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Ak.H.a.6 -0 6 7 6 Centre Analytical Laboratories. Inc. 3 04 8 R esearch D rive Phone: (814) 231-8032 State C ollege, PA 16801 www .centrelab.com Fax: (814) 231-1253 or (814) 231-1580 Analytical Report FluorochemicarCharacterization of Water and Sediment Samples Port St. Lucie Resampling (E00-2003) Centre Analytical Laboratory Report No. 023-014P Testing Laboratory Centre Analytical Laboratory, Inc. 3048 Research Drive State College, PA 16801 3M Environmental Laboratory Contact Kent R. Linustrom Bldg. 2-3E-09 P .O .B ox 33331 St. Paul, MN 55133-3331 Phone: (651)778-5352 Requester Dale Bacon Ph.D. 3M Environmental Technology & Safety Services Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 PAGE 1 0 F 5 1 Introduction Results are reported for the analysis of a series of water and sediment samples received by Centre Analytical Laboratories, Inc. (C entre) from the 3M Environmental Laboratory. The samples were collected from Port St. Lucie, Florida and are part of 3M Project E00-2003. The Centre study number assigned to the project is 023-014. Specific fluorochemical characterization by liquid chromatography / tandem mass spectrometry (LC /M S/M S) and ion chromatography w as requested for all samples. A total of 45 sam ples' were received for analysis. The samples w ere prepared and analyzed by LC /M S/M S for the following list of fluorochemicals: Table 1: Target Analysis Compound Nam e Perfluorooctane Sulfonate Perfiuorooctane Sulfonvlamide Perfluorooctanoate Acronvm PFOS PFOSA POAA The analytical methods used for water sam ples were validated by Centre. Th e validation protocol and results are on file with Centre. T h e methods w ere modified for the sediment samples, however the procedures have not been fully validated for this matrix. Data presented here is the highest quality data available at this time. 2 Sample Receipt The samples w ere submitted in individual plastic containers and w ere not preserved. Forty-five individual sample containers w ere received. Sam ples were received on 7/25/00. The samples were collected between 7 /18/00 and 7 /19/00. Chain-of-custody information is presented in Attachment A. 3 Holding Times The analytical method used was validated against a maximum holding tim e of 14 days. Stability after this time period has not been validated, however it should be noted that field fortifications have shown acceptable recoveries at the 100 ng/L for periods longer than 14 days. [ i PAGE 2 OF5 000993 4 Methods - Analytical and Preparatory 4.1 LC/MS/MS 4.1.1 Sam ple P reparation fo r L C /M S /M S A n alysis W ater samples w ere initially treated with 200 uL of 250 m g/L sodium thiosulfate solution to remove residual chlorine. Solid phase extraction (S P E ) was used to prepare the samples for. LC/M S/M S analysis. A forty-milliliter portion of sam ple was transferred to a C 18 S P E cartridge. The cartridge was first eluted with 5 m L o f 40% methanol in w ater solution. The eiuate was discarded and the SPE column was then eluted with 100% methanol. A 5 m L portion of methanol was collected for analysis by LC /M S /M S. This treatm ent resulted in an eight-fold concentration o f the samples prior to analysis. For the sediment and sludge sam ples, a representative portion of sam ple (5 gram s) was first extracted into 5 ml of methanol. T h e extracts w ere filtered and diluted to a final volum e of 40 mL with Type I water. The diluted extracts w ere then treated in the sam e m anner as the water samples, beginning with the solid phase extraction. 