ANALYTICAL SCIENCES MAY 2004, VOL.

20
2004 The Japan Society for Analytical Chemistry

793

Evaluation of a Microwave-Assisted Extraction Technique

for the Determination of Polychlorinated Biphenyls and
Organochlorine Pesticides in Sediments
Masahiko NUMATA, Takashi YARITA, Yoshie AOYAGI, and Akiko TAKATSU
National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology,
Tsukuba Central 3, Umezono, Tsukuba 3058563, Japan

A microwave-assisted extraction (MAE) technique for the determination of polychlorinated biphenyls (PCBs) and
organochlorine pesticides (OCPs) in marine sediment samples has been investigated. The analytes were extracted under
different treatment conditions, such as temperature, time and extraction solvent. They were quantified by an isotopedilution method, and the observed concentrations and recovery yields obtained under different conditions were compared.
The results of a comparison between this MAE and other extraction techniques, such as pressurized fluid extraction,
saponification, sonication, and Soxhlet extraction, are also given in this report. The techniques gave comparable results
with the values obtained by other extraction techniques and the certified values in the samples. However, the observed
concentration values of mono- and dichlorinated biphenyls varied depending on the extraction temperature.
(Received November 28, 2003; Accepted March 17, 2004)

Polychlorinated biphenyls (PCBs) and organochlorine

pesticides (OCPs) are representative persistent organic
pollutants (POPs).1,2 Since some of them are suspected to be
carcinogens or endocrine disrupters, the determination of PCBs
and OCPs in the environment is important to evaluate their risk.
The extraction step is the most critical for the trace analysis of
organic compounds, because incomplete extraction causes
inaccurate analytical results, even if the isotope dilution method
is utilized. However, the extraction efficiency of conventional
techniques, such as Soxhlet extraction, is limited by the boiling
point of the used solvent. In addition, the conventional
procedures for the determination of PCBs and OCPs are usually
tedious and time consuming.
Improving the techniques used for the analysis of POPs in
solid matrices has been widely investigated to increase the
recovery yields of analytes, to minimize waste solvents, and to
shorten the analytical procedures and time.
Emerging
techniques, microwave-assisted extraction (MAE), pressurized
fluid extraction (PFE) and supercritical fluid extraction (SFE)
need a relatively short extraction time and a small amount of
solvent.36 They sometimes give higher recovery yields of the
analytes compared with conventional Soxhlet extraction or
saponification, because the extraction temperature can be
increased higher than the boiling point of the extraction solvent
under atmospheric pressure by performing the extraction
procedures in closed pressure-resistant vessels. Among the
emerging techniques, MAE has some advantages. High sample
throughput is realized by a simultaneous sample treatment with
microwave irradiation in an oven. Possible degradation of some
compounds caused by contact with metals7,8 can be avoidable,
because metal vessels are unnecessary. In addition, the MAE
apparatus is relatively simple and reliable, because high To whom correspondence should be addressed.
E-mail: mas-numata@aist.go.jp

pressure pumps or valves are unnecessary.

Although the MAE technique was recently introduced as an
official method for environmental analysis, such as the EPA
Method 35469 and ASTM D6010,10 application of the technique
to the certification of reference materials is not reported. The
optimization of MAE procedures and comparison with other
extraction techniques were reported in many articles.1119
However, a combination of the MAE technique and the isotopedilution method has not been employed, except a few cases.16
National Metrology Institute of Japan in National Institute of
Advanced Industrial Science and Technology (NMIJ/AIST) has
been preparing some matrix reference materials, such as
sediments and biological tissues, for environmental analysis.
Primary methods20 have the highest quality of measurement,
and are essential to the certification of reference materials.
Among the primary methods, only the isotope dilution method
can be applied for the quantification of analytes in matrix
samples. In addition, we have applied more than two analytical
methods for their certification to avoid any possible procedural
bias. Since the combination of the high-efficiency extraction
technique, MAE and a primary measurement method, isotope
dilution, is a candidate analytical method for the determination
of PCBs and OCPs in the sediment reference materials, the
effects of the extraction conditions, such as temperature, time
and solvents, on the determination of some chlorinated biphenyl
(CB) congeners and OCPs have been studied. The analytical
results obtained by the optimized MAE technique and those
obtained by other extraction techniques, such as PFE and
Soxhlet extraction, have been compared to evaluate the MAE
technique as a tool for certification of the matrix reference
materials that we are planning to develop.

