[Note]
Development and Application of Simultaneous Analytical

Method for

Perfluorinated Compounds in Waste Samples by LC/MS/MS
Mihoko YOSHIDA1, Shusuke TAKEMINE2 and Chisato MATSUMURA2
1 Water Environment Division, Hyogo Prefectural Institute of Environmental Sciences,3-1-27, Yukihira-cho, Suma-ku, Kobe, Hyogo 654-0037, Japan, 2 Environmental Safety Division,

LC/MS/MS を用いた廃棄物中における有機フッ素化合物 (PFCs)の一斉分析法の開発及び適用
吉田
１

光方子 1

秀祐 2

竹峰

松村

千里 2

兵庫県環境研究センター 水質環境科（〒654‑0037 神戸市須磨区行平町 3‑1‑27），2 安全科学科

The investigation was carried out to establish the simultaneous and high sensitive analysis for theperfluorinated compounds (PFCs) in waste sample.
In pretreatment of the waste, the extraction efficiency of three techniques; accelerated solvent
extractor (ASE), soxhlet extraction and ultrasonic extraction were compared and examined.
Operation blank test, recovery test spiked with mass labeled PFCs (MPFCs) and content
examination in waste sample were experimented for 14 kinds PFCs.
As for the pretreatment method, the ultrasonic extraction method which had shown good results
both in the operation blank and isotope spiked recovery tests were adopted. The PFCs in waste wereextracted with methanol and separated as well as concentrated with nitrogen-gas and analyzed by
LC/MS/MS determination. And the waste was used in solid form. PFCs were detected at retention
time between 3.75~7.15 min by the technique which was established in this study. In addition, thechromatogram of waste sample shows that PFCs and isomer were detected at almost the same time
without interference. Since the existence ratios of PFCs in various wastes are different, by
establishing profile of each waste at different sources, this study will contribute to developing
countermeasures that would prevent environmental contamination of PFCs at global level.

Ⅰ

INTRODUCTION

ashazardous,

persistentandbioaccumulative1)

properties have been concerned . Thus, in May 9 th,Thefluorochemical

perfluorooctanoate(PFOA)

compounds
and

such

2009, the 4 th Conference of the Parties (COP4) for theasperfluorooctane

Stockholm

Convention

on

Persistent

Organic

sulfonate(PFOS) are stain and water repellant. It is

Pollutants adopted perfluorooctane sulfonate andthese superior properties that are widely applied toperfluorooctane sulfonyl fluoride (PFOS and PFOSF)

various fields in the modern society for pursuingin Annex B. In addition, these PFOS and PFOSF werecomfortable and convenient life styles.

designated as a class I specified chemical substances

On the other hand, negative properties of PFCs such

under the Law Concerning the Examination and1Regulationof

Manufacture,

etc.,

of

Ⅱ

Chemical

MATERIALS AND METHODS

Substances in Japan, and were subject to global
regulation. Since the further production and use of

1. Target PFCs, Reagents and Reagent preparationthese compounds will be strictly controlled, theThe target substances of the development of ourwidespread of the compounds into the environment

analytical method are 14 compounds. The target

would be reduced. However, PFCs products have still

PFCs and octanol-water partition coefficient

been widely stocked and used as well as disposed and(log Kow) are shown in Table 1. The target PFCs indischarged into our living environment. It is highly

this study were perfluorocarboxylic acids (PFCAs):10,

likely that the compounds will continue to present

perfluoro alkyl sulfonates (PFASs): 4 substances andubiquitously in whole society through the various

mass-labeled PFCs (MPFCs)

environmental routes and media.

PFCAs

In recent years, many surveys and risk assessment(MPFASs):2 for surrogate compounds. The former

have been carried out with regard to environmental

target PFCs used PFAC-MXB as standard substances,

contamination of PFCs in various media including

and the latter MPFCs used MPFAC-MXA as internal

atmosphere and water2) -9)(MPFCAs):7,

were

mass-labeled

mass-labeled

PFASs. However, little information

standard substances, these were all commerciallyhas been available with regard to the waste generated

available products. The both mixture solutions wereas a result of anthropogenic activities and transported

manufactured by Wellington Laboratories Inc. The

to waste treatment facilities. PFCs are detected in high

PFOA-13C8 used as internal standard was theconcentrations from leachate at some final disposal

product of Cambridge Isotope Laboratories. All

sites10) 11). Thus, the investigation of PFCs incompounds

werelinearchains.

