Document rOgx65kdQaOvY1kDVbqxVZkJ

... . ^RiaG-cp^o .-r - f i- i t 3 M Environmental Laboratory- Fluorine Analytical Chemistry Team Kris Hansen - Sr. Analytical Chemist Fluorine Analytical Chemistry Team Building 2-3E-09 612-778-6018 Screening o f PFOS levels in Eagles and Albatross Summary: Ten samples ofbird sera ofbird sera, five from juvenile bald eagle and five from Layson albatross, we received at the Environmental Lab. The eagle sera was collected from birds in Northern Minnesota (1 sample), the Upper Peninsula ofM ichigan (2 samples), and die Lower Peninsula of Michigan (2 samples). All five albatross samples were obtained from birds found at the Officer dnbrplot on Sand Island within the Midway Atoll in the north central Pacific Ocean. The sera samples were extracted; extracts were analyzed quantitatively far perfluorooctane sulfonate (PFOS) by high-pressure liquid chromatography-electrospray mass spectrometry (HPLC-ESMS). Analyte identification was verified by comparison o f molecular ioa-HPLC retention time o f the extracted analyte-and standard materiaL Samples were quantitatively evaluated against a five-point solvent curve. The samples of eagle sera were determined to contain 30-77 ppb perfluorooctane sulfonate (PFOS); no PFOS was detected in the albatross above the lim it of quantitation (10 ppb). Specific results and analytical parameters are attached to this report The presence ofPFOS in samples of eagle sera was verified using HPLC-ESMSMS. This technique provides an additional degree of certainty to the analyte identification by specifically momtormg fragments daughter ions (m/z=80, 99, 130,180,230) characteristic of the PFOS primary ion (m/z TM499). The presence of low levels afPFOSA, pexfluorooctanesulfonylamide, was also confirmed in each of the samples of eagle sera. Experim ental summary: Sample preparation: Ion-pairing extraction In a pH controlled environment an ion-pairing reagent tetrabutyl ammonium sulfate (TBA), is used to extract the analyte from the m atrix Anionic compounds, like PFOS and pexfluorooctanoate (POAA), are selectively targeted by the cationic reagent Subsequent to the formation, of the TBA-anion pair, the analyte is transferred to a non-polar organic solvent (ethyl acetate), dried, and reconstituted in methanol for HPLC-ESMS analysis. HPLC: Characteristic retention timesfo r PFOS In HPLC, an aliquot of the extract is injected and passed through a chromatographic column. Based on the affinity of the analyte for the stationary-phase in the column relative to the liquid mobilephase passing through the column, the analyte is retained for a characteristic amount of time. For example, in a standard solution, PFOS may elute at 10.5 minutes. Retention times between a standard PFOS solution and the analyte extracted from sera in this analysis were matched to within 1% on the HPLC system. ES/MS: Detection and monitoring o fthe molecular ion Analysis ofPFOS standards indicates that the primary ion characteristic ofPFOS is m/z * 499 amu, corresponding to the mass of the anionic surfactant (CJFnSQj-). This ion was monitored selectively to maximize sensitivity. A scan of m/z9 100 to 1210 (negative only) was also collected. 000530 05/08/98 l ES/MSMS: Confirmation o fanalyte Identification Several samples in this set were analyzed by ESMSMS to verify the identity aftheFFO S analyte ion. ES-MSMS is very similar to ESMS, except that it adds an additional dimension of certainty to compound identification- As in ESMS, a compound specific ion is selected. After selection, the selected ion is characterized further by smashing it apart with high-energy gaa As a result o f the mmhing, ionic fragments, characteristic of the molecule, are created and detected. For example, for PFOS analysis, ion 499 is selected as the compound specific primary ion. This ion is smashed into other ions such as 80 amu (corresponding to SQQ, 99 amn (corresponding to FSQj"), 130 amu (corresponding to CFzS O f), 180 amu (C3F4SO1 ) and 230 amu (CjFSO')> I f PFOS is present in the pm pW of