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KnvironnuTital Tit'hmilojjv and Svnicts I'O Hi |\ <; i l | Si. Haul. \|\ H - i l i l h i: 77N (>-+-42 3M Laboratory Report LCMSMS Analysis of Extracts reported in: "Preliminary Report Analysis of Perfluorinated Compounds in Environmental Samples'1by P. Jones and K. Kannan Report number FACT-GEN-008 Testing Laboratory 3M Environmental Technology & Safety Services 3M Environmental Laboratory Fluorine Analytical Chemistry Team (FACT) 2-3E-09 935 Bush Avenue, St. Paul, M N 55106, Laboratory Contact Kris Hansen, Ph.D. Bldg. 2-3E-09 P.O .B ox 3331 St. Paul, M N 55133-3331 Phone: (651)778-6018 FAX: (651) 778-6176 Requester 3M/Battelle Exposure Team (c/o Susan Beach) 3M Company Environmental Lab 2-3E-09 St. Paul, MN 000514 PAGE 10F 8 J.U Evr/m vW E V T .U LABORATORY REPORT NO. FACT-GEN-008 A' 1 Introduction Sample extracts, prepared by P. Jones and K. Kannan according to FACT-M-4.0, were screened using a M icromass Platform H a single quadrapole LCMS. These same extracts were re-screened by FACT itong a M icromass Quattro II, a triple quadrapole instrument (LCMSMS), which provides a more selective analysis than a single quad instrum ent Interferences that may provide a false positive response in LCMS analysis can be elim inated with the LCMSMS. Extracts from samples o f sea eagle plasma, bald eagle plasma, and fish were analyzed quantitatively for PFOS using the LCMSMS. In general, PFOS levels determined by LCMSMS were approximately h alf of those determ ined using LCMS. It is likely that matrix interference at or around mass 499 complicated the original LCMS analysis. This type o f matrix interference near mass 499 has been observed in other biological sam ples.For the LCMSMS analysis, quantitation was based on the 499 -> 99,130 daughter ions response. In the LCMSMS analysis, low levels o f PFOS (< 5 ppb) were detected in several o f the fish samples; these values are significantly lower than those reported by Jones and Kannan It is likely that a m atrix interferent caused an anomolously high response in the LCMS analysis. No PFOS above the lim it of detection was detected in the remaining fish samples analyzed by LCMSMS. Again, this is in contrast to the LCMS analysis. Additionally, all samples o f eagle plasma were screened for the following fluorochemicals: PFOSA, FFOSAA, M 570, M 556, POAA, PFHS, and PFDS (see Appendix B for definitions o f FACT acronyms). Very low levels (< 5 ppb) of PFOSA were observed in the North American bald eagle plasma samples. No PFOSAA, M 556, POAA, or M570 was detected in ary samples. PFHS was detected in every Baltic sea eagle plasma sample, while PFDS was preliminarily (no standard material available for confirmation) detected in every North American bald eagle plasma sample. This data is screening quality only. Only 2 high level (250-ppb) PFOS matrix spike samples (eagle plasm a) were extracted and analyzed 2 Sam ple Receipt P. Jones and K. Kannan delivered samples to the Environmental Lab. The samples were extracted and analyzed by them using an Environmental Lab LCMS on March 15-19,1999. After LCMS analysis, die extracts were submitted to FACT for LCMSMS analysis. There was no extraction paperwork subm itted w ith the samples. It is assumed that sample volume and final extract volume were the same. 3 H olding Times There is no holding time criteria associated with these samples for LC/ESMSMS analysis. 