Methanolwas

waste will be an important information source

originally for residual agrochemical analysis use

to develop countermeasures for PFCs pollution.
In this study, sensitive method by using LC/MS/MS

obtained from Wako Junyaku Kogyo (Wako Purefor the determination of PFCs in waste samples wasreagents with the measurement of substances wasdeveloped and presented.

confirmed. The 100ug/L-standard solution for theChemical Industries, Ltd.). No interference of thecalibration

curve

was

preparedwith

2000ug/L-PFAC-MXB in methanol.

PFASs

PFCAs

Table 1

Target compounds (PFCs) and octanol-water partition coefficient (log Kow)

compoundabbreviation

carbonnumber

Perfluoropentanoic acid
Perfluorohexanoic acid
Perfluoroheptanoic acid
Perfluorooctanoic acid
Perfluorononanoic acid
Perfluorodecanoic acid
Perfluoroundecanoic acid
Perfluorododecanoic acid
Perfluorotridecanoic acid
Perfluorotetradecanoic acid
Perfluorobutane sulfonate
Perfluorohexane sulfonate
Perfluorooctane sulfonate
Perfluorodecane sulfonate

PFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
PFDoDA
PFTrDA
PFTeDA
PFBS
PFHxS
PFOS
PFDS

5
6
7
8
9
10
11
12
13
14
4
6
8
10

2

structual formulamolecular
log K owweightCF3(CF2)3COOH 264.0
CF3(CF2)4COOH 314.1
CF3(CF2)5COOH 364.1
CF3(CF2)6COOH 414.1
CF3(CF2)7COOH 464.1
CF3(CF2)8COOH 514.1
CF3(CF2)9COOH 564.1
CF3(CF2)10COOH 614.1
CF3(CF2)11COOH 664.1
CF3(CF2)12COOH 714.1
CF3(CF2)3SO3H 300.1
CF3(CF2)5SO3H 400.1
CF3(CF2)7SO3H 500.1
CF3(CF２)9SO3H 600.1

n.a.
3.26
3.82
4.30
4.84
5.30
5.76
6.41
n.a.
n.a.
n.a.
n.a.
5.25
n.a.

*n.a.: not available

Table 2

Characterization of waste samples

Sample No.

1

2

3

4

5

6

water content
ratio (%)

37.0

11.1

34.4

0.9

52.3

57.7

pH

6.8

8.0

7.6

dewateredsludgesludge

black

white

appearance
color

7.9
automobile shredded
shreddersolid
residue
residue
black
gray

7.4

6.8

sludgesludge

brown

white

procedure,

operation

blank

the

test

without

2. Waste samples

interference from the waste and recovery test using

The details of the characteristics of the waste samples

real waste samples spiked with 1ng MPFCs weresuch as water content, pH, and appearance are shown

carried out at the same time. In preparing samples,in Table2. The waste samples are dewatered sludge,

1ng of MPFCs was spiked to the waste sample asautomobile shredded residues (ASR), incombustible

surrogate.

general solid wastes generated from effluent treatment

The sample solutions extracted by ASE or soxhlet

facilities and incinerating process.

extraction were concentrated to about 1ml withnitrogen injection. The PFCs adsorbed on the3.

