Environ. Sci. Technol. 2004, 38, 4064-4070
Detection of Perfluorooctane Surfactants in Great Lakes Water BRYAN BOULANGER,† JOHN VARGO,‡ JERALD L. SCHNOOR,† AND K E R I C . H O R N B U C K L E * ,† University of Iowa, Department of Civil and Environmental Engineering, SC 4105, Iowa City, Iowa 52240, and University Hygienic Laboratory, 102 Oakdale Campus, Iowa City, Iowa 52242
Widespread use of perfluorooctane surfactants has led to ubiquitous presence of these chemicals in biological tissues. While perfluorooctane surfactants have been measured in blood and liver tissue samples of fish, birds, and mammals in the Great Lakes region, data for the aqueous concentrations of these compounds in the Great Lakes or other ambient waters is lacking. Sixteen Great Lakes water samples were analyzed for eight perfluorooctane surfactants. The monitored perfluorooctane surfactants were quantitatively determined using single quadrupole HPLC/ MS and qualitatively confirmed using ion trap MS/MS. Additionally, PFOS was quantitatively confirmed using triple quadrupole LC/MS/MS. Concentrations of PFOS and PFOA in the two lakes ranged from 21-70 and 27-50 ng/L, respectively. Analysis also showed the presence of PFOS precursors, N-EtFOSAA (range of 4.2-11 ng/L) and FOSA (range of 0.6-1.3 ng/L), in all samples above the LOQ. PFOSulfinate, another precursor, was identified at six of eight locations with a concentration range, when present, of 99 transition)
single quad
% difference
LOLA8-1A LOLA8-2A LOLA8-3A LOLA8-4A LOLA8-5A LOLA8-1B LOLA8-2B LOLA8-3B LOLA8-4B LOLA8-5B Blank 1-1 Blank 1-2 Blank 1-3 Blank 1-4 Blank 1-5 ER91-1A ER91-2A ER91-3A ER91-4A ER91-5A ER91-1B ER91-2B ER91-3B ER91-4B ER91-5B
14 27 21 13 2.4 nda 56 17 (0.7)c nd nd nd nd nd nd (0.8) 24 6.6 (0.6) nd (0.7) 18 11 2.7 (0.5)
14 25 20 12 2.2 nd 46 15 (0.3) nd nd nd nd nd nd (0.05) 22 6.1 (0.2) nd nd 17 10 2.4 (0.1)
0.0 7.4 4.8 7.7 8.3 -b 18 12 8.3 7.6 5.6 9.1 11 -
and ) nondetectable. b Dash represents samples outside of the calibrated range of both instruments. c Values in parentheses are extrapolated values. Analytes present but at levels less than the lowest standard in the calibration curve ( 99 transition, varied less than 18% for all sample extracts analyzed within the calibrated range (Table 5). Concentrations in the extracts at two months were a factor of 8 higher than the seven month samples analyzed by both methods, suggesting that storage of our extracts was an issue. Water concentrations of PFOS and PFOA in the Great Lakes are comparable to concentrations measured in other surface waters despite the difference in methods (Table 6). PFOS in the lakes fall within the concentration range of those reported for water samples collected during 3M’s initial study of surface water near perfluorochemical production facilities in Columbus, GA, Port St. Lucie, FL, Decator, AL and Mobile, AL (23). Lake Erie PFOS concentrations are in the same concentration range of samples taken upstream of a production facility in the Tennessee River but are lower than water concentrations measured downstream of the plant (18). Mean PFOS concentrations in Lake Ontario are 1.7 times greater than the mean PFOS concentrations in Lake Erie but are not statistically different at the 95% confidence level. PFOS concentrations in both lakes are an order of magnitude lower than water samples collected after a spill of aqueous fire fighting foam (AFFF) in Etobicoke Creek outside of Toronto, Canada (6). PFOS concentrations reported for both lakes are higher than PFOS mean concentrations reported for Lake Biwa, Osaka Bay, and Ariake Bay in Japan but are comparable to PFOS concentrations reported for Tokyo Bay and the Tama River in Japan (7). PFOA concentrations are statistically the same in Lake Erie and Lake Ontario. PFOA
TABLE 6. Concentrations of Perfluorooctane Surfactants in Surface Water Reported in the Literature Presented with Values from This Study compound
site
Municipal Marina, Columbus, GA Martin County Marina, Port St. Lucie, FL Drain Pond, Port St. Lucie, FL Flint Creek, Decatur, AL Mobile River, Mobile, AL Three Mile Creek, Mobile, AL Etobicoke Creek, Toronto, Canada Tennessee River, Decator, AL Tokyo Bay, Japan Osaka Bay, Japan Lake Biwa, Japan Ariake Bay, Japan Tama River, Japan Lake Erie, Canada/USA Lake Ontario, Canada/USA PFOA Municipal Marina, Columbus, GA Drain Pond, Port St. Lucie, FL Flint Creek, Decatur, AL Mobile River, Mobile, AL Etobicoke Creek, Toronto, Canada Tennessee River, Decator, AL Lake Erie, Canada/USA Lake Ontario, Canada/USA N-EtF OSAA Lake Erie, Canada/USA Lake Ontario, Canada/USA PFOSu lfinate Lake Erie, Canada/USA FOSA Lake Erie, Canada/USA Lake Ontario, Canada/USA
sample size
concentration range (ng/L)
year
group
4 2
55-83 137-138 4.5 × 104 to 5.1 × 104 108-114 34.7-43 32-39 nd to 2.2 × 106 16.8-144 8-59
