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Centre Analytical Laboratories, Inc.
3048 Research Drive State College, PA 16801
www.centrelab.com
^P hone: (814) 231-8032
Fax: (814) 231-1253 or (814) 231-1580
Analytical Report
Fluorochemical Characterization of Sediment and Sludge Samples Cleveland, TN (W1973)
Centre Analytical Laboratory Report No. 023-014Q (Revision 1)
Revision Date 3/27/01
Testing Laboratory Centre Analytical Laboratory, Inc.
3048 Research Drive State College, PA 16801
3M Environmental Laboratory Contact Kent R. Lindstrom Bldg. 2-3E-09 P.O. Box 33331
St. Paul, MN 55133-3331 Phone: (651)778-5352
Requester Kris Hansen Ph.D. 3M Environmental Technology & Safety Services
Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331
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1 Introduction
Results are reported for the analysis of a series of sediment and sludge samples received by Centre Analytical Laboratories, Inc. (Centre) from the 3M Environmental Laboratory. Landfill leachate samples were not collected from this city. The samples were collected from Cleveland, Tennessee and are part of 3M Project W1973. The Centre study number assigned to the project is 023-014.
Specific fluorochemical characterization by liquid chromatography / tandem mass spectrometry (LC/MS/MS) was requested for all samples. A total of 7 samples were received for analysis.
The samples were prepared and analyzed by LC/MS/MS for the following list of fluorochemicals:
Table 1: Target Analysis
Compound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonylamide Perfluorooctanoate
Acronym PFOS PFOSA POAA
The analytical methods used for originally developed for water samples and were validated by Centre. The water sample validation protocol and results are on file with Centre. The methods were modified for the sediment and sludge samples. The procedures have not been fully validated for these matrices. Data presented here is the highest quality data available at this time.
2 Sample Receipt
The samples were submitted in individual plastic containers and were not preserved. Seven individual sample containers were received. Samples were received on 7/28/00. Sample collection dates were not supplied. Chain-of-custody information is presented in Attachment C.
3 Holding Times
The analytical method used was validated against a maximum holding time of 14 days in water samples. Stability after this time period has not been validated. However, it should be noted that field fortifications in water and other matrices have shown acceptable recoveries at 100 and 1000 ng/L for periods longer than 14 days.
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4 Methods - Analytical and Preparatory
4.1 LC/MS/MS
4.1.1 Sample Preparation for LC/MS/MS Analysis
Water samples (field blanks) were initially treated with 200 uL of 250 mg/L sodium thiosulfate solution to remove residual chlorine. Solid phase extraction (SPE) was used to prepare the samples for LC/MS/MS analysis. A forty-milliliter portion of sample was transferred to a C18 SPE cartridge. The cartridge was first eluted with 5 mL of 40% methanol in water solution. The eluate was discarded and the SPE column was then eluted with 100% methanol. A 5 mL portion of methanol was collected for analysis by LC/MS/MS. This treatment resulted in an eight-fold concentration of the samples prior to analysis.
For the sediment and sludge samples, a representative portion of sample (5 grams) was first extracted into 5 ml of methanol. The extracts were filtered and diluted to a final volume of 40 mL with Type I water. The diluted extracts were then treated in the same manner as the water samples, beginning with the solid phase extraction.
4.1.2 Sample Analysis by LC/MS/MS
In HPLC, an aliquot of extract is injected and passed through a liquid-phase chromatographic column. Based on the affinity of the analyte for the stationary phase in the column relative to the liquid mobile phase, the analyte is retained for a characteristic amount of time. Following HPLC separation, ES/MS provides a rapid and accurate means for analyzing a wide range of organic compounds, including fluorochemicals. Electrospray is generally operated at relatively mild temperatures; molecules are ionized, fragmented, and detected. Ions characteristic of known fluorochemicals are observed and quantitated against standards.
A Hewlett-Packard HP1100 HPLC system coupled to a Micromass Ultima MS/MS was used to analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). Samples were extracted on 8/21/00 and analyzed by MS/MS between 8/23/00 and 8/28/00. The HPLC and MS/MS methods used for analysis and instrument parameters can be found in Attachments D.