794

Experimental
Samples and reagents
Two marine sediment samples were used in this study.
Sediment D was collected from a bay of Kyusyu island as a
candidate matrix reference material for environmental
analysis.21 A certified reference material for the analysis of
organic pollutants in marine sediment, SRM1944,22 was
obtained from the National Institute of Standards and
Technology (USA).
Surrogate solution and syringe spike solution were prepared
from solutions of each isotope labeled compounds (CB15, 28
70, 101, 170, 180, 194, 209-13C12: 50 g/ml, Wellington
Laboratories, Canada; -HCH-13C6, 4,4-DDE-13C12, 4,4-DDDd8: 100 g/ml, Cambridge Isotope Laboratories, USA; 4,4DDT-13C12: 100 g/ml, Dr. Ehrenstorfer, Germany; chlorinated
biphenyl (CB) congener numbers are represented as IUPAC
number).23 The calibration solutions for gas chromatograph/
high resolution mass spectrometry (GC/HRMS) were prepared
from native compounds (CB15, 28, 70, 101, 180, 194, 209;
purity > 98%, Cambridge Isotope Laboratories, USA; -HCH: >
99%, Wako Pure Chemical Industries, Osaka, Japan; 4,4-DDE:
neat, Supelco, USA; 4,4-DDD, 4,4-DDT: > 99%, Dr.
Ehrenstorfer, Germany) and the PCB-13C12 solutions described
above. Some PCB and pesticide analysis-grade reagents
(acetone, toluene, dichloromethane, hexane, and anhydrous
sodium sulfate: Kanto Chemical, Tokyo, Japan) were used for
the extraction procedures.

ANALYTICAL SCIENCES MAY 2004, VOL. 20

Table 1

Operational parameters of normal phase HPLC

Instrument

Gulliver system, Jasco

UV detector: Jasco UV-975
Analytical column YMC-Pack NH2 10 mm i.d. 150 mm
Guard column
YMC-Guard Pack NH2 10 mm i.d. 30 mm
Mobile phase
A: hexane; B: dichloromethane
Gradient
100% A (7.5 min) 91% A, 9% B (30.0 min)
Flow rate
4.0 ml min1
Injection volume 950 l
Detection
245 nm

Fig. 1 Flow diagram of sample preparation for the determination of

PCB congeners and OCPs in sediment samples. Sox, Soxhlet
extraction; Sap, saponification/hexane extraction.

ml). After mixing the contents by shaking, the surrogate

solution was added into the cell. The content was extracted
with hexane/acetone (1:1, v/v) for 30 min using a PFE system,
ASE 200 (Dionex, USA) at 150C, 15 MPa. The extraction was
repeated once under the same condition. The obtained extract
was cleaned up by an activated copper-powder treatment, SPE,
and nHPLC, as described above.25

