Use of the Semipermeable Membrane Device as an in Situ Sampler of Waterborne Bioavailable PCDD and PCDF residues at Sub-Parts-per Quadrillion Concentrations.

Metadata:

• Identification_Information
• Data_Quality_Information
• Spatial_Data_Organization_Information
• Entity_and_Attribute_Information
• Distribution_Information
• Metadata_Reference_Information

Identification_Information:

Citation:

Citation_Information:

Originator:

Lebo, Jon. A., Robert W. Gale, Jimmie D. Petty, Donald E. Tillitt, James N. Huckins, John C. Meadows, Carl E. Orazio, Kathy R. Echols, and Dennis J. Schroeder

Originator:

U.S. Geological Survey, Biological Resources Division, Columbia Environmental Research Center

Originator: Lloyd E. Inmon

Originator: U.S. Fish and Wildlife Service

Publication_Date: 199511

Title:

Use of the Semipermeable Membrane Device as an in Situ Sampler of Waterborne Bioavailable PCDD and PCDF residues at Sub-Parts-per Quadrillion Concentrations.

Description:

Abstract:

Semipermeable membrane devices (SPMDs) were used to passively sample aqueous polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in Bayou Meto, Arkansas. The two sites were upstream and downstream from the confluence with a tributary that delivers PCDDs and PCDFs to the Bayou. Following dialysis, cleanup, and fractionation, four replicate 17-g SPMD samples from each site were analyzed by gas chromatography/mass spectrometry (GC/MS), and four were evaluated by H4IIE bioassay. Traces of only octachlorodioxin (OCDD) and heptachlorodioxins (HpCDDs) were detected in samples from the upstream site. The four samples from below the tributary contained averages of 1550+/- 80 pg of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 1640+/-80 pg of 2,3,7,8-tetrachlorodibenzofuran (TCDF), and lesser quantities of other congeners. The TCDD equivalents obtained by bioassay of replicate SPMD samples agreed well with results obtained by GC/MS. The quanitites of 2,3,7,8-TCDD and 2,3,7,8-TCDF sequestered by SPMDs at the downstream site were used to estimate the aqueous concentrations for both compounds as 2 pg/L.

Purpose:

The primary objective of the study was to supplement previously assembled information on the contaminant problem at Bayou Meto. The water at two sites in Bayo Meto was sampled in situ with SPMD for aqueous PCDD and PCDF residues. All 2,3,7,8-chlorinated congeners and all Cl4-Cl8 PCDD and PCDF homologs were targeted for analysis. An integral part of the primary objective was to use SPMD-derived data to estimate aqueous concentrations of TCDD at a severely contaminated Bayou Meto site. SPMDs have not been extensively used for sampling PCDDs and PCDFs (Prest, 1992), and a second objective of the work was to demonstrate their potential for monitoring these classes of contaminants. Dialyzates from environmentally exposed SPMDs have been shown to be readily amenable to evaluation by Microtox (Johnson, B.T., 1993) and Mutatox (Johnson, B.T., 1992 and Johnson, B.T., 1993). To fulfill a third objective of this study, dialyates from SPMDs exposed at Bayou Meto were evaluated by an H4IIE bioassay procedure to demonstrate that the SPMD sampling technique is also complementary to this bioassay.

Time_Period_of_Content:

Time_Period_Information:

Range_of_Dates/Times:

Beginning_Date: 19930801

Ending_Date: 19930828

Currentness_Reference: observed

Status:

Progress: Complete

Maintenance_and_Update_Frequency: None planned

Spatial_Domain:

Description_of_Geographic_Extent: Bayo Meto, Arkansas

Bounding_Coordinates:

West_Bounding_Coordinate: -93

East_Bounding_Coordinate: -92

North_Bounding_Coordinate: 35

South_Bounding_Coordinate: 34.5

Keywords:

Theme:

Theme_Keyword_Thesaurus: None

Theme_Keyword: SPMDs

Theme_Keyword: semipermeable membrane devices

Place:

Place_Keyword_Thesaurus: None

Place_Keyword: Jacksonville, Arkansas

Place_Keyword: Arkansas

Place_Keyword: AR

Place_Keyword: Bayou Meto, Arkansas

Access_Constraints: none

Use_Constraints: none

Point_of_Contact:

Contact_Information:

Contact_Organization_Primary:

Contact_Organization:

U.S. Geological Survey, Biological Resources
Division, Columbia Environmental Research Center

Contact_Person: Jon A. Lebo

Contact_Address:

Address_Type: mailing and physical address

Address: 4200 New Haven Road

City: Columbia

State_or_Province: Missouri

Postal_Code: 65201

Contact_Voice_Telephone: (573) 876-1837

Contact_Facsimile_Telephone: (573) 876-1896

Contact_Electronic_Mail_Address: Jon_Lebo@usgs.gov

Cross_Reference:

Citation_Information:

Originator:

Jon A. Lebo, Robert W. Gale, Jimmie D. Petty, Donald E. Tillitt, James N. Huckins, John C. Meadows, Carl E. Orazio, Kathy R. Echols, and Dennis J. Schroeder

Originator:

U.S. Department of the Interior, Biological Resources Division, Columbia Environmental Research Center

Originator: Lloyd E. Inmon.

Originator: U.S. Fish and Wildlife Service

Publication_Date: 199511

Title:

Use of the Semipermeable Membrane Device as an in Situ Sampler of Waterborne Bioavailable PCDD and PCDF residues at Sub-Parts-per Quadrillion Concentrations.

Series_Information:

Series_Name: Environmental Science and Technology

Issue_Identification: vol. 29, no. 11

Publication_Information:

Publication_Place: unknown

Publisher: American Chemical Society

Other_Citation_Details: pp. 2886-2892

Data_Quality_Information:

Attribute_Accuracy:

Attribute_Accuracy_Report: unknown

Logical_Consistency_Report: not applicable

Completeness_Report: unknown

Lineage:

Methodology:

Methodology_Type: Field

Methodology_Identifier:

Methodology_Keyword_Thesaurus: None

Methodology_Keyword: study design

Methodology_Description:

SPMDs were deployed at two sites in Bayou Meto, Arkansas, in August 1993 and were allowed to passively sample aqueous PCDD and PCDF residues for 28 days. The average water temperature over the sampling period was 32 degrees. Site 1 is just upstream of the confluence of Rocky Branch Creek with Bayou Meto, and site 2 is immediately downstream from the confluence and is downstream form the outlets of both of Jacksonville's water treatment plants. The SPMDs consisted of 87 cm. lengths (average weight 3.35 g) of 2.54-cm wide layflat polyethylene tubing (86 micrometer average wall thickness) with 1.0 mL (0.91 g) of triolein (1,2,3-tri[cis-9-octadecenoyl] glycerol) heat-sealed inside. Shrouds fabricated from 0.9 m lenghs of 0.3-m diameter galvanized steel culvert were used to protect the SPMDs during the 28 day sampling period. After installation of the SPMDs in the shrouds, the ends of the shrouds were covered with protective metal screens. Two shrouds, each containing 16 SPMDs, were deployed at each of the two sampling sites. Bayou Meto is 10-15 m wide in the Jacksonville area; the two shrouds placed at each site were deployed near opposite shorelines. The shrouds were allowed to rest on the bottom of the Bayou and were securely tethered with braided steel cables to trees and other fixed objects. Because SPMDs have a propensity to sequester vapor-phase contaminants (Petty et al, 1993) they were sealed inside solvent-rinsed virgin paint cans for shipment to and from the sampling sites. An additional can containing the field blank SPMDs was transported to each sampling site. The two SPMDs constituting each field blank were exposed to air only while the corresponding water sampling SPMDs were being installed in or removed from their shrouds, and they were kept sealed in their cans throughout the interim. After the 28 day sampling period, the cans containing the field blank and Bayou -exposed SPMDs were shipped back to the laboratory in an ice-filled cooler and were kept in a freezer until analyses of the SPMDs began.