Equipment

andinstrumentation,

LC/MS/MS

cartridge were then eluted with 2mL methanol. The

analytical condition

eluent was concentrated to about 1mL using the

The solid phase extract cartridge adopted Precep-C

TurboVap LV. The pretreated solution extracted byagri (short) (Wako Pure Chemical Industries, Ltd.).

ultrasonic extraction was measured up to 10ml and

The target measurement substances were passed

TurboVap LV. The pretreated solution extracted bythrough the cartridge and adsorbed to the cartridge

ultrasonic extraction was measured up to 10ml andusing a Sep-Pak Concentrator System Controller Plus

1mL aliquot of the 10ml extract was taken for(Waters) by 10 mL/min. The extraction solution wasdetermination. Then 1ng of PFOA-13C8 standard

concentrated in TurboVap LV (Zymark) with nitrogen.

solution was spiked as internal standard to theAnalytical conditions of LC/MS/MS are shown in

obtained extract, as described above. And 5EL

Table 3. As for the ultrasonic generator, ULTRA

was injected into the LC/MS/MS for determination.

SONIC

ONE

For the measurement of minimum detection limit

Corporation) was used. A model 05PR-22 (Hitachi)(MDL), sample6 which contains little or no PFCs was

was used as the centrifugal separator. DIONEX

taken. The waste was spiked with standard mixture

ASE-200 (DIONEX) was selected for the Accelerated

methanol

Solvent Extractor (ASE). The pulverized wastes wereconcentration of 2ng/g. The recovery test was

prepared by vibrating sample mill (TI-100, HEIKO

repeated for 7 times and the results were used forCo.), and sieved with 0.5mm-mesh after drying

calculating MDL by using the following equation.

AUTOMATICWASHER(AS

solutionandadjusted

to

the

final

overnight at 50 degrees Celsius.
MDL = 2 × s × t(n-1,0.05)
4. Development of PFCs analysis technique in wastes : standard deviationand Examination of the preprocessing methodt(n-1,0.05) : t value of n-1 degree ofThefollowing

three

extraction

methods

freedom, level of significance 5%

werecompared and discussed for sample pretreatment:
ASE, soxhlet extraction in Methanol for 12hours andultrasonic extraction with Methanol. In each3

Table 3

Analytical condition for PFCs with LC/MS/MS

LC condition
Instrument
ACQUITY UPLC
(waters)
ColumnUPLC BEH C18
2.1×50mm
Retention gap Column UPLC BEH C18
2.1×100mm
Mobile PhaseA : 10mM Ammonium Acetate aq B : Acetonitrile
Gradient
0.0 → 8.0 min
B: 1 → 95%
8.0 → 8.1 min
B: 95 → 1%
Flow rate
0.3 mL / min
Column temp.
50℃
Injection volume
5µL
MSMS condition
Instrument
Ionization Mode
Desolvation temp
Cone gas flow
Collision gas flow

ACQUITY TQD
ESI (-)
300 ℃
20 L / hr
0.1 mL / min(waters)
Source temp.
120 ℃
Cappillary voltage
2kV
Desolvation gas flow 800 L / hrPFCAs

263.00313.00363.00413.00463.00513.00563.00613.00663.00713.00217.00315.00417.00467.00515.00565.00615.00

Product ion
Qnt.
Idt. 1
219.00269.00118.90318.90169.00368.90169.00418.90169.00468.90219.00518.80269.00568.90168.90618.80169.00668.70169.00172.00270.00371.90422.90469.80219.00519.80269.60569.90269.50PFASs

299.00399.00499.00599.00403.00503.00

79.90
79.90
79.90
79.90
83.90
79.90

Precursor ion
Compound name
PFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUdDA
PFDoDA
PFTrDA
PFTeDA- 13C 4MPFCAs PFBA
PFHxA
- 13C 2PFOA
- 13C 4PFNA
- 13C 5PFDA
- 13C 2PFUdDA- 13C 2
PFDoDA- 13C 2
PFBS
PFHxS
PFOS
PFDS
MPFASs PFHxS
PFOS- 18O 2
- 13C 4

4

98.90
98.90
98.90
98.90
103.0099.00

Idt. 2130.00130.0079.90

ConeCollision
Voltage Energy
18
9
18
9
18
11
18
11
18
13
21
13
18
15
24
15
24
17
24
15
15
13
15
11
27
11
24
15
21
14
21
17
24
14
51
57
69
80
55
65

37
46
55
67
47
56

Ⅲ RESULTS AND DISCUSSION

those of the PFCs extracted by ultrasonic extraction

MPFCAsmethod were under 1ng/g-wet. The contamination

M PFO S0

process. The concentrations of the other PFCs and

M PFH xS

confirmed cross contamination in the operation

20

M PD oD A

detected by the ASE and soxhlet extraction. The result

40

M PFU nD A

and PFHpA in PFCAs that exceeded 7ng/g-wet were

Ultrasonic60

M PFD Aare shown in Fig.1. High concentrations of PFHxAM PN AThe results of operation blank by using the 3 methods

Soxhlet80

M PFO A

Result of the pretreatment procedure

ASE

M PFH xA

1.