000515 PABE20FS J.U EXtr'IROXMEXTAL U BO RATO RY REPORT NO FACT-GEN-008 4 Methods - Analytical and Preparatory A nalytical m ethods FACT-M -3.1, Extraction of Potassium Perfluorooctanesulfonate or Other Fluorochemical Compounds from Serum or Other Fluid for Analysis Using HPLC-Electrospray/Mass Spectrometry: mndifirH by n o t extracting a matrix curve for use in quantitation. A pre-existing curve, extracted from rabbit sera, was used for quantitation. This modification will have the greatest effect on the fish samples. Extraction efficiencies o f most of the target fluorochemicals from the fish tissues are likely to be significantly lower than those from the plasm a For this reason, LCMSMS reported values for the fish tissue samples should be considered to be minimum. FACT-M -4.1, Analysis if Potassium Perfluorooctanesulfonate or Other Fluorochemical in Scrum or Other Fluid Using HPLC-Electrospray/Mass Spectrometry: modified by quantitating samples versus a standard curve extracted from rabbit sera, not from the sample matrix. H PLC/ESM S an d HPLC/ESM SM S In HPLC, an aliquot of extract is injected and passed through a reverse phase liquid chromatographic colum n Based cmthe affinity o f 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 time. For example, in a standard solution PFOS may elute at 8.0 minutes. Retention times between a standard PFOS solution and the analyte extracted from groundwater in this analysis were matched on the HPLC system to within 1%. Following HPLC separation, ESMSMS provides a rapid and accurate means for analyzing a wide range o f organic compounds, including fluorochemicals. Electrospray, an ionization technique used primarily for detection o f molecular ions, is generally operated at relatively m ild temperatures. Molecules are ionized, and a prim ary ion, characteristic of the analyte, is selected This ion is bombarded with high-energy gas; subsequent collisions create smaller secondary ionic fragments unique to the primary ion, which are detected For example, for PFOS (CgFnSQO analysis, ion 499 is selected as the characteristic primary io n This ion is fragmented into other ions such as 80 amu (corresponding to SCV), and 130 amu (CF2SCV)- Each o f these secondary fragments is detected and can be used to differentiate PFOS from other compounds that m ight have the same characteristic 499 amu primary ion, but different chemical compositions and secondary ion fragmentation patterns. Analysis 5.1 Quantitative Analysis For both the LCMS and LCMSMS analysis, quantitative results are based upon comparison o f analyte peak area in the sample with analyte peak areas generated using a standards extracted from rabbit sera. The extraction efficiency o f PFOS from sera o f other animals has been determined to be between 75-95% at all levels within the range of quantitation. It is likely that the extraction efficiency o f PFOS from eagle plasma is approximately the same. 5.2 Qualitative Analysis Eagle plasma sample extracts were qualitatively screened for PFOSA, PFOSAA, M 556, M570, POAA, PFHS, and PFDS. During the analysis, the extracts were bracketed by a minimum number of standards to monitor analyte retention time. Other than relative comparisons, no quantitative results are available. No PFDS standard material is available. Preliminary identification of PFDS in the extracts is based upon response of 3 reasonable daughter ions (599->80,99,130) at a reasonable retention time. 000516 PAGE3 OF5 JM EVVIRONMENT.-IL LABORATORY REPORT NO. FACT-GEN-008 5.3 Blanks Two container blanks were provided and extracted by Jones and Kannan. Extraction blanks were also prepared. No analytes were detected in the extracts of either the container blanks or the extraction blanks. 5.4 Matrix Spikes One PFOS m atrix spike at 250 ppb was prepared for each of two eagle plasma samples. Both m atrix spikes showed greater than 80% recovery. 5.5 Laboratory Control Samples Laboratory Control Samples are not a component o f this study. 5.6 Sample Related Comments A ll data is screening quality only. All analytical results offish tissue extracts should be considered to be very prelim inary, as the extraction efficiency o f the target fluorochemicals from matrices is not characterized. 