Microwave-assisted extraction
The sediment sample (2.5 g of sediment D or 0.8 g of
SRM1944) was accurately weighed into a Teflon PFA
extraction cell (approximately 100 ml volume, GreenChem
Plus, CEM, USA). After the addition of the surrogate solution
(0.4 ml of 2,2,4-trimethylpentane solution), the sample was
extracted with 20 ml of hexane/acetone (1:1, v/v), acetone,
dichloromethane, toluene or hexane.
Because less-polar
solvents do not absorb microwave energy efficiently, 5 ml of
water was added in the case of toluene or hexane extraction.
The cells were covered with pressure-resistant holders, and
were heated with sporadic irradiation of microwave (150 200
W per cell) at 100 145C for 5 30 min (temperature ramp: 15
min) using a microwave extraction system MARSX (CEM,
USA). Upon termination of the microwave irradiation, the cells
were air-cooled. After cooling, the organic solvent layer was
centrifuged at 3000 rpm for 3 min to remove the solid residues.
The obtained supernatant was cleaned up by a method of
Schantz et al.24 with some modifications.21,25 The supernatant
was treated with activated copper powder and anhydrous
sodium sulfate to remove elemental sulfur and water. After
filtration with a PTFE membrane filter (pore size, 0.2 m), the
solution was passed through a solid phase extraction (SPE)
silica cartridge (500 mg silica in a 3 ml cartridge, International
Sorbent Technology, England). Then, PCBs and OCPs were
recovered with 15 ml of a dichloromethane/hexane mixture
(1:9, v/v). The eluent was concentrated and then loaded onto a
normal phase liquid chromatography (nHPLC) system (Table
1). For GC/HRMS analysis, the collected two fractions (3 17
min fraction, PCBs, 4,4-DDE and 4,4-DDT; 20 25 min
fraction, more polar OCPs [4,4-DDD and -HCH]) were mixed.

Saponification
The analytical procedures were followed as a Japanese official
method for PCB determination, Endocrine Disrupting
Chemicals Interim Investigation Manual26 (Chapter I:
Determination of polychlorinated biphenyls).
After the
addition of the surrogate solution, the sediment sample was
treated with 50 ml of an ethanolic potassium hydroxide (1 M)
solution and 10 ml of water at room temperature by shaking for
1 h. The CB congeners were extracted with hexane. Then, the
hexane layer was shaken with sulfuric acid (98%) to remove
most of the pigments. The hexane layer was passed through a
column containing 5 g of silica gel (moisture content, 5%;
Kanto Chemical) to remove any polar constituents. The column
was washed with 40 ml of hexane to recover CB congeners.

Pressurized fluid extraction

The sediment sample and 12 g of anhydrous sodium sulfate
were weighed in an extraction cell (stainless-steel; volume, 11

Sonication
The analytical procedures were followed as a Japanese official
method for OCP determination, Endocrine Disrupting

Soxhlet extraction
A mixture of the sediment sample and 10 g of anhydrous
sodium sulfate was placed into a filter paper thimble, and the
surrogate solution was added. The sample was loaded on an
automated Soxhlet extraction system, B-811 (BCHI,
Switzerland), and then extracted with 250 mL of nhexane/acetone (1:1, v/v) for 36 h. The extract was cleaned up
by SPE and nHPLC, as described above.

ANALYTICAL SCIENCES MAY 2004, VOL. 20

795

Fig. 2 Example of a GC/HRMS chromatogram of PCB congeners and OCPs in the sample solution
obtained by the MAE technique. Extraction temperature, 115C; extraction time, 10 min; solvent,
hexane/acetone (1:1); GC/HRMS parameters are represented in Table 2.

Chemicals Interim Investigation Manual26 (Chapter II:

Determination of organochlorine pesticides, polybrominated
biphenyls and benzo[a]pyrene). After the addition of the
surrogate solution and 5 ml of water, the sediment sample was
extracted with acetone by mechanical shaking and ultrasonic
irradiation (10 min each). Then, the extraction procedures were
repeated twice. The obtained extract was treated with a sodium
chloride aqueous solution (5%, w/w) and hexane. The hexane
layer containing OCPs was passed through a silica-gel column
(described previously). The column was eluted with 40 ml of
hexane, followed by 40 ml of hexane/acetone (19:1, v/v) to
recover the OCPs.
Determination of PCBs and OCPs by GC-MS
Analyses of the CB congeners and OCPs in the extracts
obtained from different extraction and cleanup techniques (Fig.
1) were performed using a GC/HRMS system (AutoSpec,
Micromass, UK). After the syringe spike was added to the
sample solution, the solution volume was reduced to 0.2 ml by
means of a rotary evaporator and nitrogen gas stream. A
portion of the solution (1.0 l) was analyzed with the system
(Table 2). The CB congener peaks on the chromatogram were
Representative
assigned by following some reports.27,28
chromatograms of the analytes and their internal standards are
shown in Fig. 2.
Analytical results are represented as dry-mass base in this
report. The moisture contents of the samples were determined
gravimetrically. The samples were dried at 105C for 6 h, and
the moisture contents were calculated from weighing before and
after drying.