Methodology_Citation:

Citation_Information:

Originator: Petty, J.D., Huckins, J.N. & Zajicek, J.L.

Publication_Date: 1993

Title:

Application of Semipermeable Membrane Devices (SPMDs) as passive air samplers.

Series_Information:

Series_Name: Chemosphere

Issue_Identification: 27

Other_Citation_Details: pp. 1069-1624

Methodology_Type: Lab

Methodology_Identifier:

Methodology_Keyword_Thesaurus: None

Methodology_Keyword: dialysis

Methodology_Keyword: cleanup

Methodology_Keyword: fractionation

Methodology_Description:

The SPMDs were thawed and subjected to an exterior cleanup that removed periphyton, adhering sediment particles, and carbonates from the polyethylene. This cleanup consisted of alternately rinsing the SPMDs with running tap water and vigorously brushing the polyethylene with a toothbrush, then briefly immersing the SPMDs in 1 M HCl, rinsing them with water, then acetone, and allowing them to air-dry. All SPMDs from the same shroud were regarded as identical. The 16 SPMDs from each shroud were randomly pooled into four 4-SPMD samples; each sample thus consisted of 3.64 g of triolein and 13.4 g of polyethylene. Four 4 -SPMD samples from each site (two samples from each shroud) were subjected to an analytical scheme that culminated in analysis by gas chromatography/mass spectrometry (GC/MS) and four 4-SPMD samples from each site (two samples from each shroud) were subjected to a less elaborate scheme that culminated in H4IIE bioassay. One of the four SPMDs that constituted each sample that would be analyzed by GC/MS was opened, spiked with 600 pg of each of 15 ¹³C-labeled PCDD and PCDF procedural internal standards, and then resealed. (None of the samples destined to undergo bioassay were spiked with surrogates.) The four SPMDs constituting each sample were placed in a glass canning jar, 900 mL of hexane was added, and the jar was capped with an aluminum foil-lined lid. To minimize the quantities of lipids and polyethylene oligomers in the dialyzates, the dialyses were conducted at 18 degrees C (i.e., at subambient temperature (Meadows, 1993). The analytes were allowed 48 hours to dialyze into the hexane. The dialyzates were concentrated by rotary evaporation and then subjected to a sequence of two reactive/chromatographic cleanups previously described by Feltz (1995). The 2-cm i.d. glass columns used in the first cleanup were packed with, from bottom-top, potassium silicate (Lebo, 1989); sulfuric acid-impregnated silica gel; and coarse silica gel impregnated with sulfuric acid. Dichlormethane was the eluant for the first chromatographic cleanup. For the second cleanup, 1-cm i.d. columns were packed with, from bottom-top, silica gel; potassium silicate; and sulfuric acid-impregnated silica gel. The concentrated eluates from the first cleanup were applied, and the analytes were eluted with 3% (v/v) Ch2Cl2 in hexane. The eluates from the second reactive/chromatographic cleanup were treated with copper to remove elemental sulfur, then were concentrated by rotary evaporation. The concentrated solutions were fractionated by size exclusion chromatography (SEC). A Phenogel column (22.5-mm i.d.. x 250 -mm; 10 micromilimeter particles; 100-A pore size; Phenomenex, Torrance, CA) was used for the SEC; the mobile phase was 20% (v/v) CH2Cl2 in hexane pumped at 4.0 mL/min. The first 72 mL of the eluates from the SEC column was discarded; the collected fractions extended from 72 to 240 mL of the eluates. The collected fractions from SEC were concentrated by rotary evaporation. Further fractionations were not performed for those sample destined to be evaluated by H4IIE bioassay; the solutions were transferred to vials, isooctane (keeper solvent) was added, and the solutions were evaporated to 150-micro liter volumes.

Methodology_Citation:

Citation_Information:

Originator:

Meadows, J., Tillitt, D.E., Huckins, J., Schroeder, D.