Recovery rate [% ]100

MPFASsFig.2 Recovery rate with MPFCs

level of PFCs was not as significant as to affect theanalysis seriously. The result of the recovery test of
the samples from 1 to 4 spiked with 1ng MPFCs is

2. Content examination in the waste sample

shown in Fig.2. The 3 color bar charts show the

The results of content in waste sample1-4 with every

average recovery rate. The recovery rate of themethod to compare extraction efficiency show in

MPFHxA and MPFDoA by the ASE, soxhlet

Fig.3.

extraction, as well as MPFHxS by the ASE were

The PFCs content were indicated to be deducted with

under 60%, while the rest of the recovery rates show

the content obtained by the operation blank. In

no significant differences among the extraction

ultrasonic extraction method, each sample were

methods. Despite the use of wastes in various forms

analyzed repeatedly 3 times and showed the range ofnd properties as target samples, the recovery rates ofconcentration (black bar line), the average (red bar

the samples from 1 to 4 were not significantly

charts). PFCs were detected from all waste samples.

affected by the extraction methods used in the study.

As an example of PFCs analysis, the PFCAs

It is, therefore, concluded that extraction canchromatograms of the standard solution (20ng/L) andbe performed by either technique without athe sample1 are shown in Fig.4, and the PFASs

problem.

chromatograms are shown in Fig.5, respectively. In
the chromatogram of standard solution (left), PFCAs
9.1

was

7.6

ASE

7.1

0.8

between3.75~7.15

min.

The

SoxhletPFCAs and isomer were detected almost at the same

Ultrasonictime

without

interferences.

And

the

minimum

detection limit values of PFCs obtained by ultrasonic

0.6

extraction method were 1.4 - 3.9ng/g.

0.4
0.2

PFDS

PFOS

PFBS

PFHxS

PFTeDA

PFTrDA

PFDoDA

PFDA

PFCAs

PFUnDA

PFNA

PFOA

PFHxA

PFHpA

0

PFPeA

Concentration (ng/g-wet)

6.7

detected

chromatograms of waste sample (right) show that

PFASs

Fig.1 PFCs concentration of operational blank

5

100

100

40

PFOS

PFDS

PFOS

PFDS

PFTeDA

PFTeDAPFBS

PFTrDA

PFTrDA

PFHxS

PFDoDA

PFDoDA

PFPeA

PFDS

PFOS

PFBS

PFHxS

PFTrDA

PFTeDA

PFDoDA

PFDA

PFNA

PFOA

PFHpA

PFUnDA

0

PFPeA

10

0
PFHxA

20

10

PFDA

30

20

PFUnDA

30

50

PFDA

40

60

PFUnDA

50

70

PFNA

60

PFOA

70

Sample 2

80

PFHpA

80
Concentration[ng/g-wet]

90

ASE
SoxhletUltrasonic

PFHxA

Sample 1

Concentration[ng/g-wet]

90

20

Sample 3

Sample 4
Concentration[ng/g-wet]

10

0

10

PFBS

PFHxS

PFNA

PFOA

PFHpA

PFPeA

PFDS

PFOS

PFBS

PFHxS

PFTeDA

PFTrDA

PFDoDAPFUnDA

PFDA

PFNA

PFOA

PFHpA

PFPeA

PFHxA

0
PFHxA

Concentration[ng/g-wet]20

Fig.3 PFCs concentration in waste sample comparing extraction between different 3 methods
C14 PFTeDA

