1、 A Guide for the Use of Semipermeable Membrane Devices (SPMDs) as Samplers of Waterborne Hydrophobic Organic ContaminatsRegulatory and Scientific AffairsPUBLICATION NUMBER 4690MARCH 2002A Guide for the Use of Semipermeable Membrane Devices (SPMDs) as Samplers of Waterborne Hydrophobic Organic Contam
2、inats PREPARED UNDER CONTRACT BY James N. Huckins Jimmie D. Petty Harry F. Prest* Randal C. Clark David A. Alvarez Carl E. Orazio Jon A. Lebo Walter L. Cranor B. Thomas Johnson Columbia Environmental Research Center U.S. Geological Survey USDI 4200 New Haven Road Columbia, MO 65201 *California Analy
3、tical Division Agilent Technologies, Inc. 1601 California Avenue Palo Alto, CA 94303 MARCH 2002 iiACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: API STAFF CONTACT Thomas W. Purcell, Ph.D., Sr.
4、 Environmental Scientist PAST AND CURRENT MEMBERS OF THE BIOMONITORING TASK FORCE Dr. Raymon Arnold, Exxon Biomedical Sciences, Inc. Marie Benkinney, Mobil Oil Corporation Dr. Philip Dorn, Equilon Enterprise Janis Farmer, BP PLC Dr. William Gala, Chevron Texaco Company Dr. Jerry Hall Dr. Michael Har
5、rass, BP Chemicals Denise Jett, Phillips Petroleum Company Dr. Eugene Mancini, ARCO James OReilly, ExxonMobil Production Company Dr. Lawrence Reitsema, Marathon Oil Company Alexis E. Steen, ExxonMobil Corporation Michael Swindoll, ExxonMobil Biomedical Michael Tucker, Occidental Chemical Company Car
6、l Venzke, Citgo Petroleum Corporation CONTRACTORS ACKNOWLEDGMENTS WE THANK DR. JEFF WHYTE FOR HIS TECHNICAL ASSISTANCE IN THE COMPLETION OF THIS WORK. THE INSIGHTS OF DR. KEES BOOIJ, DR. ROBERT GALE AND DR. DON MACKAY ON THEORY AND MODELING ARE GREATLY APPRECIATED. WE ALSO ACKNOWLEDGE THE INTEREST A
7、ND SUPPORT OF SCOTT FOLWARKOW OF THE WESTERN STATES PETROLEUM ASSOCIATION, AND GARY RAUSINA OF THE CHEVRON RESEARCH AND TECHNOLOGY COMPANY. WE GIVE SPECIAL THANKS FOR THE GUIDANCE OF DR. WILLIAM GALA AND ALEXIS STEEN. FINALLY, WE DEDICATE THIS WORK TO THE MEMORY OF GARY RAUSINA. iiiTABLE OF CONTENTS
8、 Section Page EXECUTIVE SUMMARY ES-1 1. INTRODUCTION.1-1 SYSTEM DESCRIPTION AND RATIONALE1-4 2. SAMPLING OVERVIEW .2-1 APPLICABILITY OF SPMDs 2-1 METHOD SELECTION .2-3 Integrative 2-4 Equilibrium.2-5 COMMENTS ON AMBIENT CONCENTRATION EXTRAPOLATIONS 2-7 Accuracy of Water Concentration Estimates.2-7 S
9、YNOPSIS OF PERFORMANCE RELATED VARIABLES.2-9 DEPLOYMENT 2-11 3. THEORY AND MODELING.3-1 MODELS FOR ESTIMATION OF WATER CONCENTRATION.3-3 Groundwater Concentration Estimation.3-6 Sediment Pore Water 3-7 SAMPLING APPROACH AND KINETICS3-8 RATE CONTROL 3-11 FACTORS AFFECTING UPTAKE RATES. 3-13 Sampler D
10、esign. 3-14 Molecular Properties. 3-14 Environmental Properties . 3-16 CALIBRATION DATA . 3-23 PERMEABILITY/PERFORMANCE REFERENCE COMPOUNDS (PRCS). 3-31 ivTABLE OF CONTENTS Section Page 4. STUDY CONSIDERATIONS.4-1 SOURCE AND PREPARATION OF SPMDS4-1 Preparation and Evaluation of Materials4-1 SPMD Ass
11、embly 4-2 SPECIFICATIONS OF THE STANDARD SPMD 4-3 STORAGE AND TRANSPORT4-4 PRECAUTIONS/PROCEDURES DURING DEPLOYMENT AND RETRIEVAL4-5 DEPLOYMENT METHOD.4-7 EXPOSURE DURATION AND ENVIRONMENTAL VARIABLES.4-8 5. SPMD ANALYTICAL CHEMISTRY5-1 QUALITY CONTROL5-1 SPMD-Fabrication Blanks.5-2 SPMD-Process Bla
12、nks5-2 Reagent Blank.5-3 Field-Blank SPMDs5-3 PRC Samples.5-4 SPMD Spikes.5-5 Procedural Spikes5-5 Expected QC Results.5-6 PROCESSING AND RESIDUE ENRICHMENT.5-7 Potential SPMD Specific Interferences. 5-10 INSTRUMENTAL ANALYSIS. 5-12 DATA FORMAT AND COMPARABILITY. 5-14 vTABLE OF CONTENTS Section Page
13、 6. BIOASSAY OF SPMD EXTRACTS OR DILUENTS6-1 MICROTOX AND MUTATOX .6-4 MFO-EROD 6-8 OVERVIEW OF ADDITIONAL ASSAYS 6-10 POTENTIAL INTERFERENCES. 6-12 7. COMPARiSIONS TO BIOMONITORING ORGANISMS.7-1 8. CONCLUSIONS .8-1 REFERENCES .R-1 APPENDIX A SOURCES OF SPMD INFORMATIONA-1 APPENDIX B EXAMPLES OF APP