5 Analysis
5.1 Calibration
A 7-point calibration curve was analyzed at the beginning and end of the analytical sequence for the compounds of interest. The calibration points were prepared at 0, 25, 50, 100, 250, 500, and 1000 ng/L (ppt) for LC/MS/MS analysis. The instrument response versus the concentration was plotted for each point. Using linear regression with 1/x weighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determination (r2) were determined. A calibration curve is acceptable if r >.0.985 (r2 > 0.970).
Calibration standards are prepared using the same SPE procedure used for samples.
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Calibration check standards were analyzed periodically (every three to five sample injections) throughout the analysis sequence. Compliance is obtained if the standard analyte concentrations are within +/-20% of the actual value.
For the results reported here, calibration criteria were met.
5.2 Blanks
Extraction blanks were prepared and analyzed with every extraction batch of samples. The extraction blanks should not have any target analytes present at or above the concentration of the low-level calibration standard. For these samples, the extraction blanks were compliant.
Instrument blanks in the form of clean methanol solvent were also analyzed after every highlevel calibration standard, and after known high-level samples. Again, the blanks should not have any target analytes present at or above the low-level calibration standard. For the samples presented here the instrument blanks are compliant.
5.3 Surrogates
Surrogate spikes are not a component of the LC/MS/MS analytical methods.
5.4 Matrix Spikes
Matrix spikes were prepared for every field sample using all compounds of interest. Matrix spike recoveries are given in Attachment B.
5.5 Duplicates
All field samples were analyzed in duplicate. Results are given along with the sample results in Attachment A.
5.6 Laboratory Control Samples
For LC/MS/MS analyses, Milliq water was spiked with all compounds of interest at 25 and 250 ng/L during each extraction set. All recoveries for all compounds were between 70-130% in each LCS. Results are given along with the raw data in Attachments D.
5.7 Sample Related Comments
Empty containers were submitted as filed blanks. The containers were treated with 40 mL of Milliq water and analyzed as per the method. There are no other sample related comments for this data set.
6 Data Summary
Please see Attachment A for a detailed listing of the analytical results. Field blank water results are reported in parts per trillion (ppt) (ng/L). Sediment and sludge sample results are reported in parts per billion (ppb) (ug/Kg) on both an as-received and dry-weight basis.
7 Data/Sample Retention
Samples are disposed of one month after the report is issued unless otherwise specified. All electronic data is archived on retrievable media and hard copy reports are stored in data folders maintained by Centre.
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8 Attachments
8.1 Attachment A: Results 8.2 Attachment B: Matrix Spike Recoveries 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data
9 Signatures
ydohn M.iv i. FI ilad ihied irtyJOperations Manager
4M
KevinIJ Lloyd, Vice Piresident
Other Lab Members Contributing to Data Karen Smith
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ANALY _______ I_____________________________________________________________
Centre Analytical Laboratories, Inc.
3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253
Analytical Results W1973 Cleveland, Tennessee (GEN 013)
3M Sample Identification
MC-110K Sediment Site 1 MC-110K Sediment Site 1 dup MC-111K Sediment Site 2 MC-111K Sediment Site 2 dup MC-112K Sediment Site 3 MC-112K Sediment Site 3 dup MC-144K POTW Sludge MC-144K POTW Sludge dup
PFOS (ug/Kg) (as received)
NQ ND NQ NQ NQ NQ 30.5 34.1
PFOSA (ug/Kg) (as received)
ND ND NQ NQ ND ND 0.441 0.446
POAA (ug/Kg) (as received)
ND ND NQ NQ ND ND 0.817 0.741
3M Sample Identification
MC-110K Sediment Site 1 MC-110K Sediment Site 1 dup MC-111K Sediment Site 2 MC-111K Sediment Site 2 dup MC-112K Sediment Site 3 MC-112K Sediment Site 3 dup MC-144K POTW Sludge MC-144K POTW Sludge dup
PFOS (ug/Kg) (dry weight)
NQ ND NQ NQ NQ NQ 116 130
PFOSA (ug/Kg) (dry weight)
ND ND NQ NQ ND ND 1.68 1.7
POAA (ug/Kg) (dry weight)
ND ND NQ NQ ND ND 3.11 2.82
Limit of Detection (LOD) for the procedure is appoximately 0.08 ug/Kg for all compounds (as received) Limit of Quantitation (LOQ) for the procedure is 0.20 ug/Kg for all compounds (as received) ND - Compound not detected NQ - Compound detected at a level between the LOD and LOQ. Result is not quantifiable. ND < LOD < NQ < LOQ
% Solids
79.4 79.4 88.07 88.07 81.71 81.71 26.26 26.26
Please refer to the reverse side for our standard terms and conditions.