Publication_Date: 1993

Title:

Large-scale dialysis of sample lipids using a semipermeable membrane device.

Series_Information:

Series_Name: Chemosphere

Issue_Identification: 26

Other_Citation_Details: pp. 19003-2006.

Methodology_Citation:

Citation_Information:

Originator:

Feltz, K.P.; Tillitt, D.E.; Gale, R.W.; Peterman, P.H.

Publication_Date: 1995

Title:

Automated HPLC fractionation of PCDDs and PCDFs and planar and nonplanar PCBs on C18-dispersed PX-21carbon.

Series_Information:

Series_Name: Environ. Sci. Technol.

Issue_Identification: 29

Other_Citation_Details: pp. 709-718.

Methodology_Citation:

Citation_Information:

Originator: Lebo, J.A.; Zajicek, J.L; May, T.W.; Smith, L.M.

Publication_Date: 1989

Title:

Large-scale preparation of potassium hydroxide-modified silica gel adsorbent.

Series_Information:

Series_Name: J. Assoc. Off. Anal. Chem.

Issue_Identification: 72

Other_Citation_Details: pp. 371-373

Methodology_Type: Lab

Methodology_Identifier:

Methodology_Keyword_Thesaurus: None

Methodology_Keyword: dialysis

Methodology_Keyword: cleanup

Methodology_Keyword: fractionation

Methodology_Description:

Samples to be analyzed by GC/MS were subjected to two additional fractionation procedures described elsewhere (Feltz et al, 1995; Echols, 1992). The concentrated eluates from the SEC fractionation were transferred to autoinjector vials for fractionation on a porous graphitic carbon column (4.6-mm i.d. x 100-mm Hypercarb; Keystone Scientific, Bellefonte, PA). The fractionation procedure was developed to isolate PCDDs and PCDFs from PCBs, chlorinated napththalenes, chlorinated diphenyl ethers, and other potential interferents (Echols, 1992). The chromatographic apparatus used in the carbon fractionation included a Perkin Elmer Series 410 pump and Perkin Elmer ISS 200 autosampler (Perkin Elmer, Inc., Norwalk, CT), a Foxy 200 fraction collector (Isco, Inc., Lincoln, NE), and a Valco N60 six-port, air-actuated switching valve (Valco Instruments Co., Inc., Houston, TX). The mobile phase was pumped at 2.5 mL/min throughout the multi-segment gradient program; Upon sample injection, hexane was pumped for 4 minutes, at which time an 8-min linear gradient to 40% (v/v) toluene in hexane was begun. From 12 until 32 minutes, 40% (v/v) toluene in hexane was pumped isocratically for 60 minutes. At 32 min, the direction of the flow through the column was reversed, and toluene was pumped isocratically for 60 min. The eluate resulting from the first 30 min of this reverse-flow toluene segment of the solvent program was collected by the fraction collector as the PCDD/PCDF fraction. In preparation for the next sample injection, the direction of the flow through the column was switched back to forward, and the mobile phase composition was changed via gradient to hexane.

Methodology_Citation:

Citation_Information:

Originator:

Feltz, K.P.; Tillitt, D.E.; Gale, R.W.; Peterman, P.H.

Publication_Date: 1995

Title:

Automated HPLC fractionation of PCDDs and PCDFs and planar and nonplanar PCBs on C18-dispersed PX-21carbon.

Series_Information:

Series_Name: Environ. Sci. Technol.

Issue_Identification: 29

Other_Citation_Details: pp. 709-718.

Methodology_Citation:

Citation_Information:

Originator: Echols, K.R.