4.1.2 Sam ple A n alysis b y LC /M S /M S 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 o f tim e. Following HPLC separation, ES/M S provides a rapid and accurate m eans for analyzing a w ide range of organic compounds, including fluorochem icals. Electrospray is generally operated at relatively mild temperatures; molecules are ionized, fragm ented, and detected. Ions characteristic of known fluorochemicals are observed and quantitated against standards. A Hewlett-Packard HP1.100 HPLC system coupled to a Micromass Ultima M S/M S w as used to analyze the sam ple extracts. Analysis w as performed using selected reaction monitoring (SR M ). W ater samples were extracted between 8/15/00 and 8/17/00 and analyzed by M S/M S between 8/18/00 and 8/23/00. Sedim ent and sludge samples were extracted on 8/18/00 and were analyzed by M S/M S on 8/21/00. T h e HPLC and M S/M S methods used for analysis and instrument param eters can be found in Attachments D and E. 5 Analysis 5.1 Calibration A 7-point calibration curve w as analyzed at the beginning and end of the analytical sequence for the compounds of interest Th e calibration points w ere prepared at 0, 25, 50, 100, 250, 500, and 1000 ng/L (ppt) for LC /M S /M S analysis. The instrument response versus the concentration was plotted for each p o in t Using linear regression with 1/x weighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determination (r2) w ere determined. A calibration curve is acceptable if r > 0 .9 8 5 (r2 > 0.970). Calibration standards are prepared using the sam e SPE procedure used for samples. PAGE3 OF5 000334 Calibration check standards w ere analyzed periodically (every three to five sam ple injections) throughout the analysis sequence. Com pliance 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 o f samples. The extraction blanks should not have any target analytes present at or above the concentration of the low-level calibration standard. For these sam ples, the extraction blanks w ere compliant. Instrument blanksjn. the form of clean m ethanol solvent w ere 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 instalm ent blanks are compliant. I 5.3 Surrogates Surrogate spikes are not a component o f the LC /M S/M S analytical methods. 5.4 Matrix Spikes Matrix spikes w ere prepared for every field sam ple using all compounds of in terest Matrix spike recoveries are given in Attachm ent C . Field spikes w ere submitted with the w ater sam ples. Field spike recoveries are also included in Attachment C . The results from the 200 ppt field spike for sam ple Q SW Palm C ity-C -FM S200ppt A indicate that this sample was spiked at 1000 ppt rather than 200 ppt. The results for I QSW P aim C ity-C -FM S-200ppt B indicate a 2 00 ppt spiking concentration. 5.5 Duplicates I All field samples w ere analyzed in duplicate. Results are given along with the sam ple results in Attachment B. 5.6 Laboratory Control Samples I For LC/M S/M S analyses, Milliq w ater was spiked with all compounds of interest at 25 and 250 ng/L during each extraction set. All recoveries for all compounds w ere between 70-130% in each LCS. Results are given along with the raw data in Attachments D and E. I 5.7 Sample Related Comments There are no other sam ple related comments for this data set. I 6 Data Summary I Please see Attachm ent B for a detailed listing of the analytical results. Surface w ater results are reported in parts per trillion (ppt) (ng/L). Sedim ent and sludge sam ple results are reported in parts per billion (ppb) (ng/g) on both an as-received and dry-weight basis. I I I 0 0 S 9 S PAGE 4 OF 5 I 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. 