6.00

7.00
8.00
9: MRM of 2 Channels ES663 > 618.8 (PFTrDA01)
2.69e5

3.00

7.09

4.00

5.00

6.00

100

C13 PFTrDA

7.00
8.00
9: MRM of 2 Channels ES663 > 618.8 (PFTrDA01)
4.29e4

C10 PFDS

0
4.00
090721-010

5.00

6.00

5.00

6.00

7.00
8.00
8: MRM of 7 Channels ES6.54 613 > 568.9 (PFDoA01)
2.66e5100

0
2.00
090721-029

4.00

5.00

6.00

7.00
8.00
7: MRM of 4 Channels ES6.19 563 > 518.8 (PFUdA01)
2.43e5100%

C11 PFUnDA
3.00

4.00

5.00

6.00

7.00
8.00
6: MRM of 9 Channels ES513 > 468.9 (PFDA01)
2.29e5

5.85

%

100

C10 PFDA

C8 PFOS

0

Time
2.00

3.00

4.00

5.00

6.00

7.00

8.00

4.00

5.00

6.00

5.13

100

7.00
8.00
4: MRM of 8 Channels ES413 > 368.9 (PFOA01)
2.46e5%

C8 PFOA
4.00

5.00

6.00

4.74

%

7.00
8.00
3: MRM of 2 Channels ES363 > 318.9 (PFHpA01)
2.51e5C7 PFHpA

0
2.00
090721-010

3.00

4.00

5.00

6.00

4.30

100

7.00
8.00
2: MRM of 5 Channels ES313 > 269 (PFHxA01)
1.83e5

5.00

6.00

3.00

4.00

5.00

6.00
5.85

100

%

7.00
8.00
1: MRM of 3 Channels ES263 > 219 (PFPeA)
1.45e5C5 PFPeA
Time
3.00

4.00

5.00

6.00

7.00
8.00
4: M RM of 8 Channels ES399 > 79.9 (PFH xS01)
85

5.00

6.00

7.00
8.00
2: M RM of 5 Channels ES299 > 79.9 (PFBS01)
99

5.00

6.00

7.00

4.99
5.49
4.93
5.19
4.90

100

7.00
8.00
2: M R M of 5 Channels ES299 > 79.9 (P FB S01)
8.90e40
4.00
090721-029
100

4.18
4.04 4.23

7.00
8.00
6: MRM of 9 Channels ES513 > 468.9 (PFDA01)
4.04e44 .43

C4 PFBS

0

Tim e
4.00

5.00

6.00

7.00

8.00

0

Tim e
4.00

8.00

0

Fig.5 PFASs chromatogram

Time
2.00

3.00

4.00

5.00

6.00

090721-029
5.50
5.50

100

5.40

0
2.00
090721-029

3.00

4.00

5.00

8.00

(Left:

standard

20ng/mL,

Right:

waste

5.51
5.52

6.00

5.13

100

7.00

5: MRM of 3 Channels ES463 > 418.9 (PFNA01)
1.58e47.00
8.00
4: MRM of 8 Channels ES413 > 368.9 (PFOA01)
6.44e4

3. Comparison of the concentrations of PFCs in solid0
2.00
090721-029

3.00

4.00

5.00

6.00

4.74

100

waste and pulverized waste

7.00
8.00
3: MRM of 2 Channels ES363 > 318.9 (PFHpA01)
1.18e4

Figure 6 shows the result of the content examination

0
2.00
090721-029

3.00

4.00

5.00

6.00

4.30

100

using two kinds of waste samples that were treated

7.00
8.00
2: MRM of 5 Channels ES313 > 269 (PFHxA01)
1.11e4differently; a solid waste sample directly extracted by

4.19

0
2.00

6.00

4.31

100

2.00
090721-029

3.00

4.00

5.00

6.00

5.00

6.00

3.76

100

3.58

ultrasonic methanol extraction method and a solid

7.00
8.00
1: MRM of 3 Channels ES263 > 219 (PFPeA)
5.03e3waste sample which has been pulverized prior to