Results and Discussion

Effect of the extraction solvent
The extraction solvent, temperature, time, moisture content of
sample, microwave power, cycles of extraction would affect the
extraction efficiency in the MAE technique.4 In this study,
effects of relatively important factors (solvent choice, extraction
temperature and time) were investigated. The effects of the

Table 2

Operational parameters of GC/HRMS

GC conditions:
Mobile phase
Injection
Column
Column
temperature
MS conditions:
Ionization mode
temperature
Mass resolution
Detection mode
Monitoring ion
(target compound)

Helium, 276 kPa (constant pressure)

Splitless, 200C
HT-8 (SGE), 0.22 mm i.d. 50 mm,
film thickness: 0.25 m
60C (2 min) 15C min1
170C 3.5C min1 300C (6 min)
Electron ionization (35 40 eV)
250C
> 10000
Selected ion monitoring
222.0003 (CB15), 234.0406 (CB15-13C12)
257.9587 (CB28), 269.9986(CB28-13C12)
289.9224 (CB70), 301.9626 (CB70-13C12)
323.8834 (CB101), 335.9237(CB101-13C12)
393.8025 (CB180), 405.8428 (CB170,180-13C12)
427.7646 (CB194), 439.8038 (CB194-13C12)
13
C12)
497.6826 (CB209), 509.7229 (CB209
218.9116( -HCH), 224.9317 ( -HCH-13C6)
235.0081(4,4-DDD), 243.0583 (4,4-DDD-d8)
235.0081(4,4-DDT), 247.0484 (4,4-DDT-13C12)
317.9351(4,4-DDE), 329.9735(4,4-DDE-13C12)

extraction solvents on the PCB and OCP analysis in sediment D

are given in Tables 3 and 4. Since we applied the isotopedilution method, differences between the calculated
concentration values were not significant among the tested
solvents, except for extraction with hexane, in contrast with the
results obtained from the absolute calibration method in
An increase in the extraction
previous reports.3,5,12,14,16
efficiency by the addition of water to less-polar solvents was
reported.14 However hexane-extraction gave a significantly low
recovery of the analytes and surrogates.
Such a low recovery was improved by using more polar
solvents. Although extraction with acetone gave the highest
(not significant) concentration values of some compounds, the

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ANALYTICAL SCIENCES MAY 2004, VOL. 20

Table 3 Concentrations of CB congeners and OCPs in sediment D, and the recovery yields of surrogates obtained by MAE with polar
solvents
Acetone

Hexane/acetone(1:1)

CB15
CB28
CB70
CB101
CB180
CB194
CB209
-HCH
4,4-DDE
4,4-DDD
4,4-DDT

Dichloromethane

Concentrationa/ng g1

Recoveryg, %

Concentrationa/ng g1

Recoveryg, %

Concentrationa/ng g1

Recoveryg, %

2.27 0.08
33.9 0.2
60.5 1.1
30.6 1.0
8.58 0.58
1.92 0.13
1.51 0.35
4.70 0.39
5.71 0.12
13.2 0.9
5.59 0.92