3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253
Analytical Results W1973 Cleveland, Tennessee (GEN 013)
3M Sample Identification
PFOS (ng/L)
PFOSA (ng/L)
POAA (ng/L)
MC-113K Field Blank MC-114K Field Blank MC-145K Field Blank
ND ND ND ND ND ND ND ND ND ND ND ND
Limit of Detection (LOD) for the procedure is approximately 2.5 ng/L for PFOS and PFOSA and 7.5 ng/L for POAA
Limit of Quantitation (LOQ) for the procedure is 25 ng/L for all compounds
ND - Compound not detected
NQ - Compound detected at a level between the LOD and LOQ. Result is not quantifiable.
ND < LOD < NQ < LOQ
Please refer to the reverse side for our standard terms and conditions.
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Attachment B: LC/MS/MS Laboratory Spike Recovery
Sample ID: Spiked Amount (ng/L):
MC-110K 250
PFOS PFOSA POAA
Sample Concentration
(ng/L)
2.9 0 0
Matrix Spike Result (ng/L)
225 238 237
Matrix Spike Result
(% Recovery)
88.8 95.2 94.8
Criteria (Pass / Fail)
PASS PASS PASS
Lower Recovery Limit:
70
Upper Recovery Limit:
130
Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only.
Concentrations represent amounts of compound present in the sample extract
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Attachment B: LC/MS/MS Laboratory Spike Recovery
Sample ID: Spiked Amount (ng/L):
MC-111K 250
PFOS PFOSA POAA
Sample Concentration
(ng/L)
11.7 3.3 12.9
Matrix Spike Result (ng/L)
249 237 285
Matrix Spike Result
(% Recovery)
94.9 93.5 108.8
Criteria (Pass / Fail)
PASS PASS PASS
Lower Recovery Limit:
70
Upper Recovery Limit:
130
Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only.
Concentrations represent amounts of compound present in the sample extract
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Attachment B: LC/MS/MS Laboratory Spike Recovery
Sample ID: Spiked Amount (ng/L):
MC-112K 250
PFOS PFOSA POAA
Sample Concentration
(ng/L)
9.1 0 0
Matrix Spike Result (ng/L)
235 217 240
Matrix Spike Result
(% Recovery)
90.4 86.8 96.0
Criteria (Pass / Fail)
PASS PASS PASS
Lower Recovery Limit:
70
Upper Recovery Limit:
130
Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only.
Concentrations represent amounts of compound present in the sample extract
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Attachment B: LC/MS/MS Laboratory Spike Recovery
Sample ID: Spiked Amount (ng/L):
MC-144K 250
PFOS PFOSA POAA
Sample Concentration
(ng/L)
3810 55.2 102
Matrix Spike Result (ng/L)
4081 126 221
Matrix Spike Result
(% Recovery)
108.4 28.3 47.6
Lower Recovery Limit:
70
Upper Recovery Limit:
130
PFOS sample concentration is greater than 10X the spiking amount
Concentrations represent amounts of compound present in the sample extract
Criteria (Pass / Fail)
PASS FAIL FAIL
3M Environmental Laboratory
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Telephone: Sample Receiving: (651) 778-4948 Alternate: (651) 778-6753 FAX: (651)778-6176
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