secondary fragments is fftw led at the detector. Q uality control summary: Due to sample size limitations, duplicate extraction and matrix spike analysis were not earned out on these samples. Quantitation o fPFOS levels was determined relative to a standard solvent curve instead of an extracted matrix curve. As the extraction efficiency ofFFOS is unknown, these results should be considered semi-quantitative and o f screening qualify. The standard curve was analyzed twice, aivt jf w the cm ipi One 230-ppb calibration wag analyzed five recovery was acceptable at S7%. Minimal quality control was associated with this analysis. I f more precision is required, the extracts may be re-analyzed. Lim it o f Quantitation The low standard analyzed with these samples was 10 ppb; this is the lim it o f quantitation associated with the analysis. Instrum ental specifics: HPLC system Hewlett Packard Series 1100 Liquid Chromatograph Column:Keystone Betasil C u 2 x 100 mm S jun particle size Flow rate: 300 pL/min. Solvent A: 2.0 mM Ammonium Acetate Solvent B: M ethanol Solvent Gradient: 43 to 90 %B in 9.30 mins. Hold at 90 %B for 3.50 mins. Return to 43 S B in 1.50 mins. Hold at 45 S B fbr 3J mins. Injection volume: 10 jiL Injections / sample: 1 Electrospray mass spectrometer Micromass Platform II API Mass Spectrometer, "Chick" MassLynx 2.4 Software Cone voltages: -60v Mode: electrospray negative Source temperature: 115 G Analyzer vacuum pressures: 0.000043 mBar, 0.000079 mBar Ions: 499,413, 369 Electrode: cross-flow 000531 05/08/98 2 & *ctrosprayMSMS Micromass Quattro II APIMan Spectrometer, "Madeline" MassLysx 3.1 Software Conevoltages: -60v Collision gas energy: 45 V Mode: dectrospcay negative Source temperature: 115 "C Analyzervacuum pressures: 0.000043 mBar, 0.000079 mBar PrimaryIon: 499; 498 Daughter ions: 80,99,130,180,230; 78 Electrode: Z-spray 05A)8/98 000532 3 LOCATIONS AND DATA FROM AVIAN BLOOD PLASMA SAMPLES TO: 3M Corporation Minneapolis, Minnesota BY: John P. Giesy and Associates Hilltop Place 2355 Bravender Road Williaznston, Michigan 48895 July 18,1994 000533 Avian blood plasma samples collected from two species, the bald eagle (Haliaeetus leucocephalus) and the Laysan albatross (Diomedea immutabilis) were sent to 3M for analysis for CgFI7S02 and C,F17C02. Additional data for these blood samples follows: Laysan albatrosses All samples o fLaysan albatrosses were collected from the Officers Club plot on Sand Island within the Midway Atoll in the north-central Pacific Ocean. Table 1 provides additional data on the birds sampled: Table 1. Band number, year bird was banded, age at collection o f blood sample, blood sample number, and date blood was collected for 5 Laysan albatrosses from Midway Atoll, north-central Pacific Ocean. Band Number 1247-60080 1247-60095 1367-32659 1137-90880 1067-19156 Year Banded 1993 1993 1985 1987 : 1978 Collection Age 0 0 8 6 15 Sample Number LAC 08093 LAC 09593 LA 616 LA 607 LA 617 Date Collected 18 May 1993 18 May 1993 13 Dec 1992 13 Dec 1992 13 Dec 1992 No other data on organochlorine pesticides from these birds is currently available, however, a seperate split sample o f each has been archived. Bald eagles All samples o fbald eagles were collected within the Midwest, with one from Minnesota, and two each from the upper and lower peninsulas o f Michigan (Figure 1). Table 2 provides additonal data on the birds sampled: 000534 000535 Table 2. Band number, location, county, region, date o fblood sample collection, sex, weight, and age in days o f5 nestling bald eagles from Minnesota and Michigan. Band No. 629-31740 629-31748 629-14593 629-39332 I 629-39339 ' Location Devil's Lake Slate River Falls Steve's Island Caulkins Creek Pickerel Channel County Menominee Baraga St. Louis Otsego Emmet Region U. Peninsula, MI U. Peninsula, MI Voyageurs N P.M N L. Peninsula, MI L. Peninsula, MI Date Collected 1989 1989 17 June 1992 3 June 1993 5 June 1993 Sex Unknown Unknown Male Female Female Weight Age in Days Unknown Unknown Unknown Unknown 2.7 kg 82 4.85 kg 228 4.25 kg 163