81 12
73 11
74 7
78 9
85 4
89 3
93 6
67 12
82 9
63 10
107 42

2.29 0.08
34.1 1.1
61.3 1.0
30.9 0.8
8.59 0.26
1.77 0.07
1.12 0.05
5.16 0.21
6.03 0.08
13.6 0.6
6.44 1.51

77 45
66 16
69 13
74 15
70 8
65 13
59 11
48 5
71 8
58 15
91 34

2.28 0.13
33.9 0.4
59.5 0.1
31.0 0.7
8.04 0.26
1.76 0.05
1.16 0.06
5.45 0.02
5.80 0.17
13.0 0.6
5.71 0.67

83 20
61 5
65 12
68 13
67 13
61 3
58 5
46 12
70 16
48 10
68 10

a. Extraction: 115C, 10 min; values as average of 3 measurements (3 extractions); error, SD. b. Recovery yields of surrogates through
extraction and cleanup.

Table 4 Concentrations of CB congeners and OCPs in

sediment D, and the recovery yields of surrogates obtained by
MAE with different solvents
Toluene
Concentrationa/
ng g1
CB15
CB28
CB70
CB101
CB180
CB194
CB209
-HCH
4,4-DDE
4,4-DDD
4,4-DDT

Recoveryb,
%

2.27 0.04
86 12
33.0 1.0
70 4
58.7 0.7
71 5
29.8 1.1
75 5
7.46 0.32
68 4
1.53 0.07
67 1
1.08 0.17
64 0
5.23 0.04
65 5
4.35 0.03
136 12
12.5 0.1
20 1
n.d.c

Hexane
Concentrationa/
ng g1

Recoveryb,
%

1.87 0.07
28.2 1.3
50.7 2.0
26.2 0.9
7.12 0.48
1.54 0.18
1.36 0.51
4.78 0.67
4.31 0.51
12.0 2.3
6.89 4.97

50 1
45 3
47 5
50 5
49 9
44 4
41 3
40 8
54 9
43 14
52 27

a. Extraction: 115C, 10 min; values as average of 3 measurements

(3 extractions); error, SD.
b. Recovery yields of surrogates through extraction and cleanup.
c. The peak of 4,4-DDT-13C12 on the chromatogram was overlapped
on other peaks.

variations of the values were larger in most cases. Judging from

the color of the obtained extract, this phenomenon may have
been caused by large amounts of the concomitants extracted
with acetone. Hexane/acetone (1:1, v/v) was used for the
following experiments, because the recovery yields of the most
analytes were the highest among the tested solvents. Also, the
solvent was used for a temperature-dependent experiment by
reason of safety, because the vapor pressure of dichloromethane
and acetone is higher.
Effect of the extraction temperature and time
The effects of the process temperature and time on the
analytical results and the recovery yields of the surrogates in the
sediment D are shown in Figs. 3 and 4. Because the behaviors
of CB70, CB180, CB194 and 4,4-DDT were almost the same
as the temperature and time dependences of CB101 and CB28,
they were omitted from the graphs. The stabilities of the tested
analytes were checked in advance. The hexane/acetone solution
of the analytes was irradiated with microwaves, and heated at