4 Bata Summary Extracts from samples o f sea eagle plasma, bald eagle plasma, and fish were analyzed quantitatively for PFOS using The LCMSMS. In general, PFOS levels determined by LCMSMS were approximately h alf o f those determ ined using LCMS. It is likefy that m atrix interference at or around mass 499 complicated the LCMS analysis. For the LCMSMS analysis, quantitation was based on the 499 -> 99,130 daughter ions response. M atrix interference at 499 has been observed in otherbiological samples. Low levels o f PFOS (< 5 ppb) were detected in several o f the fish samples; these values are significantly lower than those reported ty Jones and Kannan. It is likely that a matrix interfererd caused an anomolously high response in the LCMS analysis. This type o f anomaly has been observed by FACT on other samples analyzed by LCM S and LCMSMS. No PFOS above the lim it of detection was detected in the remaining fish samples analyzed by LCMSMS. Again, this is in contrast to the LCMS analysis. Additionally, all samples of eagle plasma were screened for the following fluorochemicals: PFOSA, PFOSAA, M 570, M 556, POAA, PFHS, and PFDS (see Appendix B for definitions o fFACT acronyms). Very low levels (< 5 ppb) of PFOSA were observed in the North American bald eagle plasm a samples. No PFOSAA, M 556, POAA, or M570 was detected in any samples. PFHS was detected in every Baltic sea eagle plasma sample, while PFDS was preliminarily (no standard material available for confirmation) detected in every North American bald eagle plasm a sample. This data is screening quality only. Only 2 high level (250-ppb) PFOS matrix spike samples (eagle plasma) were extracted and analyzed. - 7 Data / Sample Retention Samples and extracts will be retained for fixture evaluation, if necessary. 000S17 PAGE 4 OF 8 3M ENVIRONMENTAL LABORATORY REPORT NO. FACT-GEN-008 9 Attachments 8.1 A ttach m en t A : Table o f LCMSMS Results for the Analysis o f Eagle Plasm a and F ish Tissue Sam ples 8.2 A ttach m en t B : Table o f FACT acronyms and form ulas 8.3 A ttach m en t C : D ata associated with LCM SM S analysis 8.4 A ttach m en t D : LCM S report by P. Jones and K. Kannan to te re s .'m .. /./... A __/SK^...{..^ -^ L & * * = . HaroldJohnson, Ai od Chemist 4 1 ^ V l tt D ate K ris Hansen, P h D ., FACT Group Leader D ate 000518 PAGE6 OF5 3M Environmental Lab - Fluorine Analytical Chemistry Team FA CT-G EN -008 Sam ple n um ber WTEA-SW E-93-020 WTEA-SW E-93 -017 W TEA-SW E-93-012 629-38263 629-38264 629-07411 629-35547 629-36389 629-37030 629-37021 T issue: Sea Eagle Plasm a Sea Eagle Plasm a Sea Eagle Plasm a B ald Eagle Plasm a Bald Eagle Plasm a B ald Eagle Plasm a B ald E agle Plasm a B ald Eagle Plasm a B ald Eagle Plasm a B ald E agle Plasm a L o c a tio n : B altic B altic B altic N. Am erica N. Am erica N. Am erica N. Am erica N. Am erica N. Am erica N. A m erica DEPFOS/mL PFHS? 125 detected 93 detected 215 detected 165 198 494 1047 226 371 374 PFDS? detected detected detected detected detected detected detected F980086 F970312 F970310 1998095 F97187 1998095 1998064 1998064 F980081 F970181 F97002 1998064 C arp, whole body Lake T rout whole body Lake T rout whole body B row n Trout m uscle C iscow et m uscle Brow n Trout Liver C hannel C atfish egg C hannel C atfish egg Lake T rout, whole body Lake T rout, whole body W alleye, whole body C hannel C atfish m uscle P ine River, MI Siskiw it, M I Sislriw it, M I D etroit River, M I L ake Superior D etroit River, M I Lake S t C laire, M I Lake S t C laire, M I Pine R iver, M I Lake Superior D etroit River, M I Lake S t C laire, M I BLD BLD BLD BLD BLD BLQ BLQ BLQ BLQ BLD BLD BLD BLQ = below lim it o f quantitation (10 ppb) B ID = lim it o f detection (approxim ately 1 ppb) 3M Confidential -Attomey/Client W ork Product Privileged - Do N ot Disclose 000519