14、LICATIONS B-1 APPENDIX C ADDITIONAL CALIBRATION DATA.C-1 APPENDIX D WATER CONCENTRATION EXTRAPOLATIOND-1 viLIST OF FIGURES Figure Page 1-1 A Standard Lipid-Containing SPMD .1-3 1-2 Exploded Views of the Nonporous Membrane Size Exclusion Phenomenon.1-6 2-1 Plot of the Three Phases of SPMD Uptake.2-6
15、3-1 Profile of an SPMD Showing Potential Barriers to Analyte Mass Transfer or Uptake 3-13 3-2 Linear Regression Analysis of the Biofouling Mediated Percent Reduction (%Ib) in Native PAH Uptake, as a Function of Log Kow. 3-19 3-3 Effect of Temperature and Log Kow on PP PAH Rs Values 3-22 3-4 Illustra
16、tion of Why the Permeability Reference Compound (PRC) Approach can be used to Adjust SPMD Sampling Rates 3-31 4-1 For Storage and Shipping, SPMDs are Placed in a Clean Metal Can.4-5 4-2 A Commercially Available Stainless steel Deployment Apparatus with a Capacity of 5 Standard SPMDs4-8 5-1 Key Aspec
17、ts of the SPMDs Sampling and Analysis Process 5-9 5-2 Illustration of Potential Problems Associated with Lipid Normalization of SPMD and Biota Chemical Concentrations: Kinetics versus Equilibrium 5-16 6-1 Illustration of SPMD in vitro Bioassay and Immunoassay Protocol6-5 6-2 Ethoxyresorufin O-deethy
18、lase (EROD) Induction in H4IIE Rat Hepatoma Cells Exposed to an SPMD Dialysate. 6-11 7-1 Comparison of the Patterns of Organic Contaminant Uptake Rates (as Related to Log Kows) by SPMD and Across Fish Gills.7-3 7-2 Comparison of Alkylated PAHs Residence Time in SPMDs and Oysters (Crassotrea gigas) 7
19、-8 B-1 GC-MS Comparison of Ion Chromatograms of Extracts from Mussels (Mytilus edulis) and SPMDsB-4 B-2 Comparison of PAHs Detected by GC-PID in SPMDs and Clams (Corbicula fuminea).B-5 viiLIST OF TABLES Table Page 3-1 Summary of SPMD PP PAH Sampling Rates, Exchange Coefficients, and Partition Coeffi
20、cients Derived from a 10 C Freshwater Flow-Through Exposure and Static Exposures. 3-25 3-2 Summary of SPMD PP PAH Sampling Rates, Exchange Coefficients, and Partition Coefficients Derived from a 18 C Freshwater Flow-Through Exposure and Static Exposures. 3-26 3-3 Summary of SPMD PP PAH Sampling Rate
21、s, Exchange Coefficients, and Partition Coefficients Derived from a 26 C Freshwater Flow-Through Exposure and Static Exposures. 3-27 3-4 Summary of SPMD Organochlorine Pesticides Sampling Rates Derived from a 10 C Freshwater Flow-Through Exposure 3-28 3-5 Summary of SPMD Organochlorine Pesticides Sa
22、mpling Rates Derived from a 18 C Freshwater Flow-Through Exposure 3-29 3-6 Summary of SPMD Organochlorine Pesticides Sampling Rates Derived from a 26 C Freshwater Flow-Through Exposure 3-30 6-1 Toxicological Evaluation of Polyaromatic Hydrocarbons (PAHs) with Microtox Basic Test and Mutatox6-7 6-2 U
23、se of Microtox and Mutatox to Determine the Toxicity of SPMD Concentrates 6-8 7-1 Comparison of the SPMD Membrane and Respiratory Lamellae (gills) of Fish7-5 7-2 Comparison of SPMD and Oyster (Crassotrea gigas) Exchange Kinetics for Selected PAHs 7-7 C-1 PCB Congener Uptake Rate Constants for SPMDs
24、C-2 C-2 Whole SPMD (lipid plus membrane) Uptake Rates (11 C and 19C) for PCDDs, PCDFs and PCBs C-6 C-3 Physicochemical Properties and Standard SPMD (Whole Device) Uptake Kinetic Parameters (10 C) for Selected Insecticide.C-7 viiiLIST OF TABLES Table Page D-1 Estimate of Water Concentration from SPMD
25、s Exposed to 10 C Water for 21 Days Using the Excel Calculator D-5 D-2 Estimate of Water Concentration from SPMDs Exposed to 18 C Water for 21 Days Using the Excel Calculator D-9 D-3 Estimate of Water Concentration from SPMDs Exposed to 26 C Water for 60 Days Using the Excel Calculator D-13 ixABBREV