Publication_Date: 1992

Title:

Chromatographic behavior of polychlorinated biphenyls, dibenzodioxins and dibenzofurans on porous graphitic carbon and the development of an automated fractionation system

Publication_Information:

Publication_Place: Columbia, Missouri

Publisher: University of Missouri

Methodology_Type: Lab

Methodology_Identifier:

Methodology_Keyword_Thesaurus: None

Methodology_Keyword: dialysis

Methodology_Keyword: cleanup

Methodology_Keyword: fractionation

Methodology_Description:

The collected eluates from the porous graphitic carbon column were concentrated by rotary evaporation and then were subjected to final fractionations on columns of alumina (Feltz et al, 1995). The alumina (3.6 g of basic alumina in 5-mL serological pipettes) was prewashed with 5% (v/v) CH2Cl2 in hexane, the concentrated PCDD/PCDF solutions (in nonane) were applied, and the alumina was washed with 12 mL of 5% (v/v) CH2Cl2 in hexane. the resultant eluate was discarded, and the PCDDs and the PCDFs were eluted with 15 mL of CH2-Cl2. Eluates collected from alumina were transferred to conical autoinjector vials. Into each vial was spiked 1.0 ng of ¹³C₁₂-1,2,33,4-TCDD, the instrumental internal standard. The solutions were evaporated with streams of nitrogen to about 10 microliter volumes.

Methodology_Citation:

Citation_Information:

Originator:

Feltz, K.P.; Tillitt, D.E.; Gale, R.W.; Peterman, P.H.

Publication_Date: 1995

Title:

Automated HPLC fractionation of PCDDs and PCDFs and planar and nonplanar PCBs on C18-dispersed PX-21carbon.

Series_Information:

Series_Name: Environ. Sci. Technol.

Issue_Identification: 29

Other_Citation_Details: pp. 709-718.

Methodology_Type: Lab

Methodology_Identifier:

Methodology_Keyword_Thesaurus: None

Methodology_Keyword: analysis by GC/MS

Methodology_Description:

GC/MS analysis was performed using an HP 5890 Series II GC interfaced to a Finnigan-4023 quadrupole MS. An HP 7673 autosampler was used to inject 2 of 10 microliters of the purified dialyzates. The analytes were chromatographed on a 60-m x 250 micrometer i.d. (0.25-micrometer film thickness) DB-5 capillary column with an initial hold of 1 minute at 120 degrees Centigrade, followed by a ramp to 210 degrees Centigrade at 20 degrees per minute, then to 300 degrees Centigrade at 3 degrees Centigrade per minute, with a final hold of 15 minutes. Mass windows were established for each of the homolog groups and were monitored sequentially during the temperature program. Within each mass window, three or four ions were measured for positive identification of each analyte

Methodology_Type: Lab

Methodology_Identifier:

Methodology_Keyword_Thesaurus: None

Methodology_Keyword: H4IIE Bioassay

Methodology_Description:

The H4IIE bioassay procedures were as reported by Tysklind et al. (1994). The H4IIE rat hepatopma cells were seeded in 96-well quadriplicate microtiter plates at 7000 cells/ well in 250 microliter of D-MEM culture media (Tillitt et al, 1991). After a 24 hour incubation period, the cells were dosed with sample extracts or with standards in 5-microliter volumes of isooctane. The cells were exposed, in quadruplicate, to six different concentrations of the samples in a 4-fold dilution series. The samples' responses were calibrated against those of TCDD standards for the determination of TCDD equivalents (TCDD-EQ). TCDD standards were dosed at eight concentrations: 0; 0.069; 0.206; 0.617; 1.85; 5.5; 16.7; and 50 pg/well. Ethoxyresorufin-O-dethylase (EROD) activity in the H4IIE cellls was measured kinetically (Tysklind et al, 1994) in a fluorometric plate reader (Cytofluor 2300, Millipore Corp., Bedford, MA). Linear portions of the dose-response curves were used to compare the relative potencies of the samples with those of the standards of TCDD. The determination of TCDD equivalents (TCDD-EQ) was by slope-ratio assay (Finney, 1980), as previously described (Ankley et al, 1991) and were calculated as previously described (Tillitt et al, 1991; Ankley et al 1991).

Methodology_Citation:

Citation_Information:

Originator:

Tysklind, M.; Tillitt, D.; Eriksson, L.; Lundgren, K.; Rappe, C.