the highest tested temperature (145C) for 10 min. Because the

recovery yields of all analytes were higher than 95%,
degradation of the analytes would be negligible.
The observed values of the concentration of most CB
congeners reached plateaus at under 115C. The observed
values of the concentration and the recovery yields of most CB
congeners and 4,4-DDE reached plateaus within 10 min at
115C. Instead of elongation of the MAE process, the effect of
repeating the extraction was also investigated. The extraction
residue was extracted again, and the obtained supernatants were
combined. Although it gave a slightly higher recovery yields of
the analytes, the concentration values were not improved.
The reason for the relatively low reproducibility of 4,4-DDD
quantification is unclear. The use of a deuterium-substituted
compound as a surrogate of 4,4,-DDD could cause an error,
because the deference in the physical properties between
deuterium and hydrogen are larger than in the case of 13C and
12
C. Because 4,4-DDD is one of the most polar analytes, the
absorption on sediment particles, the inner surface of glassware
or the stationary phase of chromatograph may enhance such an
effect.
As shown in Fig. 3, the obtained concentration values of
CB15, 4,4-DDD and -HCH in sediment D depended on the
extraction temperature. Such the temperature dependence was
also observed in the case of other mono- and dichlorinated
biphenyl congeners. However, there is no significant difference
between the recovery yields of these isotope labeled compounds
under high and low temperature extraction, On the other hand,
when the extraction residue at 100C was extracted at 145C,
the amounts of native CB15 and native polar OCPs in the
extracted solution were almost equivalent to the difference
between the observed values at both temperatures, and the
concentrations of their surrogates in the extract were almost
negligible (data not shown). These results would mean that
these compounds (mono- and di-CBs, and relatively polar
OCPs) bind the sediment particle firmly. Also, the exchange
between the isotope labeled compound in solution and native
compounds adsorbed on the particles may be very slow at low
temperature. This phenomenon may be caused by the trapping
of aged pollutants into the three-dimensional structure of clay
In particular, the
minerals or humic substances.29,30
determination of accurate mono- and di-CB concentrations
would be problematic, because the concentration values did not
reach a plateau, even at the maximum temperature in the tested

ANALYTICAL SCIENCES MAY 2004, VOL. 20

797

Fig. 3 CB congener (A) and OCP (B) concentrations as a function of the MAE process temperature.
Extraction time, 10 min; solvent, hexane/acetone (1:1); values as an average of 3 measurements (3
extractions): , CB15; , CB28; , CB101; , CB209; , -HCH; , 4,4-DDE; , 4,4-DDD; error bars,
SD (standard deviation).

Fig. 4 CB congener (A) and OCP (B) concentrations as a function of the MAE process time. Extraction
temperature: 115C, solvent, hexane/acetone (1:1); values as an average of 3 measurements (3 extractions);
, CB15; , CB28; , CB101; , CB209; , -HCH; , 4,4-DDE; , 4,4-DDD; error bars, SD
(standard deviation).

conditions (145C). Such a temperature dependence has not

been reported, because the extraction temperature was up to
130C and only tri- to deca-CB congeners were the target of
analysis in most of previous studies. Although the contribution
of the mono- and di-CBs to the total toxicity of PCBs is low,
such a possible error should be considered in the case of a PCB
pollution source apportioning based on the congener profiles.
Method comparison
Principally, the isotope-dilution method has the highest
accuracy among quantification methods that can be applied to
the analysis of matrix samples. However, the equilibrium
between native analytes adsorbed on a solid matrix and isotopelabeled surrogates is not realized in some case, as in the case of
CB15. Because the achievement of isotope equilibrium cannot
be evaluated practically, the recovery yield should be as high as
possible for the accurate determination of analytes. In general,
higher temperature extraction, such as MAE and PFE, gives a
more complete recovery and isotope equilibrium compared with
low-temperature processes, such as sonication and Soxhlet.
Extraction by semi-continuous processes, such as Soxhlet and
PFE, would give a higher recovery of the analytes, but an error

may be caused by loss of surrogates or insufficient time for the

exchange of surrogates and native analytes adsorbed into the
matrices, compared with batch processes, such as sonication and
MAE. In the case of MAE, a decrease in recovery of the
analytes may be caused by re-absorption on extraction residues
in the period of cooling before solid-liquid separation. In this
study, the analytical results obtained using MAE were
compared with those obtained by other extraction techniques to
evaluate the feasibility of the MAE technique. As shown in
Tables 5 and 6, the analytical results obtained using the MAE
technique agreed with the certified values concerning the
concentration of the analytes, and the results obtained by other
extraction techniques, except for CB15 and -HCH. The
recovery yields of the surrogates obtained by the MAE
technique (typically 70 to 100%) were almost the same, or
slightly higher, compared with other extraction techniques. The
relatively high analytical results of CB15 and -HCH obtained
by the MAE and PFE techniques would reflect an improvement
of the recovery from the matrices.

