LAAN-A-LM-E052

No.C81Liquid Chromatography Mass Spectrometry

Analysis of PFCs in Environmental Water Using Triple Quadrupole LC/MS/MS [LCMS-8030]Organofluorine compounds such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are highly stable chemical compounds which are widely used as water repellents, oil repellents and coating agents. These compounds do not decompose easily in the natural world due to their stability. Reports of their detection in rivers, streams, tap water, food, as well as in the atmosphere and in human blood has led

to concern of their effect on the human body as environmental pollutants.Here we conducted the simultaneous analysis of PFOA, PFOS, and related compounds using the LCMS-8030. The results of an environmental water moni tor ing study that we conducted are a lso presented.

n Impurity Delay Method

* The Impurity Delay Method is different from the test method specified by the International Organization for Standardization (ISO) and the Japan Industrial Standards (JIS).

Depending on the analytical conditions, PFOA existing in the mobile phase, in the online degasser, as well as in the flow line can become concentrated in the analytical column. Consequently, this PFOA impurity may be detected at the same time as the PFOA injected as the sample analyte. In order to separate the impurity PFOA existing in the HPLC system from

the analyte PFOA in the sample, a delay column was installed between the mixer and the sample injector. This method of delaying elution of the impurity until after elution of the analyte is called the Impurity Delay method (Fig. 1) and allows analysis of PFOA at different times (Fig. 2).

Degasser

Solvent Delivery Unit

System Controller

Auto Sampler

Column Oven

Mixer

Delay Column

Mass Spectrometer

Analysis Column

Fig. 1 Impurity Delay Method

2.5 5.0 7.5 10.0 12.5 15.0 17.5 min

0.0

1.0

2.0

3.0

4.0

5.0

(×10,000)

Blank (50 % MeOH injected)Blank (Sample not injected)PFOA 1000 ppt

Impurity PFOA

Fig. 2 Chromatogram of PFOA

Compounds Q1 Q3* CE (V)

%RSD (10 ppt,

n=6)LOQ (ppt)

LOD (ppt)

PFHpA [C7] 362.90 319.00169.15

1017 4.57 4.45 1.33

PFOA [C8] 412.90 368.95169.05

1020 6.81 5.46 1.64

L-PFHxS [C6] 398.90 80.0599.05

4037 9.29 7.97 2.39

PFNA [C9] 462.90 419.00219.10

1017 1.33 4.44 1.33

PFDA [C10] 512.90 468.90219.05

1217 5.92 4.98 1.49

PFOS [C8] 498.90 80.1099.15

3939 9.39 9.97 2.99

PFUdA [C11] 562.90 519.00169.00

1222 7.18 4.50 1.35

PFDoDA [C12] 612.90 568.95169.30

1220 3.95 3.72 1.12

PFTrDA [C13] 662.90 618.90169.15

1428 4.89 4.51 1.35

PFTeDA [C14] 712.90 668.90169.00

1429 5.55 4.04 1.21

Fig. 3 shows a chromatogram of 10 perfluorocarbons, which includes PFOA, PHOS and related compounds. Table 1 shows the quant i ta t ion resul ts . Area reproducibility (%RSD) was less than 10 % in every case when averaging 6 measurements of each substance at 10 ppt. Further, the quantitation limit (S/N=10) was less than 10 ppt and the detection limit (S/N=3) was less than 3 ppt. Fig. 4 shows the calibration curves for PFOA and PFOS. Excellent l inearity was obtained within the range of 5 to 1000 ppt, and similar results were obtained for the other compounds.

Table 1 Analysis Results for PFCs

Q3*: Upper – Quantifier Ion Lower – Qualifier Ion

SHIMADZU CORPORATION. International Marketing Division3. Kanda-Nishikicho 1-chome, Chiyoda-ku, Tokyo 101-8448, Japan Phone: 81(3)3219-5641 Fax. 81(3)3219-5710

No.C81

8.0 10.0 12.0 14.0 16.0 min

0.0

0.2

0.4

0.6

0.8

1.0(×100,000)

PFHpA

PFOA

L-PFHxS

PFNA

PFDA

PFOS

PFDoDA

PFTrDA

PFTeDA

PFUdA

0 250 500 750 Conc. (ppt)0.0

0.5

1.0

1.5

2.0

Area (×10,000)

0 250 500 750 Conc. (ppt)0.0

0.5

1.0

1.5

Area (×100,000)

PFOS [C8] R2=0.9993174

PFOA [C8] R2=0.9998063

Fig. 3 Chromatograms of PFCs (each 1 ppb, 10 μL injected) Fig. 4 Calibration Curves of PFOS [C8] and PFOA [C8] (5-1000 ppt, n=6)

n Analysis of Environmental WaterWe conducted analysis of environmental water samples (River A, River B, Waste Water C, Tap Water D). The collected samples were filtered through a 0.45-μm filter and analyzed without performing preconcentration. The results are shown in Table 2.

PFOA was detected in all of the environmental water samples. Additionally, other PFCs were detected at the ppt level. These results demonstrated that high-sensitivity analysis with high repeatability is possible with the LCMS-8030.

Table 2 Analysis Results for PFCs in Environmental Water

River Water A River Water B Waste Water C Tap Water DPFHpA [C7] - - - (1.2)PFOA [C8] 10.2 15.6 (2.0) 16.4L-PFHxS [C6] - (4.7) - -PFNA [C9] - 12.3 - (1.6)PFDA [C10] - - - -PFOS [C8] - 10.3 - -PFUdA [C11] - - - -PFDoDA [C12] - - - -PFTrDA [C13] (2.1) (2.3) (1.3) -PFTeDA [C14] - - - 5.7*Values in parentheses are outside the calibration curve range. nit: ppt

Table 3 Analytical Conditions

Column : Shim-pack FC-ODS (2.0 mm I.D. × 150 mm L., 3 μm) Probe Voltage : -3.5 kV (ESI-negative mode)Delay Column : Develosil Packed Column C30-UG-5 (4.0 mm I.D. × 35 mm L.) Nebulizing Gas Flow : 1.5 L/minMobile Phase A : 5 mmol/L Ammonium formate - water Drying Gas Flow : 10 L/minMobile Phase B : Acetonitrile DL Temperature : 250 °CGradient Program : 25 %B (0 min) – 85 %B (20 min) – 25 %B (20.01 – 30 min) BH Temperature : 400 °CFlow Rate : 0.2 mL/min DL Voltage/Q-array Voltage : Using default valuesInjection Volume : 10 μLColumn Temperature : 40 °C