%

4.00
3.75

5.00

6.10

0
3.00

7.00
8.00
4: M R M of 8 Channels ES399 > 79.9 (PF Hx S01)
1.23e5C6 PFHxS

0
4.00
090721-010%%

C6 PFHxA

100

6.00

5.23

6.00

4.62

0
2.00
090721-010

5.00

5.00

%

3.00

100

4.00
090721-010

4.00
090721-029

7.00
8.00
7: MRM of 4 Channels ES-

5.04

0
2.00
090721-010

0

%

3.00

6.00

3.19e4%%

C9 PFNA0
2.00
090721-010

5.00

6.19 563 > 518.8 (PFUdA01)

US-P1

5: MRM of 3 Channels ES463 > 418.9 (PFNA01)
1.87e5

5.50

100

4.00

7.00
8.00
6: M RM of 9 Channels ES499 > 79.9 (P FO S01)
84

6.15

0

5.76

PFAC-20090721-010

7.00
8.00
8: MRM of 7 Channels ES6.53 613 > 568.9 (PFDoA01)
5.22e4100

0
2.00
090721-029

5.99
6.12

6.43

3.00

6.00
5.61

6.00

100

0
2.00
090721-029

5.00

100

%

0
2.00
090721-010

5.00

%

%

3.00

4.00

100

C12 PFDoDA

0
2.00
090721-010

3.00

%

4.00

%

3.00

0
4.00
090721-029

6.77

%

0
2.00
090721-010

7.00
8.00
6: M R M of 9 Channels ES49 9 > 79.9 (PFO S01)
1.31e5

5.98

100

%

%

%

100

0
2.00
090721-029

6.83

%

5.00

8: M RM of 7 Channels ES599 > 79.9 (PFD S01)91

6.40 6.55 6.77

100

%

4.00

090721-029

%

3.00

8: M R M of 7 Channels ES599 > 79.9 (PFD S01)
1.55e5

6.67
6.68

100

%

100

%
0
2.00
090721-010

090721-010

10: MRM of 2 Channels ES713 > 668.7 (PFTeDA01)
4.57e4090721-029

%

100

%

10: MRM of 2 Channels ES713 > 668.7 (PFTeDA01)
2.81e5090721-010

U S-P1

PFAC-20

US-P1

PFAC-20

7.00

8.00

0

Time
2.00

3.00

4.00

7.00

being extracted by ultrasonic methanol extraction

8.00

Fig.4 PFCAs chromatogram

method, as an example, sample1 and sample3. The(Left: standard 20ng/mL, Right: waste sample 1)

concentrations of PFCs in the solid sample and thepulverized sample were nearly the same for waste
sample1 (dewatered sludge). On the other hand, thewaste sample3 (ASR) shows higher concentrations of
PFCs in the solid state than the pulverized one.
6

10

60

sample3

solid
waste

40

concentration (ng/g)

pulverized
waste

20

8

solid
waste

6

pulverized
waste

4
2

PFDS

PFOS

PFBS

PFHxS

PFODA

PFHxDA

PFTrDA

PFTeDA

PFDoDAPFDA

PFUnDA

PFNA

PFOA

PFPeA

PFDS

PFOS

PFBS

PFHxS

PFODA

PFHxDA

PFTrDA

PFTeDA

PFDoDAPFDA

PFUnDA

PFNA

PFOA

PFHpA

PFHxA

PFPeA

PFHpA

0

0

PFHxA

conｃentration (ng/g)