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ANALYTICAL SCIENCES MAY 2004, VOL. 20

Table 5 Concentrations of CB congeners and OCPs in the

NIST SRM1944 obtained by different extraction techniques
MAEa
Concentrationd
/ng g1

Official methodb
Concentrationd
/ng g1

28.2 0.8
84.1 3.4
71.6 1.8
61.6 2.2
40.2 3.4
10.4 0.9
7.45 0.18
0.21 0.21
78.9 2.2
123 6

15.5 0.3
75.6 3.8
70.1 2.5
61.6 1.1
38.8 0.6
10.5 0.6
7.36 0.28
0.14 0.02
80.3 2.3
111 7

CB15
CB28
CB70
CB101
CB180
CB194
CB209
-HCH
4,4-DDE
4,4-DDD

Certified valuesc
Concentratione
/ng g1
80.8 2.7
73.4 2.5f
44.3 1.2
11.2 0.33
6.81 0.33
86.0 12.0
108 16

a. Solvent: hexane/acetone (1:1), 130C, 10 min.

b. CB congeners and OCPs were determined by saponification and
ultrasonic extraction, respectively.
c. Certified values calculated from results obtained by Soxhlet
extraction and PFE (Ref. 18).
d. Values as average of 3 measurements (3 extractions); error, SD.
e. Error: expanded uncertainties.
f. CB101 + CB90.

Table 6 Concentrations of CB congeners and OCPs in

sediment D obtained by different extraction techniques
MAEa
PFEd
Official methodb Soxhletc
ConcentConcentConcentConcentratione/ng g1 ratione/ng g1 ratione/ng g1 ratione/ng g1

CB15
CB28
CB70
CB101
CB180
CB194
CB209
-HCH
4,4-DDE
4,4-DDD
4,4-DDT

2.29 0.05
34.2 0.4
61.2 0.9
30.4 0.5
8.27 0.57
1.82 0.19
1.18 0.07
5.02 0.34
5.85 0.01
12.4 0.6
5.53 1.01

1.80 0.10
31.0 1.5
59.2 1.3
30.7 1.1
7.84 0.61
1.75 0.11
1.39 0.26
3.73 0.53
5.63 0.05
12.5 0.8
6.73 1.68

2.28 0.06
34.6 0.7
61.3 0.8
32.6 1.0
10.0 1.5
1.86 0.25
1.14 0.07
5.04 0.36
5.83 0.22
12.5 2.1
4.90 0.04

2.41 0.06
35.3 0.4
62.8 0.3
32.8 0.1
9.57 0.14
1.81 0.09
1.30 0.24
4.80 0.33
5.81 0.18
13.6 0.7
6.02 0.37

a. Solvent: hexane/acetone (1:1), 130C, 10 min.

b. CB congeners and OCPs were determined by saponification and
ultrasonic extraction, respectively.
c. Solvent: hexane/acetone (1:1), 36 h extraction.
d. Solvent: hexane/acetone (1:1), 150C, 15 MPa, 30 min 2 cycles.
e. Values as average of 3 measurements (3 extractions); error, SD.

Conclusion
As a result of evaluations, the MAE technique was found to be
suitable as an accurate alternative to conventional extraction
techniques. Although more investigation would be necessary to
determine mono- and di-CB congeners accurately, the highly
efficient extraction technique, MAE, would be the preferred
technique for the certification of analytes, such as PCBs and
OCPs. We are planning to develop some certified reference
matrix materials for environmental analysis, such as PCBs and
OCPs in marine sediments. The accurate, high samplethroughput, and low solvent consumption technique, MAE, will
be used as one of the extraction techniques in certifying the
matrix reference materials by combining the isotope dilution

method.

References
1. V. Lang, J. Chromatogr., 1992, 595, 1.
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