26、IATIONS AND ACRONYMS A Area (cm2 or m2) of an exchanging surface such as the SPMD membrane Angstrom, 10-10 meters API American Petroleum Institute ACGIH American Conference of Governmental and Industrial Hygienists B Biofilm or periphyton layer, lower case for subscript BAF Bioaccumulation factor (t
27、ypically, concentration in whole tissue divided by concentration in water), includes both respiratory and dietary routes of chemical uptake C Chemical concentration in a medium, subscript specifies type of medium (Cw in this work is limited to residues dissolved in water) cal Calibration, i.e., labo
28、ratory generated data characterizing SPMD performance under controlled conditions CERC Columbia Environmental Research Center of the US Geological Survey CF Concentration factor in an SPMD, i.e., concentration in the whole SPMD divided by concentration in water C.V. Coefficient of variation, also ca
29、lled relative standard deviation, derived by dividing the sample mean into the standard deviation D Diffusion coefficient (cm2 or m2 / s or d) DOC Dissolved organic carbon, operationally defined as organic carbon that passes through a 0.2 m or 0.45 m filter d Day(s), or density e Subscript for excha
30、nge or loss (note that most subscripts denote the type of medium) F Flux; relative to Darcys Law (Fw) the units are L or m3/s or d, whereas relative to mass transfer of chemical across a barrier (Fc) the units are typically ng/s or d (also can be expressed as ng/d cm2) f Field, i.e., derived from fi
31、eld exposures xEC50 Toxicant concentration where 50% of test organisms exhibit adverse effects, i.e., effects concentration at the 50% level ECD Electron capture detector EROD Ethoxyresorufin O-deethylase, an enzyme, which is used as a bioindicator of planar aromatic contaminants g Gram GC Gas chrom
32、atography GPC Gel permeation chromatography, also referred to as size exclusion chromatography (SEC) h Hydraulic head, generally denoted as h and represents the difference in hydraulic head between the upper most point and the bottom of the strata or formation I Impedance to mass transfer or resista
33、nce K Equilibrium partition coefficient between two separate phases identified by subscripts, generally expressed as a dimensionless value k Rate constant (a unit mass specific coefficient, given in units of mL/dg or 1/d) or mass transfer coefficient (cm or m/s), subscripts denote direction of chemi
34、cal movement (rate constant) or type of medium (mass transfer coefficient) L Liter, or lipid Lf Length of a water bearing formation, used in groundwater modeling LDPE Low density polyethylene, layflat tubes with no additives used as SPMD membrane LLE Liquid-liquid extraction, the two phases must be
35、largely immiscible l Effective thickness of a barrier (e.g., aqueous boundary layer) to the mass transfer of chemicals M Mass xim Membrane or the LDPE tube used to make SPMDs mol Mole n Nano, one billionth of a mass unit. MDL Minimum detection limit for a specific chemical and method MQL Method quan
36、titation limit for a specific chemical MW Molecular weight OCs Organochlorine pesticides o A subscript referring to “overall” or the lipid-like solvent “octanol” P Permeability coefficient, it is defined as Dm Kmw for mass transfer in polymers with units of cm2 or m2/s or d, and is called hydraulic
37、conductivity (i.e., Phc) in groundwater modeling with units of velocity, i.e., cm or m/s or d p Pico, one trillionth of a mass unit PCBs Polychlorinated biphenyls PCDDs Polychlorinated dibenzo-p-dioxins PCDFs Polychlorinated dibenzofurans PAHs Polycyclic Aromatic Hydrocarbon, a class of compounds la