8 Attachments 8.1 Attachment A: Chain-of-Custody 8.2 Attachment B: Results. 8.3 Attachment C: Matrix Spike Recoveries 8.4 Attachment D: LC/M S/M S Raw Analytical D ata (Surface W ater Sam ples) 8.5 Attachment E: LC/M S/M S Raw Analytical D ata (Sedim ent and Sludge Sam ples) 9 Signatures Kevin J Uoyd, Vice President D a te D a te Other Lab Mem bers Contributing to Data K aren Sm ith PAGE 5 OF 5 000996 ANALYTICAL REPORT fSBESSN. Centre A nalytical V W S B a . Laboratories. Inc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 A n aly tica l R es u lts E 00-2003 P o rt S t. L u cie , F L R esam plin g (w a te r s am p les) 3M S am p le Id e n tific atio n M D W P IN -R -O -C M D W P IN -R -O -C dup M D W P IN -lim e -C M D W P IN -Lim e-C dup M D W PO ut -C M D W PO ut-C dup N P W W T P E ff-C N P W W TP E ff-C dup N P W W TP C C -C N P W W TP C C -C dup PSLF Leach-C PSLF Leach-C dup T W # 2 Fire D ept-C T W # 2 Fire D ept-C dup SW #3 SH -C SW #3 SH -C dup T W # 3 Penpark-C T W #3 P enpark-C dup SW #1 Penpark-C SW #1 Penpark-C dup TW #1 Holiday Inn-C TW #1 Holiday Inn-C dup S W #2 M CM -C S W #2 M CM -C dup Q S W Palm City-C Q S W Palm City-C dup Blind Dup C1 Blind Dup C1 dup Blind Dup C2 Blind Dup C 2 dup PFO S (n g /L ) * -7* <25 <25 <25 <25 <25 <25 14.7 J 16.6 J 8 5 .5 7 8 .8 429 425 <25 <25 7.8 J 5.4 J <25 <25 5.2 J 4.1 J <25 <25 7.7 J 9.3 J 2930 2850 <25 <25 8.0 J 9.8 J P FO S A (n g /L) <25 <25 . <25 <25 <25 <25 <25 <25 4 .4 J 3 .5 J 7.0 J 8.0 J <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 3 0.0 2 7.5 <25 <25 <25 <25 PO AA (ng /L) <25 <25 <25 <25 <25 <25 15.1 J 14.1 J 4 2.9 4 0.2 1030 1020 <25 . <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 9 6 .9 97.1 <25 <25 <25 <25 J - Com pound is present, but below the reporting limit o f 25 ng/L. T h e result is an estim ated value. M ethod Detection Limits are approxim ately 2 .5 ng/L for PFO S and P F O S A and 7 .5 ng/L for POAA. P lease re fer to th e reverse side fo r o u r standard term s an d conditions. 000937 ANALYTICAL REPORT 4& 8SS^ Centre Analytical VWWBk Laboratories. Inc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 A n aly tica l R es u lts E 0 0-2 00 3 P o rt S t. L u cie, FL R esam p lin g (so lid s) 3M S am p le id e n tific a tio n N P W W T P Sludge-C N P W W T P Sludge-C dup SED #3 SH -C SED #3 SH -C dup SED#1 P enpark-C SED#1 Penpark-C dup SED #2 M CM -C SED#2 M C M -C dup PFO S (u g /K g ) * -r (as received ) 1 .3 6 1 .3 0 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 PFO SA (u g /K g ) (as re ce iv ed ) < 0 .2 0 0 < 0.200 < 0 .2 0 0 < 0 .2 0 0 < 0.200 < 0.200 < 0.200 < 0.200 - PO A A (ug/K g) (a s received ) < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 3M S am p le Id e n tific a tio n N P W W T P Sludge-C N P W W T P Sludge-C dup SED #3 SH -C SED #3 S H -C dup SED#1 Penpark-C S E D # t P enpark-C dup SED#2 M CM -C SE D #2 M C M -C dup PFO S (u g /K g ) (d ry w e ig h t) 6 2.9 6 0.2 < 0.261 < 0 .2 6 1 < 0.263 . < 0.26 3 < 0.304 < 0 .3 0 4 PFO SA (ug /K g ) (dry w eig h t) < 9 .3 < 9 .3 < 0.261 < 0.261 < 0.263 < 0.263 < 0 .3 0 4 < 0.304 PO A A (ug/K g) (d ry w eig h t) < 9 .3 < 9 .3 < 0.261 < 0 .2 61 < 0.263 < 0.263 < 0.304 < 0.304 J - Com pound is present, but below the reporting lim it. T h e result is an estim ated value. Please refer fo the reverse sid e fo r o u r standard term s and conditions. - V r-'x 'i 000998 BEST COPY AVAILABLE z Adsdhiotiwonnaolnsasmoupthlinmgaspites Environmental Sampling Sites North of Port St. Lucie, FL 000999  - * Vrt Adsdhiotwionnaolnsanmorpthlinmgaspites BEST COPY AVAILABLE Environmental Sampling Sites South of Port St. Lucie, FL