Publication_Date: 1994

Title:

A toxic equivalency factor scale for polychlorinated dibenzofurans

Series_Information:

Series_Name: Fundam. Appl. Toxicol.

Issue_Identification: 22

Other_Citation_Details: p. 277-285

Methodology_Citation:

Citation_Information:

Originator: Tillitt, D.E.; Giesy, J.P.; Ankley, G.T.

Publication_Date: 1991

Title: (Article about testing in the bioassay)

Series_Information:

Series_Name: Arch. Environ. Sci. Technol.

Issue_Identification: 25

Other_Citation_Details: p. 87

Methodology_Citation:

Citation_Information:

Originator: Finney, D.J.

Publication_Date: 1980

Title: Statistical Methods in Biological Assay

Publication_Information:

Publication_Place: London, United Kingdom

Publisher: Charles Griffin

Methodology_Citation:

Citation_Information:

Originator:

Ankley, G.T.; Tillitt, D.E.; Giesy, J.P.; Jones, P.D.; Verbrugge, D.A.

Publication_Date: 1991

Title: unknown

Series_Information:

Series_Name: Can J. Fish. Aquat. Sci.

Issue_Identification: 48

Other_Citation_Details: pp.1685-1690.

Process_Step:

Process_Description: unknown

Process_Date: unknown

Spatial_Data_Organization_Information:

Indirect_Spatial_Reference: Based on local reference names.

Entity_and_Attribute_Information:

Overview_Description:

Entity_and_Attribute_Overview:

Entity - Bayo Meto stream; Associated attributes - polychlorinated dibenzoz-p-dioxins (PCDDs) and polychorinated dibenzofurans (PCDFs).

Entity_and_Attribute_Detail_Citation: unknown

Distribution_Information:

Distributor:

Contact_Information:

Contact_Organization_Primary:

Contact_Organization:

U.S. Geological Survey, Biological Resources
Division, Columbia Environmental Research Center

Contact_Person: Christopher Henke

Contact_Position: Webmaster

Contact_Address:

Address_Type: mailing and physical address

Address: 4200 New Haven Rd

City: Columbia

State_or_Province: MO

Postal_Code: 65201

Contact_Voice_Telephone: 573-875-5399

Contact_Facsimile_Telephone: 573-876-1896

Contact_Electronic_Mail_Address: chris_henke@usgs.gov

Distribution_Liability:

Although these data have been processed successfully on a computer system at the U.S. Geological Survey, no warranty expressed or implied is made regarding the accuracy or utility of the data on any other system or for general or scientific purposes, nor shall the act of distribution constitute any such warranty. This disclaimer applies both to individual use of the data and aggregate use with other data. It is strongly recommended that these data are directly acquired from a U.S. Geological Survey server, and not indirectly through other sources which may have changed the data in some way. It is also strongly recommended that careful attention be paid to the contents of the metadata file associated with these data. The U.S. Geological Survey shall not be held liable for improper or incorrect use of the data described and/or contained herein.

Custom_Order_Process: Please contact distributor.

Metadata_Reference_Information:

Metadata_Date: 200004

Metadata_Contact:

Contact_Information:

Contact_Organization_Primary:

Contact_Organization:

Raytheon Information Technology and Scientific
Services (ITSS)

Contact_Person: Cheryl Solomon

Contact_Position: Ecosystem Coordinator

Contact_Address:

Address_Type: Mailing and Physical Address

Address: 4500 Forbes Boulevard

City: Lanham

State_or_Province: MD

Postal_Code: 20706

Country: USA

Contact_Voice_Telephone: 301 794-3049

Contact_Facsimile_Telephone: 301 794-3164

Contact_Electronic_Mail_Address: solomon@gcmd.nasa.gov

Metadata_Standard_Name:

NBII Content Standard for National Biological Information Infrastructure Metadata

Metadata_Standard_Version: December 1995

Metadata_Access_Constraints: None

Metadata_Use_Constraints: None