log,K,ow,+17.50,R=0.88,n=17,0.00,20.00,40.00,60.00,80.00,100.00,3.00,3.50,4.00,4.50,5.00,5.50,6.00,6.50,7.00,log,K,ow,Recovery%,Correlations of Recoveries%and log,K,ow,of OCPs,(Preconcentrated by TECAMs),2026/10/22,53,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,2026/10/22,54,0.0,5.0,10.0,15.0,20.0,25.0,-HCH,-HCH,-HCH,Concentration(ng/l),0.0,5.0,10.0,15.0,20.0,25.0,A,B,0.0,5.0,10.0,15.0,20.0,25.0,30.0,0.0,5.0,10.0,15.0,20.0,25.0,30.0,-HCH,-HCH,-HCH,Concentration(ng/l),A,B,Monitoring OCPs in the Sewage:,Membrane extraction using TECAMs,Compared with SPE,SPE,TECAM,A:Influent B:Effluent,2026/10/22,55,Method for Long-term Monitoring Using TECAMs,Flow through water,in environment,TECAM,(1g per sample),Hexane/,Cyclohexane,Hydrophobic pollutants,Long exposure time:at least 336 hrs,Dialysis,Analysis for concentration in TECAM,Evaluate concentration in water,Predictionmodel,Mimic,bioaccumulation,2026/10/22,56,1=-HCH 2=-HCH 3=-HCH 4=,trans,-Chlordane 5=,cis,-Chlordane 6=,p,p,-DDE 7=,p,p,-DDD 8=,p,p,-DDT,0.00,0.50,1.00,1.50,2.00,2.50,1,2,3,4,5,6,7,8,Concentration(ng/L),Pre-chlorination,Coagulating sedimentation,Sand filtration,Pipe network,利用,TECAM,长期在线监测,(,放置,720 hrs),2026/10/22,57,Using TECAMs to Mimic bioconcentration of OCPs by Fish(Flow-through system,t=480 hrs,Log Kow,BCF or log K,tw,Lindane,Aldrin,Heptachlor-epoxide,p,p,-DDT,HCB,3,4,5,3.00,4.00,5.00,6.00,Rainbow Trout,TECAM,2026/10/22,58,小结,被动式半渗透膜采样器被用来模拟有机污染物在生物体内富集并浓缩于脂肪组织的过程，是长期监测（,time-integrated,）持久性有毒有机污染物的工具；,利用被动式生物模拟采样技术测得的目标污染物浓度被认为是生物有效态浓度，可广泛应用于生物积累、生物降解、生物测试、生态风险评价等各项研究中，具有很大发展潜力,