38、rgely derived by the production and use of fossil fuels PP Priority pollutant; a chemical or group of chemicals (e.g., the 16 PAHs that are emphasized in this work) listed by the US Environmental Protection Agency (EPA) as contaminants of concern POC Particulate organic carbon PRC Permeability (memb
39、rane control) or performance (aqueous boundary layer control) reference compound; defined as a noninterfering (analytically) compound spiked into SPMD lipid that is used to relate laboratory calibration data for SPMDs to actual in situ sampling rates or to develop in situ calibration data QC Quality
40、 control xiiRs Sampling or clearance rate which is applicable only to the linear uptake phase, not unit-mass or -volume specific, operationally defined as a standard 1-g triolein SPMD and given in L / d or mL / d R2 Correlation coefficient, ratio of the sum of squares due to the regression equation
41、divided by the sum of the squares about the mean s Second(s) SA Surface area SEC Size exclusion chromatography, used interchangeably with GPC in this work SG Silica gel, an adsorbent (normal phase) used for cleanup and fractionation of certain classes of chemicals SOP Standard operating procedure SP
42、E Solid phase extraction SPMD Semipermeable membrane device, consists of a thin film of lipid, or another sequestration phase, sealed inside a LDPE tube of appropriate specifications TCDD 2,3,7,8-tetrachlorodibenzo-p-dioxin TEQ Toxic equivalents to TCDD TWA Time weighted average, generally refers to
43、 the TWA chemical concentration during an exposure period t Time, given in units of “d” or “s” u Uptake, used as a subscript USGS United States Geological Survey V Volume (mL, L or m3) of a matrix such as water, lipid and membrane VD Lebas molar volume of a molecule w Water, used as a subscript xiii
44、 Micron (10-6 m) relative to distance, and micro relative to mass (106 gram, i.e., microgram) and volume (106 L, i.e., microliter) Proportional to hw Viscosity of water at a specific temperature xivABSTRACT Interest in the use of an in situ passive sampling approach for assessing environmental pollu
45、tant exposure has increased worldwide. A new paradigm for aquatic exposure assessments is emerging based on the use of lipid containing semipermeable membrane devices (SPMDs), which have been shown to be highly effective samplers of hydrophobic organic contaminants in water and air. The ability of S
46、PMDs to concentrate trace (less than one-part-per-billion g/L) concentrations of dissolved lipophilic residues to measurable levels is achieved by mimicking specific mechanisms of the aquatic bioconcentration (the uptake concentration of a substance by an organism from the surrounding medium e.g., w
47、ater, excluding the dietary route) process. The purpose of this document is to provide basic information and guidance on SPMD technology, and its appropriate use in aquatic systems. Emphasis is given to methods, applications, and theoretical issues related to the use of SPMDs for monitoring priority
48、 pollutant polycyclic aromatic hydrocarbons (PP PAHs), but other classes of hydrophobic organic contaminants are covered as well. This document includes key information on SPMD background, rationale, theory and modeling, technical considerations, supplier/source, chemical analysis and quality contro
49、l, bioassay screening, comparability to biomonitors, examples of use, and sources of addition information. However, covering all potential environmental applications (e.g., vapor phase sampling) and relevant research results is beyond the scope of this work. Finally, use of this guide does not obviate the need for proper review and oversight procedures prior to the initiation of a project with SPMDs. ES-1 EXECUTIVE SUMMARY BACKGROUND AND SPMD DEVELOPMENT Environmental researchers have long recognized the tendency of some aquatic organisms to concentrate trac