sample1

Fig.6 Comparison solid waste with pulverized waste

Ⅳ CONCLUSIONS2)Murakami M., Takizawa S.：Current Status andFuture Prospects of Pollution in Water
Environments by perfluorinated surfactants,
Journal of Japan Society on Water
Environment, 33(8), 103-114 (2010)3)Harada K., Saito N.,Inoue K., Yoshinaga T.,
Watanabe T., Sasaki S., Kamiyama S., Koizumi
A.：The Influence of Time, Sex and Geographic
Factors on Levels of perfluorooctane sulfonate andperfluorooctanoate in human serum over the Last
25 years, J. of Occupational Health, 46,
141-147(2004)
4)Lien N.P.H., Fujii S., Tanaka S.：PFOS and PFOA
contamination in Surface Water and Drinking Water
in Kinki Area, The 41st Annual Conference of Japan
Society on Water Environmental, 497(2007)5)Sasaki K., Yaegashi K., Saito N.：Perfluorooctane
sulfonate(PFOS) and perfluorooctanoate(PFOA),
Environmental Monitoring Report 2004:
37-59(2004)
6)Yoshida M., Kobuke Y., Nakano T.：
Contamination of PFOA and PFOS in the rivers of
Hyogo pref. Japan, Organohalogen Compounds,69,
2881-2884(2007)
7)Matsumura C., Takemine S., Yoshida M., Nakano
T.：Contamination of perfluorinated compounds inwater environment of Hyogo prefecture, 18th
Symposium on Environmrntal Chemistry Programs
and Abstracts, 592-593 (2009)8)Matsumura C., Takemine S., Yoshida M., Suzuki
M., Yamamoto A., Tsurukawa M., Nakano T.：
Contamination of perfluorinated compounds in theriver water of Hyogo pref. Japan, Organohalogen
Compounds,71, 2315-2319(2009)9)Yoshida M., Matsumura C., Takemine S., Okuno
T., Nakano T., Yamamoto A., Tokai A., Morioka T.：
Risk assessment of PFOA, PFOS and determinationof perfluorinated compounds in blood,
Organohalogen Compounds, 71, 2605-2608(2009)

The analysis method for PFCs in waste samples wasestablished.
Ultrasonic extraction method was employed, whichgave good results as a pretreatment method, for both
operation blank and isotope recovery tests. These
analytical procedures are composed by methanol
extraction,

centrifugation,

concentration

withnitrogen-gas and determination by LC/MS/MS. And
the waste was used in solid form.
PFCs were detected at retention time between
3.75~7.15 min without interferences.
MDL was 1.4 - 3.9ng/g. It was confirmed that thismethod was applicable for PFCs analysis in waste
samples. As the result, the difference existence ratios
of PFCs in various wastes was shown, establishingprofile of each waste at different sources became
possible.
The result indicates that the existence ratios of PFCs
in various wastes are different, which leads to thepossible establishment of a profile of each waste
generated from different sources.

REFERENCES
1)Kannan K., Corsolni S., Falandysz J., Fillmann G.,
Kumar KS., Loganathan BG, Mohd MA, Olivero J,
Van Wouwe N., Ho Yang J.,Aldous K.M.：
Perfluorooctanesulfonate and related
fluorochemicals in human blood from several
countries, Environ. Sci. Technol., 38,4489-4495(2004)

710)Yagi M., Yamaji A., Shibutani I.：Tendency offluorinated organic compounds in the process ofleachate disposal of final landfill site, 18th
Symposium on Environmrntal Chemistry Programs
and Abstracts, 558-559 (2009)11)Kurihara M., Yoshizawa T., Oishi O., Fujimura
Y., Kojima H.：Study of PFCs in water treatment ofdisposal site, 19th Symposium on Environmrntal
Chemistry Programs and Abstracts, 508-509(2010)

要約

本研究は，廃棄物中において，高感度な PFCｓ
一斉分析手法を確立するために実施した．廃棄物の前処理法には，ＡＳＥ，ソックスレー，超音波抽出法の３手法を比較検討した．14 種の PFCs について，操作ブランク試験，同位体を用いた添加回収試験，固形及び粉砕廃棄物を用いた含有量試
験などを実施した．
その結果，前処理法としては，操作ブランク，
同位体回収試験で良好な結果であった超音波抽出法を採用した．即ち，廃棄物中 PFCs は，メタノー
ル抽出，遠心分離，窒素ガスでの濃縮，LC/MS/MSで分析した．また，廃棄物の形状は，固形状のま
ま用いることとした．本研究で確立した手法で廃棄物の含有量を測定したところ，妨害もなく，保持時間 3.75 分〜7.15 分の間に検出できることを確認した．様々な廃棄物中の PFCs の存在割合は異なり，排出源の異なる廃棄物ごとのプロファイルを確立することで汚染防止対策に寄与できると期待される．

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